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IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 

In re Patent Application of ^"^rs-^^ Date: November 27, 2006 

Applicants: Bednorzetal. / Docket: YO987-074BZ 

Serial No.: 08/479,810 | d£c 0 iPfi J Group-Art Unit: 1751 

Filed: June 7, 1995 Examiner: M. Kopec 

For: NEW SUPERCONDUCThfesSSt^UNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 

Commissioner for Patents 

United States Patent and Trademark Office 

P.O. Box 1450 

Alexandria, VA 22313-1450 

APPEAL BRIEF 

PART iX 
CFR 37 §41 .37(c) {1)(ix) 
SECTION 1 

BRIEF ATTACHMENTS AA TO AZ; BB TO BL 
VOLUME 5 




Reg. No. 32,053 
(914) 945-3217 



IBM CORPORATION 
Intellectual Property Law Dept. 
P.O. Box 218 

Yorktown Heights, New York 10598 



AVAILABLE COPY 



BRIEF ATTACHMENT AA 





IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorzetal. 
Serial No.: 08/479.810 
Filed: June?. 1995 



Date: March 1, 2005 
Docket: YO987-074BZ 
Group Art Unit: 1751 
Examiner: M. Kopec 



For NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria. VA 22313-1450 



In response to the Office Action dated July 28, 2004, please consider the 
following: 



FIRST SUPPLEMENTAL AMENDMENT 



Sir: 



ATTACHMENT AA 



Serial No.: 08/479,810 



Page 1 of 5 



Docket: YO987-074BZ 



Powder Diffraction File 




INTERNATIONAL CENTRE FOR DIFFRACTION DATA 



Powder Diffraction File 

Alphabetical Index 
Inorganic Phases 
1989 



eration with the American Ce;am^^^°^f ^^^^^^^^^^ X-Ray 
ciation, American Society o^^^^^^^ Clay Min- 

Analytical Association, ^"tish Crystallograpn^^^^^ The Institute of Physics, 
erals Society, Deutsche Mineralog^he G^^^^^^^ ^^^^^^ „f 

T^e Mineralogical Association f^^a""^^^^^^^^^^ 

America, Mineralogical Society f ^rea .B^^^^^^^^^ je Mineralogie et de 

ciation of Corrosion Engineers, and Societe franca 

Cristallographie. 



Published by the 

IMTERNATIOMAL CEMTBE FOB WfMCWH DATA 

,601 PARK UNE . SWAHTHMORE. PA 19081-2M9 • U.SA 



Copyright c JCPDS International Centre for Diffraction Data 1989 

formerly the 
Joint Committee or, Powder Dffraciion Standards 

All riehts reserved. No part of this publication may be reproduced or transmitted in 
a"yfomoT^yanymeans, electronic ormechanical.includingphotocopy.re^^ 

or anyTnformiltion stonige and retrieval system, without permtssmn tn v,ntmg from 

the publisher. 



Printed in U.S.A. 
1989 



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BRIEF ATTACHMENT AB 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 
In re Patent Application of Date: March 14. 2005 

Applicants: Bednorzetal. Docket: YO987-0r4BZ 

Serial No.: 08/479,810 Group Art Unit: 1751 

Filed: June 7, 1995 Examiner: M. Kopec 

For NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE. METHODS FOR THEIR USE AND PREPARATION 

Commissioner for Patents 
P.O. Box 1450 
Alexandria. VA 22313-1450 

THIRD SUPPLEMENTAL AMENDMENT 

Sin 

In response to the Office Action dated July 28, 2004, please consider the 
following: 



The attachments referred to herein A to Z and AA are in the FIRST 
SUPPLEMENTAL AMENDMENT. The Attachments AB to AG are attached herein. 

Please charge any fee necessary to enter this paper and any previous paper to 
deposit account 09-0468. 




(914) 945-3217 

IBM CORPORATION 
Intellectual Property Law Dept. 
P.O. Box 218 

Yorictown Heights, New Yori< 10598 



ATTACHMENT AB 



Synttieslg of cuprate ^peroiiidiiet^rs* 



CNR Rao. R Nagarajan ami R Vljayaraohavan 

Solid and Struc^iral Chen^stry iMtt and CStR Cer»tre o( Excellence In 
Cf>emtetry. Jndian ins^tule oe^ence. Banoalor« 500012. India 

Receive 28 August 1992, In final form 19 October 1992 



AMTMt Thera Has been uii|»wedef)^ activity 

c)i^BCt^i2«i^ ol stipeiconducting cupmtes irt th« last few yem* A variety of 
syrHheHc sfirategies has been employed to prepare pure monop^lc cuprate$ of 
m^^^Uanms wHh good superconcfcictind properties. Bellas tf>« traditionaf 
cerai^ m^ttioft. other metlMklsauch as ct^edpHatloA and preciffsor metboda. the 
soHrel method^ tf«e a^lcaH fkfx 
«mptoye*«(» ttie 8yrftfi«»te of 

cond^loits suoh as high oxynen or hydrostatic pressure and low oxygen higaclty ^'e 

^l^>toyed lb the synthesis. In ti^ review, we discuss the Synthesis ol the various 

types of cuiKate stipercor^itl€tOfa afxt pofnl 

of »^ *«ef^ niettods- We have pnivkJed the necessary pr^^ 

prasei^ the crud^ litformattoo in tsi)^ form wf»efevof necessary. 



t#' Hf ai*iiih Jim* ay*>l M 
. BraroQtaeoon 

Siiicc Ihe discovcfy hi^T^ supcrconducayity ia the 
I>-Ba^CiH9 ^icm [II a yaric^ of cu|«^ super- 
o^^uotOTs wrth ^ geing Bp to 128 K have been syn- 
fbeszttd rad i^^tfai^teiked C2» 3^ No otbo^ cta^ of 
materials l»s hem wojiccd <m so wkldy and isteasdy in 
ftce&t years as have the cuprate supercomluc^ors. 
Several o^dkods s^besis have been oni^yed f<^ 
pfi^ming the a^i^Btcs» wftb the objcctii* <^ obtaining 
pure nk»K^^ias»c products with good supercotidiKrdng 
^ractemUes ti 4]. this most common methpd of syn- 
. Ibes«¥ of cuprate »iperoofidi»^ors is the traditional 
oermic ni^aK>d vMd^ to beoi employed for the prep- 
ajp^QO cf a large rmety of <»tkle materials (5]. 
AiAm^ ^^E^^df&fe ineaK>d has yiddbd many of the 
capr^^ ^iil^iilE^i^hct^!^^ diflereat syn- 

■i^hi^^ ss^^0i^^m. h^»mt necessary m order to 
cm&i^^^^^0: m tite cation coittpositi^i^ oxygen 
^^fcdld^|:^^^^8ib9a <)E)ridattoa states and carrier con- 
itoteworthy amongst these 
a^f^Si!^':.^i^^^te&tS^ or sohition routes which permit 
better mij^i^:^ ^ consbtoent cations in ordcx to 
redi^ the ^^oti iKstaoccs in the soiki state 1% 
Such methods inducte coprcdpitatton, use of precur* 
sons, the sc^^l method and the use of alkali fluxes. The 
t^ombNQ^on method or self-p^^opagattng high- 
tcmperarare synthe^ (sna^ has als(> been employed In 
tiis reyiew, we disoKs the preparation <rf cuprate 
superconductors by the i dtlferent methods, tncntioning 

• Goouibuiioii No 874 from Uie SoBd State a^kd SirorturtI Ocmwtry 



the ^;)ecsal lefiimrtia Of ea^ im^tod aiKl it^ cfi^tdittoins 
emi^c^ for Ote ^l3tesi& Ilk iaiJbk^ U wc a ^ 
the cuprate s;v^pcxc^«idacUi^ dbpnssed^ in roiciy 
aUmg wkh their $ttttctimd pamnsetci^ aiBKj w^o^^amtt 
i; values. Pr^>arative fiondid^ $pd) ^ fi^be^ tern* 
pcrature; oxy^ jnpc^sar^ ^^^tie ptessw and 
annealing coadi^tMIs are i^&d k lh^ $k»$siM^^^^ 
given in tabuhr f<»m whiem iteccssay. tl b h^^ped thai 
this review will be found asdW by p^r^:^6i8^ of the 
sttt^ect as wdl as tljosie fntshly eml!^rt»% on the syn- 
thesis of these matwials. 



2. Ceramic mettiOd 

The most coinmob mediod cf syatiiipsfiiilig inorigwiic 
sdids is by the reliction <^ the cb«^?6ii^t i62te^^ 
etevatcd temperataits. If 41 tbc ma^S^^^^ 
the method » caQcd Ac ceramic If t^ dT 

the constituents is yolatik or sensitive to the atmo- 
^hcre^ the reaction b canied out in scafed rracuated 
capsules. Ptattmun» diai or ahmwa om^^im^ are 
eniQy used for Use ^yotfiesis of me^ o^tJfaL The ^?t- 
in^ maicriab are metal ojdfite^ caitipmites, w pUi^^t% 
which are niixed, hompgams&d and a jpven 

temperature sufliciendy long fof *e r^:tkm to be 
connected, A kno«to^ df tM fbm «a^am w »^ 
in fixing the <Mnpo»tkm md cc^ltoti^ a syn- 

thesis. 

The ceramic method getterally rojuires relatively high 
temperatures (t^> to i3GQK) «^ are m^BBy 
attained by icastaacc heatmg. Becteic arc ^ dcuU 



^>^2O48/ft3/Dl00O1 + 22 S07.fiO © 1993 lOP Publishing tid 



1 



Tftbto 1, SiruclHK . ameters and approximate values o< cui 



^-rconductors. 



Cuprate 



Stnidure 



(max. vahie) 



1 La^CuO^^j 

2 ta,,^.(BajCuO^ 

3 taaCa,.,Sr,Cu,Oe 

4 YBaaCujO, 

5 YBajCu40e 

6 YjBa^GuyO,* 

7 Bi^Sr^CuOs 

a BIjCaSTjCUaOe 

9 ai^Ca^^iCugOso 

11 TlaBa^CuG^^ 

12 Ti^CaBa^Ou^Oa 

13 T^Ca2Qa3Cu^OH> 

14 TI{SaLa)CifO, 

15 Tt (Srta)CuO» 

17 nCaBa^CUaCH 

la -nSf^aYo^GaasCUaOT 

20 TKkj^BiaaCUsOif 

22 TIBaa(Lo,^C0i3CUiO» 

23 Pb^STsUio »Cao sCU30« 

24 Pba(Sr. La)3Cu30e 

25 {Pb, Cu)Sr;t(Ln, C«t)Cu^07 

25 (Pb. Cu}CSr, Eii)^ Ce^O^ 

26 Cat.^JPwOa 
2d Sr,./ld>t>iGa 



0nf*ai>; a = S.35S, /> - 5.401» c f 13.t5 A 39 

t4/fnmm; a » 3.7r9» c « 13.23 A 35 

14/mmm ; a « 3.32$, c « 19.42 A 60 

Pmmm; a 3.621, 6 3.^, c « 11.676 A 93 

Ammm; a = 3.84, 6 = 3-87, c ^ 27.24 A ^ 60 

Afmnfn;a -3^651,^ = 3.869, c *= 50L29 A 93 

Afma;a »&362,/F»5^74.cc«24JB22A 10 

A2aa : a « 5,409. 6«5.«).c = 30.93 A 92 

A2aa; a - 5^. b - 5.40, c - 37 A IK) 

P4/nimm; a ^ 3.888, c - 17.28 A ^ 

A2aa ; a « 5.468, 6 ^ 5.472, 92 

c » 23.238 A; 14/nwnm: a « 386$. c « 23^239 A 

t4/nimm ; a <ix' 3.855. - ^.318 A 119 

14/mmm : a » 3.^. c^dS.Bk m 

P4|/«R«»ni: a»a83,c^9.55 A 40 

ffM/mmm; a ^ 3.7, c 9 A 40 

P4/mmm;a«3738,c«9,01 A ^ 

P4/mmm : a =» a856. c ^ 1Z764 A 103 

P4/mmm; a « 3.80. c « 1^05 A 90 

P4/mmm; a = 380, c - 1^10 A 90 

P4A»mm ; a 3.853, c' ^ 15^13 A 1 10 

P4/fnfnm; a « 381, c « 15^23 A 120 

M^nimn:a -3-8.C-29.5 A 40 

Cmmm; a =i 5.435. ^ ^ 5 463, c « I5J8I7 A 70 

P22,2 : a - 5.333. b = &421 . c = 12.609 A 32 

P4/rfuhm:a * 3.820, 1: « 11.826 A fiO 

l^-mmni ; a « 3.837. c « A 25 

M/irnmrn; a « 3^ c « 12.07 A 30 

P4fmm^ ; a » 9^ r » 3^3$ A iip 

P4/^rnmfln;a =*3^. c = 3.393 A 40 



techniques pvc temperatures up to 33Q0 K while high- 
power CO3 lasers give temperatures up to 4300 K, The 
u^B d^dvafitages of the ceramic method arc tt» 

col The carting mixtures are iahozm^eoeous at the 
at(M!iaic levti. 

(p> When no melt b fonued diMng the re^ the 
ei^tre leao^Nfi has to occur m the solid ^te« first by a 
l^te^ boondaffy reactira at the poults df conuct 
between the compdi^ls »id later the cKfTuskm of 
the eo^s&ucnts tiirou^ the imNloct plwec. With the 
pf0^«s$ <^the reaction, diSasioii pa^ become looger 
aiui tl^ mx^km rate slower; tte ftd£ti(»i cau be 
needed up io some extent by intermittent grinding 
beHvera heating cydes. 

^ Theie is no simple way of mmitoriiig the 
ptogm of die reacticm. It fa by tmd aod enor that <^ 

coo^^stikm ttf the rea<^ioa. Iteca^se c«f i^i diifeutty, 
witib the ceraxnic method dm mSs ^ with mix- 
imts ct redtdants and i^odticts. Sqp^l^oii xsi the 
desired products from such niixtufes is <BQoult, if not 

^ nequendy it becraics difiScBli to obtain a com- 
pos^t^nally homogeneous product even where the reac- 
tion proceeds nearly to compIetioD. 

Despite the above limitatioos^ tte ceramic method is 
wkldy used Tor the syatfac^ of a tsrst vatiely of inor- 
g8«&:si^ids.Ii]i^ case of the coftfate supercoodtictorSv 



the cetamic method mvotves mixuig ai^ grjokfing tht 
con^nent ox^s» d^^boisi^^ <Nr sahs; and 

teating the mixtmc; gama&f in pdlet fbfm, at tbt 
desired ^o^Kratts^e. A mBmm variation cf the 
method fa to heat a am^i^ of tktsm pi$9i9P^ ^ 
digestiikg the inetal ma^^Bs/ca^bmis^ in coiicenttitt^ 
HNQ^ and evapqaMi^ ^ iMhi^Oii W ^ym^ 
Heatii« fa carried ih afir^ aii - api^Eipii^c Bt^ 
sfdieie. ccmtrolKng Oee; pe^^ 
nece^ary. In the case dT ^la^SE5 ai^tcs» ^ 
tte v«dat^ at»l p^snamsm i^amt of tfie d^On^ 
oxide vapour^ reactions are cainied o^t in seded tiAes 
In cc^ of die csufier i^Eqpaie^^ ^ dtiffiuna cuj^ 
rates were syntli^died tai 1^ fiimaccs. Tia& Is 
however, not l er omm e n de A A auomtsfol Qfawsis h) 
the ommic method dcpea/^ on amcd GictoES 
mdude &e n^tmt of fSm staftlos; stu^c^toh 
of oxiite^ caifipiiate^ tbe bm^BOf^ ^ ^ n^i^ 
of powders, rate of h^&g » wdl as the mctto* 
temp^ature ai»l dura^s^ 



Synthcsfa «tf alteA»-artib-dqpcd Ui^^Jki^^^^ 
(M = Ca, Sr and Ba) of iCil*?* stnumut wifli sttpcr^ 
conducting transition taiq)eratures up to 35 K is 
readily adiicved try the oeia^ tm^Ood. t^rs&Sfy^ the 
synthcss fa carried opt K9 lOKr^^ sMd£dHp?t^:lnc quan- 
tities of the oiddes aisd/ior carliDm^ arc^md 1^ K in 



oiitcn^i for ^ synth^s [11-13]. By surting with 
0jetal nitratcSj one obtains a more homogeneous start- 
ing mixtare» since the hydrated metal nitrates have low 
oielting points leading to a uniform melt in the initial 
stage of the reaction. Furthermore^ nitrates provide an 
oxidative atinos|^eTe« which is required to obtain the 
necessary oxygoi content. 

Sti^chiom^tric LajCiiO^ is an antiferromagnetic 
insutator. La2Cu04 prep^ed under high oxygen pres- 
sures, however, shows superconductivity (T^ ^ 35 K) 
since the oxygen excess introduces holes just as the alk- 
aline earth dopants [14^16]. Ij&^CmO^^^ {i up to 0.05) 
has been synthesized by anneahng La^CuO* under an 
oxygen piv^ure <rf 3 kbar at 870 K [14, 15] or 23 kbar 
at )07O K [163- Oxygen plasma has also been used to 
tncrea^ the OJt>«en content 

The next hOTiologuc La^CuO^ containing two 
CM> >y«^ Lai^sSfd^CaCujO^ (T^ 60 K), has been 
syftlh£^^ed by using high oxygen pressures [17], The 
symhesis involves heating the sample at an oxygen pres- 
sure of around 20 bar at 1240 K. The material s^epared 
at ambieiil oxy^ pressures (in air) is an insulator. 
Several other high-oxygcn*pressure preparations have 
been rcj^rted on the n = 2 member of the 
lAi+iCu2,G2«*3 honadlogous scries by making use of 
oD^n^femally avaitable Wgh-pxcssure furnace C18> 193. 
lA tMi li we have summ^ized the prep^live condi- 
^ns for 214 and related cupralc siiperconductors. 

ii «»d otker 123 cuiHrates 

Superconducting YBaaCUsO^^a with the orthprhombic 
s^inictuf e can be easily prepared by the ceramic method. 
Most <rf the investigatioiu of the 123 compound, 
YBa^CujO,.^ have been carried out on the materials 
prepared by reacting Y^Os and CuO with BaCOj [20^ 
213. It is noteworthy that Rao €t a! [21] obtained 
nioi^oif^tesu; YBa2Cttj07 its the x « 1.0 iiiiMBbeT of tht 
Y3_,Ba3>j,Gii^O,4 series. In the method em^doyed for 
|>reparinj^ VBa,Cuj07> stofcihiometric quantities of 
**iShlP>M«ity Y2O3 , BaCOj and GuO are ground ihorr 
oughly and heaM initially in powder form around 
1223 K for a peiiiod of 24 h. Following the calcination 
step, th$ pow:der is grouvxl^ pelletized and sintered at 
the same temperature ter another 24 K Rnally, anneal- 
ing is carried out in an atmosphere of oxygen around 
773 K for 24 h to €4>tain the orthorhombic 
YBa2Cuj07., jfcase showing 90 K superconductivity. 
Oxygen anneaKhg has to be carried out below the 
orthorhombic tetragonal transition temperature (-960 
K); tetragonal YfiaiCujO^.a (OA^S^l.G) is not 
supwconduGtHig. Intermittent grinding is necessary to 
obtain monopha^ homogeneous powders. This kind 
of complex heating schedule often gives rise to micro- 
scopic compositional inhomogcndties. Furthermore^ 
released from the decomposition of BaCOj can 
react with YBajCujO,-, to form non-superconducting 



fities CMT sidte prodtKSts in wpicparati^ttj^l^ 
are BaCuO^, YaBaCuO, and Y^CujQi 1^- the 
ternary phase diagram given in figure 1 iOusUates the 
complexites of this cuprate system. 

Using BaO} as the starting material has two advan- 
tages. It has a lower decompositioB temper^uie^ ^lan 
BaGOa and tbc 123 compound is tberefoxe fontied at 
relativdy low tonperatur^ BaO^ acts as aii btenial 
oxygen source and the duration of aniiealiiig in aa 
oxygen atmosphd^ is reduced to a consid^^Ue exl^v 
Sharp supercbndwrting tranisitions are observed in 
sami^ of YBajCujOT-, made using BaOj. Sight 
excess of copper in the ceramic method is r^rtcd to 
give cuprates with shaiper transitions [25]. .Prc|)ar3|ios 
of YBajCttjQ?.^ is act^mplisbed in a sh^mr period 
if one emploj^ omtal tiitrates as the starting inaterials 
[13, 23]. In taWe 2. we piresent the condi^ns odt^yed 
for preparing I B cu jMrat^ 1^ the ceramic r&ethodl 

Other rarereartb oiprates of the 12$ t;^ 
LnBaiGujO^-j whwe Ln La, Nd, S% Eu, Qd. Dy, 
Ho, Er and Tfti (afl with T, values arouiid ^K) ha^ 
also been prcprarcd by the ceramic method f26i 27}. 
Oxygen annealing of these cuprates should also be 
carried out bdow the orthorbomicrtetrago^ trail* 
sitiob tcmperalvie [3]: La. 754 K; Nd, 837 K; Gd, 
915 K; Er, 973 K; Yb, 976 K cte. Nearly 36% <tf Y eaii 
be substituted by Ca in VBajCujOt,..!. rc^^mjoo^ ^ 
barfc crystal structure [283; tie 7; dfoere^es wHh tfce 
increase in caMum ccHitent Both La ^md Sr can be isub- 
stiluted at the M site in VBaaC^aOTVi t?9-^3l J 
La, monpphasic products are obtwted for 0 ^ x^^ LO 
in YBaj^,La,Cuip7.*, the 7; (teigseasifl^ wlA ii^rc^ 
in X, In the <»se ot Sr siit^tiiudon, monoj^a^ 
products arc obtained for 0 x ^ 1*^ in 
YBaj.j^r^eujO,.,; high 7; is retained up to x ^ 1.0. 
Ccramie methods have also beeti used to prepafc 
YBaaCuj.^M^O,;., solid soJuiions* where M g^eraWy 
stands for ia transition dement of the fii^t s^es. In mo^ 



CuO 




Hgure 1. Phase diagram of the V^Oa-rBaO-CuO system at 
1220 K (from [24]), 



3 



YBaaGo^O, (124), ¥20840070,5 (247) and rtbted 

The first bulk synthj^s of YBa2Cii40g was rcpcwlcd by 
Karpiiidci er ai [34] who heated the mixture of oxides 
at 1313 K, wder an oxygen pressure of 40Q bar. Synr 
thes^ €^ YBa2Cu40s by the conventional ceramic 
method without the use of high oxygen pressure suf- 
fered from soine limitations di» to kinetic factors. Cava 
et of [353 round that additives such as alkali carbonates 
enhance the reaction rate. The procedure involves two 
steps. In the first step Y2O3 , Ba(N03)2 and CuO are 
mixed in the stoichicHuetric ratio and heated at 1023 iC 
for 16-24 h in an oxygen atmosphere. In the second 
step, the prc-reactcd po:wder is ground with an afqjrox- 
jmatdy equal volume of cithaer Na3C03 or KjCOj 
powder and pellets of the r^ulting mixture are liNE^ted 
at 1073 K in flowing oxygen for 3 days. After tte reac- 
tion, the product is washed with water to remove tfie 
exfxss alkali carbonate and dned by gentle beating in 
air. The product aflw the step has YBa^Cu^Oj as the 
inaj<mty phase (7;. 77 K) with Uttle BaCuO^ impurity. 
Other reaction rate enhancers such as NaN03, KNO3, 
ddute HNO3 and Ha^Oi have also been used suc- 
cessfully (in small quantities) to prepare YBa2Cu409 
[36-383. The 124 cupratc caa also be prepared without 
the ^cE^on of a rate enbaneer by the solid state reac- 
tion^ YiO,, RaCuOj and CuO at 1088 K in flowing 
03^i^ Synthesis of YBa2Gtt40g from the solid 
slate re^diofn b«^^w^ YB^^CujO-} and CuQ in flowing 
pxygm hfts iatbp been reported {39], The synthesb cf 
YBa^iC^t^^ by the ceramic method generally takes a 
lOi^ Htiie and requires repeated grinding and pellet- 
izing; 

Othfer rare-earth 124 cu{M^tes» LnBajCUiOg with 
Ln ?=^Eu^ Gd^ Dy, Ho and Er have been prepared by 
tfie ceramk method under an oxygen pressure of 1 atm 
[36» 4^ The 7; of these cuprates decreases with the 
ine^ea^idg Sc^ radius the rai^ Caldurh can be 
subsghited at the Y site up to 10% in YBaiCu^Og. and 

^ n^(:^«a^ from 79 K to 87 K in sudi su^ituted 
VBdjCu^^ j;4i]. Lanthanum can be substituted for 
feaiium in YBajGu^Og [42]. Single phases of 
JLa^Cu^O* have been obtained for 0^ < 0.4 
with the decreasing with increase in x, 

Extenrfve studies have been carried out on the syn- 
thesis YBaieu^Gg under high oxygen pressures [43, 
443. The P^T phase dia^am of 124, 123 and 247 cup- 
^tcs is shown in figure 2. High-oxygen pressure synthe- 

e^ss0^tt^Uy involves the solid state reaction followed 

sintterii^ under high oxygen pressures. The typical 
^!**^^^g temperature and. the |»'essure at which synthe- 
ses ^Y^jQa^Og has t>een carried oul are 1200 K and 
atm of oxygen (for 8 h). By the use of high oxygen 
Pressures [45], it is possible to prepare 124 compounds 
other rare earths such as Nd and Sm, which is 
^^lierwisc not possible under ambient pressures. 




Figuf 2. Phase diagram of the 1 24, 247 and t23 euprates 
(trom[433). 



A variety of sutestitutions has bee^ can^ <»it at 
the Y> Qa and Gu sites in YBa^Coi^Oa 
oxygen pressures, Ytlritun can )be sub^ 1©% 
by Ga in Y»aiCu40« giving a 7; of ?0% 
Ba h^ been subsdiatcd by St Wtfhout afSc^fmg 1^ 
[47]. Singlprphase iron-suhstifuted YBajCuu^^Fe^ 
(Q ^ X 3^ 0:05) has been pr^rcd at an o^xy^en pri^srie 
€^ 2d0 t^ [48]; the 7; Calk m0notoni^i^ wth^d 
ing iron concentration. 

Bordet el al [49] first reported the |wepa«itie«^ 
Y2Ba4Cu70j5 under oxygen pressure 100:^333013^. 
It was soon realized that Y3Ba4ett70i5 can be ^^^^ 
sized by tibe ceramic irhe^^ im^ a% eg^gen ^^^^ 
of I a?na by a procedare $tmi{ar to l&it etia^l^^ for 
YBijCu^O^, except the dJ^kn^^ m : 
temperature Tltcre & a; ranrow 
between 1123 K and 1143 K for ^ t^^ co^p^^ fee 
synthesized under 1 atm oxygen pressure. Tbc be^ 
simerinig tempwature at wiiidh 247 e«^ratc h 
formed k il33K. Other rare-c»1h 247 cuprates^ 
LDjBa4Cu7p,5 (Ln = Dy, ErX can abo be prepared by 
this method [36, 381 About 5% of Y can be r^qptecid by 
Ga m Y^Ba^Cii^O, , and the inercasfes to 94 K [423, 
Substitution of La at the Ba site is limited to '^10^6 ki 
YiBa^QitOjs wi^hcre the 7; deceases cwstinu^u^y witfi 
increasing lanthanum contoit [423- 

Syntteas of 247 cuprates by the bigh-|efes$ure 
oxy^h meth<»i is geheraHy carri«l out at 1203 K ill an 
oxygen pressure of around 19 bar (for 8 h). This step ti 
followed by slow cooling (typically 5 *C iriin'^) to room 
temperature at the same pressure [50). Other rare-eairth 
247 compounds, Ln^Ba^Cu^Oji (Ln = Eu, G4 I>y, Ifc 



5 




V »» rrvov cm m 

and Er). have been prepared in the oxygen pressure 
range of 14-35 bar [50], Preparative conditions for the 
124 and 247 aif»^tes are given in table 2. 

2*4, IKsnmds flutes 

Ahhou^ the ccramk method '%$ widely employed for 
the syutthesis of superoohd acting bismuth cuprates of 
the type BijiCX SrX,^,Cii,0,,-^4+, Jt is gcnciaify diffi- 
colt to obtain iiK>Qophasic conipositions; due to various 
factors [51, 521 Both thcnmodjmamic and kitwtic 
iactors arc dearly involved in determimog the ease of 
formation as weH as phasic parity of these cuprates. The 
n = 1 memb^a^ (2201) of the formula BiiSrjCuO* 
appears to be stable arouml I0S3 K and the n^2 
member, Bi^tCa. S^Cu,Oa (2122) around 1113 IC The 
n = 3 member, Bi^fCa, Sr)4Go30|o (i223)i can be 
obtatoed dose to the melting point (1123 K) after 
healing tot several days or even wedcs. Of aH the 
members d[ the Bi^Cs^ &]i,+|Gi,Oi,**^, fenaljr, Uie 
n » 2 member (2122) seems to be most stabk:. &2^y^ 
which is often used as one of the starting materials;, 
at arooi^ IICB IC Imtast^ the reaEClkm tem- 
perature ther^ore leads to prefineiitial ios$ <^ vciatile 
BijO^. This r^ults in micro-inbomo^Beities and the 
pfesence of the uareacted oxides is the final product 
Siooe these materials ccmtain so m^y cs^ioais> partial 
reac^on between varkw pairs of oxides kadtng lo the 
formaficm of tiiii»uity phases in the fin^ product 
eaaupt easily be averted. A noiewOc^y structural 
feature aO tbese tiosmuth cuprates is the presence of 
sft^^seriatt^ mp^ modidation noOung to 

do With superconductivity. 

Miost of the aboi^ proi^^ns have bera overcome by 
exuployriig tht maUix reaction mci}K>d [53, 54}. This 
metikod reduces the number of reacting compraents 
and gives better prodtu:ts. In thb method, synthe»s is 
carried out by reactmg the oxide matrix made from 
CaCOj, SrCOj and CuO with BiaO> in tbc tem- 
perature range of 1^1*1123 K in air for a minimum 
period d 48 k Qoeittbiing tbt sam{^ i$i air fijom the 
smtering tempeiatttre or bcatihg in a nitrogen almo- 
sj^iere m^>rorves the saperoonducting properties of 
bismtiQi eiipn^ The siatfiiE ita^tiofi method yidds 
«tioiiqpM^ » 2 (2122) and n » 3 (2223) compo^ticms 
sbowiiag r« values of 85 K and 110 K re^)cctiv^ [55, 
56]. Fardal mehk^ ^ a dkort pmod (^5 mm) abo 
fiavcmrs ^ ra{M formatioo ciT the A a 2 (2122} an4 
« « 3 (2223) members. 

The « « 1 xpember, Bii^jOiO^, stowing T, in the 
range 7-22 K is a ntftar oomi^ted system and has 
two structurally d^Em^ phsats near the stoidii^Mnetric 
composition [St 57-€03. Many workers have varied 
ihc ratio mi <^>tained stnglc-^iase matefiab wkh 
a 7; of iO K at a eomposttioa whkh is strcmtium defi- 
ci&iU Uz^t^t,9p^rXi^ <i13- This cuprate is bttt pre- 
pmd by reacting the oMdes and/or carbonates of the 
con^itQest Bictals at 1123 K in air £ch^ extemled periods 
of time. In figure 3 we show the pliase ^agram of the 
K-Sr-Cu-O system. The phase diagram <^ the 

ft 




R0im 3. Phase diagrafn of the 8MS<-Cu-0 syst^ at 
nio K In ah' (rrom [6G[D. 

K20.3-SrCX::aO-<:^ sy^sm «t a ^i^tant C% 
oof^oit h shovihsfn figure 4 

Sub^tuticm of a msdl amount <^ lead ibr ^ttsmi 
resiilts in supenxHKluctifig^mpla of n » 2 (211 
and n « 3 CZ223) romAms. A ihi^xb: <tf worlcm b» 
theref<»e inferred to syntl^size boili is » 2 (2122) a 
n^i (2223) numbers with substkuti^ of up 
25% in t^bi^msth [5^ €3^-6Q, 1^ 
ettber by diiect reai^^ of oxi^ nn^cjt eai^ma^ 
the caticms Q€ by the matrix reapUon mjc^bod 

Othor than Oie imtxh tm^n mih0ds, ^ 
dung (^ass roi^ ^ ami a secn^^wei mc^kedX^ 
have boc^^jMc^fed fcfr tbt s^^:x6sk ^sp^^ 
if^ bisttiuth oiprites. lu the mc3t qiiehcMng tisMhiQ 
the mhtture of starting matm^ @n the Uma of isoM 
$nd/or ca;rlK>nate} is tinted in a ptetuiimi or ^mm 
cnic^ie around 1473 K for a sbe^ pe^od faa ml: ar 
then quenched in Sqtnd nitro^ The q^^sa^ 
spedmests arc given an annciding trcailmait arotifi 
1 103 K in air to c^taui the supercOT<lw^g cryst^^ 
cuprates. This s[^^Uiod bias be^ sltown to pars^ 
both n ^ 2 (2122) and i^^d^Ki^ii « )^£2^ membei 




SrO BiO^s 
FHpur» 4v Section lhit>u^d>o phase d{40<am of t}«» 
Bi^O^-SrO^CaOfCuO s^jrstem at a consiam CuO coolant ol 
Sae mol% (from [6:^). 



3£ipi^wci piculoa inyoi^ tfx^ iic iipciiqii 

h^twcen two pimim>ts vMtih^^ xdi0^ 
sci>arattty. For cxmnpic, in the pixparation erf 
Bii.^bo.^SrjCaaOiaOjo, a precipitate <rf Fb, Sr and 
Ca (as carbonates) and one of Bi and Cu (as oxalates) 
are reacted at 1138 K in air for a minimum period of 
72 h. The duration of the reaction for the formation of 
2223 jAmt is drastically reduced by this method. 

Hie starting composition of the rcactant material 
plays an importatit role in the synthesis of these cup- 
rates. For examiid^ strontium deficiency in the /i 1 
(220}) mentor bvouis monophasic compositions [59, 
61}. Strontium deficiency also helps in obtaining a 
phaserpure n =*= 2 (2122) monber [70]. Starting with a 
4:3:3:4 stoidiicmietry of Bi:Ca:Sr:Cu, it has been 
posable to obtain a monophasic 2122 member [54, 71]. 
The A s 3 (2223) phase> oil the other hand, is either 
obtained through the substitution of Bi by Pb (up to 
25%) 0r by taking an excess of Ca and/or Cu [63-66, 
72]. Tb? ftoticm of balandng between phasic purity 
and high 7; of ihe cupntto gives rise to some ditRcuhy in 
the synthesis of these cuprates. The coexistence of some 
of the m^bers of the honiologous series, especially in 
U»e fonn of polytypic intergrowths of different layered 
sequences, is also a problem. This i^oblem is also 
cQCOUBtered with th^iiuin cuprates [73, 74]. 

The n = 4 phase, Bii.sPbo iCaiSriCu^O,^, which 
was observed in an electron micrograph along with 
n = 3 phase as an intergrowth, was synthesized in bulk 
by Rao et al [75] (with a small i>r6portion of the n = 3 
^^s^sc^ by the ceramk nvetbod. The n^4 phase has a 
lower Tc (W3 than the n« 3 phase. This 
cnprate has also been prepared by Lpsch et al [75]. 

A variety pf substitutions 1ms been carried out in 
superponducting Insmuth cuprates employing the 
oer^c method [58, 76-79]; some of them are note- 
worthy. For example; the simultaneous substitution of 
& by Pb and Sr by La in BiiSr^CuO^ results in a 
^^tiktioiwffee superconductor of the fomiula 
B^>&;j^ -jfcCuO^ with increased to 24 K [77]. 
^^iWa^i oo^ubsttta^on of Bi by Pb and Ca by Y in 
tJic >i « 2 nimber (2122) gpves a rnodulation-free supcr- 
^^uetor, ^iR)yo.>Gao ^Sr^GujOa With a of 85 K 
C^^. Rjure-earth sut»titation for Ca in BiaCaSrjCu^Og 
causes the T, lo go up to 100 K without the intro- 
4uc^ion of the ri=^3 jrtiase [5«, 78]. As mentioned 
eartttr, the n « 3 phase is stabilized by the partial sub- 
stittition of lead in place of trismuth [63--65]. Another 
^^^fcant discovery is the iodine intercalation of the 
^-2122 «Jperconductor [80]. Intercalation docs not 
S^^lly affect the superconducting properties of the 
rtl^r^' ^fly, $up>erconductivity is confined to the 
^o^cn^onal CuOj sh<Kts in these materials. 
mtA^^ of a new scries of superconducting eup- 
(ftS^r^^^ ge^neral formula BijSrjd^, _,CeJjCuj0.o 
iDiTi£222 nha<M, «H*K 1 - c« t:.. riA\ « 



fly^. - Pliasc with Ln«Sm, Eu, Gd) containing a 
CwO^^w ^^^J"^*^*)^^^ Isiyer between the two 
[8n possible by the ceramic method 

anial substitution of bismuth by lead increases 



SIS at cs^ ^m PI i^rac ^ts^WPPIPP stnia 
with ottesr taritt^c^t^^ 

As mentioned ear^^ vne do^ not sta^rt with an 
exact stoichic^eo^c cQmpositk>n to ohtmn the desired 
final product in the case of superconducting bismuth 
cupratcs. Although structural studies (sec ft^ example 
[84]) indicate the presence of bismu^ atoins over stron*- 
tium and calcium sites as well, it is no^ppsable to pr^ 
scribe an exact inldal cotnpodtk>n to obtain the d^red 
final stoichiometry. For examj^ starting Irom a 
nominal composition <rf (Ko.7^^^^<3a€^^C),, one 
ends up with the formation of the ti 3 (2223) member 
[65]. Therefore, foi the purpose of cbaraoteriztng the 
various members ctf the superconducting bismuth cup- 
rates» one starts with some arbitrary composition and 
varies the synthetic conditions suitably to obtain tl» 
desired final product in pure form. The acttial composi^ 
tions of the final cuprate are quite unexpe^ed (e.g. 
BiM3FbQ,5oSr2.04Cai.«»Cu3O^ as found from analyti- 
cal electron microspc^y [8^, In tatde 3 we hi^ve suoh 
marized the preparative conditions of all the member 
of Bij(Ca, Sr),^iCu^pj,^4+*feniiIy. 



2^ TbaQlum eitprates 

The conventioiial ceracuc method enaplaycd for the 
synthesis of 214, 123 and bisinudi cuprales has to be 
modified in the case of thallium cuprate the 
Tl2Ca^.jBa,Gu,0a.^4, tlCa,.,BaaCu,Oi.^3 and 
TlCa..,SraCtt^P2,^3 (amities dte tio ttm toxicf^ ax|d 
voladlity of thalKoim oxide. In the jear^ da^ the teae- 
tion w£ts carrkd out in an open furnace in a& or o^ge^ 
atmosptere at high temperatures {1150411801^ tot 
5-iP irSn [86, 87]. In a typical procktom, the mixture 
of reactants in the form ctf a pellet was quickly intro- 
duced into the fumape maintained at th^ desired tem- 
perature. Since mdjt-solid reai^ions take fiilace (mtt 
than solid-^olid reactions^ the product was formed 
quickly by this method [87]. Although this n^thpd 
requires a very short duration heatmg, it resi4t$ 
the loss of thallium, leading to the danger of Inj^ing 
thallium oxid^ vapour. Some wo^^Wf baye ta^cesi 
certain precautioiQiritpt to ttkast ihsi fl^^ bito 
the open laboratory, b^xt the method is^ ^ili not r^m- 
mended. FurthdrboreJ the fohnatid) of tt» xie^irpd 
phase is not ensure ttnder the c^n reaction POnjU- 
tions. Synthesis of thallium cuprates has theiefore been 
carried out in dosed containers (seaJcd tubes) by most 
workers. By tins method* both pd^^drystalline samiptes 
aiKl single crystals can be prepared, since the reaction is 
carried out over longer periods. Better control of stoi- 
chtometry» hotnogeoeity of phases and the total avoid- 
ance of tlw inhalation of toxic thallium oxide vapours 
arc s6me of the advantages of carrying oiit sealed tube 
reactions. 

Closed reaction conditions have been achieved in 
different ways. The rcactant mixture is scaled in gold 
[«8] or silver tubes [89] or in a platinum [90] or nickel 



7 



i; N H Haa a/ 



tM9 3* Preparative conditions lor the synthesis of t>isnHJth cuprates by thecer^oritc method. 



Conditions* 



Starting composHJon 



Temp. (K) 




Product 


' c W 


Ret. 


iinA 


^ A 
< u 




20 






1 A 








11^ 


^ V 


oin9*e pnoac 


10 




i-«n 


1 V 


oHf^*^ pnase 




rm 


1 IW 


3 a. 


.oH^ie pnase 




rail 


1109 


^ A 


212% ina;^>r pns^e 






1 IwQ 


2 d 




85 


mi 


1113 


3d 


2122 single phase 


65 


[70] 


1200 


Id 


2122 sin^^e phase 


e$ 


tT7] 


1140 


iSd 


2223 major pha^ 


120 




1100 


4tf 


2223maior ph^ 


105 




1153 


10 d 


2223 sln^ phase 


110 




1153 


Sd 


2223 major phase 




[65] 


1143 


5d 


2223 ntajor phase 


120 




1133 


5d 


2223 major phase 


108 


Ce43 


1273 


lOh 


2222 sin^ phase 


30 


t»1] 



BijSrsCuaO. 
BiaSfjCuOe 

BiPbSr , ^ JLa^ *.CuG« 

Bi^CaSr^^O. 

Bi,Ca,*Sr,.eOi20,'^ 

Bl^Sr^ ^CaCu^O. 
BiPt>S^3Yo,»Cao»CUaO^ 
Bi,^Ptia.«CaaSr/5U30,» 
Bi, ^P^»Ca^ftSr,^30. * 

Bio,>PtVjSrCaCu,3C. 
BICaSrCaaO. 
Bi3.2R>o..CafiSr^Cu,0, 
B*i0d,.>Ce;cKsSr,pU»O^ 



* >va me pf^pmSohscarrted out In air. 

* Obiamed tyy matrix r^c6on m^hod. 



alloy (Inoood) oontainer |]9}] closed t^jhtly with a ^3ver 
M, Ahertia^y. fbc reactam mixturt i& taken in tiic 
lonn rf a pellet, wrapped in a piatmum [92] or goW 
[93] foa and thai scaled in a quartz tube* this oiethod 
has the adviantage of carryoig out the leactioii undrar a 
vacotim. Some workers f^aoe die re^ttai^ pdtet in an 
ait^ama criidble ^] wbkh is tbcn sealed in a quartz 
ainppuie, thalli^si-exicess starttog <o«ripo$ttioos Imye 
^FC^ enjoyed ^ a few work^^ to^pcmif«^t<t fpf «he 
tfeaffim kfS9 ^ Jtactioo [95]. 

In tbe preparattc»i of the tbaOsum cmiMra^ the 
inatrix rea^n metbod is often cm^o^ Hc^ a 
wxed odd# cqnt9iim% aB the metal ions x^ber thanthe 
Vols^ tl[jaSti3tm oxkle is first pr^red by reacting the 
€x>3nre^[»6iid^ dxs^ aii4/or carb^tcs around 1^ K 
lor 24 h in iair [»,963. The finesWy prepared mixed 
<0dde is then taken with a cakidated qua&dty olTljpj 
atid heated at af^pdaie lempetatofes \& a si^tkd 
tWs m^oA ^ d wrable whda a carbonate Is MSiA 
as ^ s^rtt^ matertat Some of the ^Bi^m Cl^>rfttes 
liave been i»tt«TOd by a modified matrix metlK>d [97] 
5sl^stiii a thaffiam-cwiaiaiag pwmsor suck as 
Ba^tljOj is prefiarcd fim and thai reacted with other 
cqo^onesfts under dosed oonditioDS. ThaBiumr 
contaim^ jwtcursors are less vi;^tik than tl,d, 
so Ibat Ilie loss of thattinni is nimimizied durmg tte 
|H«pan^(Ht 

i1temo<|ynamic and ktuetic Actors associated with 
the syntfiem of thalHom cuprates are complex due to 
tb$ existence of various phases whidi arc stiwturally 
fdaied and whicb can theccfot inte^w ;with imc 
amitfaar In &ct» on^ of the coimniMi d^xts tliat occurs 
m the ^JSuni cui^^fis b the pmoioe of random inter- 
gnxwths between the various layered phases [98]. Fur- 
theciuore; siany of the &allimn» kad and btsmuth 
supGRSfxtthictors are m^astaUe phases wliidi are 
entropy jst^aHzed [99]. The temperature of the reac^ 



tion, the mnXmng ^xat tasd Ihe kai^txmipOs^ian are 
therefore ail dructal to oihlahsliig HHmo^tosk ^oda^ 
(table 4X 

The dfcct of the startmg coroposiUon is best ill|i$- 
tmted by the ionnaOe^ ol the d 3 pl^ise 1^ 
thallium cuprates (II^GHl^iC^sOteX Sy^d]iM& of this 
0ompoui^ starting frosa the sN»^4iprae^ mls^tae: e^ 
the oxides corresppndiiig to^ ideal con^ptositlm ^ien 
yields the n = 2 mraobcr ^ the ^may. U was fc^ that 
starting with compcmi^fms m €^ aii^^ JPu 
(namdy TK^jBaCu^O^* 71,Ca^iC^30Jf yidded a 
nearly pure n ^ 3 f^iasc [901 lOOfJ. t*^ H^uaJ 
position i^ however, dose to Tli tBaiCia^jCujO^. la 

case of tleaBa,GttjOi (lt23) starting from a st<»- 
cliiionictric mixture ciddes o^rre^on^g to ^ idieal 
stoidiiomdry alwa^ j^dded a lia&ctuie Of 1122 and 
2122 phases^ the rdative pvopc^ttc^ <rf^ two feeu^ 
dqpexktent on the coli£tfon& H has been ^bnionss^Uid 
ftcently [101] that tti^iuMli^^ c^npM^^ 
responding to l\i,fiiS^iOi^% {S = M to iD^ yii^ 
betW mcmc^yhasic 1 122 maAefiMs. 

-nie dialj^ of i^j^szial 4et)ja^ 

mines the nmaiber of tM> layets but cqplto^ die bofe 
coneeotratioo. As me^ioned eaitter, oi^ of the jpod 
^aiita« e(»npositicm to t^tam TkiCs^^^^^^ 
cms) is tICa,BaC!o,0, (ISI^ whieh beats ^ reb- 
tim to the oQ«nposslioA of the fioal prodi«:t ^i^^tibcr 
eacan^ is the formation di 
TTGayBa^Cu^O^ {\m\ DetaDed studies [«KJ have 
shown that the 2223 phase fomed initially transfonns 
to the 1223 phase with an hM^ea^ ^ tl^ #fati^ ^ 
beatmg. After pr^t»^ I » 

formed at the expense of the 1223 pba^ Smpar traos. 
formations have also been observed in tbit fiditmatiOB 
process <rfTlCa4BaaGaj0, wife five Gu-<> taytt^ Cmj 

The & analogue of TlCa^.,BaaCu,.02^*3 cannot be 
IHcpared in fwre forni. However, they arc stabilised by 



C^ondltipns 



Temp. (K^^ 


f I*. «e 


Gas 


Proc^McV^ 




1^. 


1148 


3h 


Sealed gold tubes 


2201 single phase 


84 


£88] 


1173 


6h 


Seated Qoldiube^ 


2122 single phase 


98 


£88] 


1150 


3h 


Sealed silica ampoule 


2122sin^e phase 


95 


[98] 


1150 


0.5 h 


Sealed silica ampoule 


2122sin^e phase 


95 


C98] 


1150 


0.5 h 


Sealed silica ampoule 


2122 single phase 


95 


[98] 


1173 


6h 


Seated gold tubes 


2223 major phase 


105 


[88] 


1123 


20 min 


Sealed silica ampoule 


2223 major phase 


106 


[95] 


1103 


12 h 










1153 


3h 


Sealed silica ampoules 


2223 major phase 


125 


[100] 


1153 


3h 


Sealed stKca ampoules 


2223 nu^CHT phase 


m 


[1O03 


1163 


3h 


Seafed^lMca ampoules 


1021 sii^le phase 


40 


[til] 


1170 


2h 


Sealed silica ampoutos 


1021 single phase 


40 


tim 


1170 


2h 


Sealed silica ampoules 


1122mafor phase 


80 


[110] 


1170 


3h 


Sealed sttica ampoules 


1122 ma^ phase + 


90 


[101] 








2122 Impurity 






1170 


3h 


Sealed silver tut>es 


1122 major phase 


90 


[101] 


1170 


3h 


Sealed silica ampoules 


1122 single phase 


90 


[104] 


1170 


3h 


Sealed silver tubes 


1122 single phase 


90 


[92] 


1163 


6h 


Sealed silica ampoules 


1223 single phase 


115 


£94} 


1198 


3-12 h 


Sealed gold tubes 


1223 single phase 


122 


[105) 


1170 


21) 


Sealed silica ampoules 


1223 major phase 


60 


Cue] 



TI^BasCuOa 
TtaCaBaaGUjO^ 

TUCasBa^OusO. 
Tt3Ca3Ba3Cu30,o 



TICa^BaCusO. 

TIjCaiBaaCuaO, 

XIBa^J-aoiCuOa 

TISrLaCuOs 

TISf2eN«*o.*Cu,0, 

TIGaEiajGujOT 

Tlo^^eaBaaGujO, 

THCaasYa5)Sr2<^207 
TIOajBajCuaOj 

Tltt.*rt>o.5Sr4Cu30. 



partly s^bslttuting Tl by Pb (or Bi) or by yltrium or 
a trivaknt rare earth [92. 104-107], Thus, 
Tlo^Pbo 5Ca,-jSrjCu^Oi,+3 shows a of -90 K for 
n = 2 ami ^mK for w = 3. TICaa,3Yo.jSr2Cu207 
also shows a T, of 90 fe. These cupratcs in the Tl/Pb- 
Ca/Ln-Sr-Cu--0 systems are prepared in a manner 
sixntlar to the Tl-Ga-Ba-Cu-O system except that 
SrCOj is used in place of BaCOj or BaO^. Sr4Tl207 
has abo been used as a starting, inaterial in some 
instant [97]. Tlw n = 1 mcmber.nMjeuOi Sr 
or Ea) is also stabilized by the siitetitotioh of Fb or Bi 
for Tt or a tmalent rare earth for Sr or Ba £108-11 1]. 
AH these compounds lowing a i; of 40 K have been 
prepared by the matrix reaction method. 

Sjm^ tha}lmm layer ^prates of the general Tormula 
^i>^2-xLniCuiO^ with A ^ Sr, Ba; Ln = Pr (Nd, 
Cc) as wcD as T1o.5pbo.5(Lni .^CcJiStjCUjO^ 
(Ln = Pr, Gd) with a fluojitc-typc LnjOj layer have 
been prep^r^ed by iflie ccf aiiiie inieAod [112, 113], The 
^-^^n^ materia seniHK>r4iictors. It has been 
shoiattt hf Lfu « id f 1143 l^iat ahiiealing TlBajCEu. 
e^jetijO^ (1222 jphase) under an oxygen pitssure of 
lOO^bu mdiie^ s^^iMui^ontfuictivity^^^ a 7; of --40 K. 

As hi tte case of b:bmuth cuprates^ the final com- 
portion of thallium cuprales is unlikely to refficct the 
C(mq)Osition of the starting mixture. Structural studies 
tW, 1153 have shown that there is cation disorder 
^twcen Tl and Ca/Sr sites. Therefore, in order to 
obtain a superconducting composition corresponding to 
^ particular copper content, one has to start with 
various arbitrary compositions and vary the synthesis 
^dityy^s^ The actual composition of the final product 
be quite unexpected (e.g. Tli.83Ba2Ca,.*4Cu30y or 
^ra6Ba2oiGuO,> as shown by analytical electron 
^crosGopy [85J. In table 4 we have listed the pre- 



parative conditions employed for the synthesis of thai- 
Rum cuprates by the cerwiic method. 

2^ Leadc^l»^es 

The conditions for the synthesk of superconducting: 
lead cuprates arc more stringent than fo^ tfte other 
copper oxide superconductors. BJfcct ^Ihfesis of 
members 6f the Pb^Sr:^ CaJC^©,^, (Lb ^ Y or 
rare earth) family by the reactioii of the com^neiit 
metal oxides or carbonates, in air Or oxyg^ at tem- 
peratures bdow 1171K b riot possMe boea^ of ti» 
high stability of SrPbQ3-rclated peroVskite oxides. Pr^- 
erential loi^ pit the more voliatite Pb© leads to mfcxo- 
inhoroogcneities. Furthermore, Pb in these c<»npoim4s 
is in the 24 state wjulc part of the Cu is m the 1 + 
state. Synthesis has therefore to be carried out un^ 
mildly reducing conditions, lypicaBy in an atmosphere 
of containing 1% Oj- The most comnipn method 
that has been onployed for tte syttibiK^is of tlHise k^d 
cuprites is the matrix teaGtipn iftelhod tliS^- P^wr 
PbjSrjCLn, Ca)Cu3Ds4* (Ln = Y or rare eartti). a 
misled ojcide coittaining all the nttia) kftts j^c^t Pb is 
made by reacting SrCOj, LnaOj or YjO^, GaCX), and 
CuO in the a^ojmate ratios around 1223 K in air for 
16 h. The mixod oxide is then taken with an ^ropri- 
ate amoiMil of PbO, ground thoroughly, pettei^ and 
healed in the 1 133-1 198 K rartgc in a flowing stream of 
nitrogen containing 1% for periods between 1 and 
16 h. Generally, short reaction times and quenching the 
product from the sintering temperatures into liquid 
nitrogen in the same ' atmosphere gfvaes bctter^uaUty 
samples. Even though this is the common method for 
preparing Pb2Sri(Ln, Ca)Cu3Qs + » il is not always 
easy to obtain samples exhibiting good, reproducible 



9i 



st^perconduciihg properties. The lead cuprates from the 
njtthod dc^bed above generally show broad tran* 
sitions in the /?-T curves with n^adve temp^ature 
codltcients resistaoce above 7^ . 

Studies of ibc dependence of t; on the caldam con- 
centration in the Pb^Sr^Y^.^Ca^CaiOa^a system [1 17) 
have shown that heating the sam|^ near the meiting 
point between 1198 and 1228 k tor 2 h and post- 
annealing in flowing nitrogen gas at a temperature 
between 673 and 773 K improves the superconducting 
jM-opertks the samples dramdtkaliy. Direct ooe-step 
syBtte»s has been achieved [! 18] by reacdng tbe metal 
oxides in sealed gold lobes around 1223 K. An altcma* 
tive route to the direct synthe^ from tivtal oxides 
and/or carbonates has also been demonstrated [119]. 
Superconducftivity near 70 K has been reported in 
Ca-frec J*b2Sr2LnCu50g+^ (Ln « Y or rare earth) 
employing the vacuum annealing procedure [120], Sob- 
s^tution ctf Pb 1^ K in Fb^2^QjP^,s^^On^$ has 
afo bees c^iied out by the ceramic tm^tbod [1213. 
About 30% <tf Ph can be substituted K and such a 
sobslttution increases tht X ^* The » » 0 

member pf the iihSri(Cai-,LnJi»CUj^.,0^>3j,^^ series 
(namdy Pb2(SrLa)Co306+A) has been prepared 
sucee^uHy this matrix reaction method [122]. 

tJt&Ke the 2213-^^ lead cu|mites;» suppcpnductn^ 
i212*type lc3^ cuf^t^ of the fonmtia 
(i^,5C^^J&^t0^^.5Cao.5)CttaO7-j are synthesized in 
an oKidxring atmosphere. Several authors have rqKHted 
<6re(^ synthesis wdl as reactions under dosed con- 
tjBtt<ms £12J-I27]. In the direct syiith^ of these cup- 
rates, care is takeia to i^event the loss of Pb by 
wrapping p^kts in gip^ or piati^m Ml [127], Roml* 
Umeial [125. !ia\^ reported the sytithe^ or i212 
lead capfsttcs ky the da^cci reaction d t$ic component 
coddes m evacuated st^ ampoules. Tliis method has 



the advantage of ai^u^g the ox'j^sn partial pressure 
required (or the sylbthesis. Botli ^l3Mype and 1212- 
type lead cuprates have been prepared usti^ the nitrates 
of the metal ioiu as the starting materiab [128]. 
Althmigh this procedure yields ^13 or 1212 phases m a 
sin^ siep^ the product obtained ^ways has impurities 
sudh as Y^O} , CuO etc 

A sopercmductiE^ lead cuprate of the fomiula (Pb, 
CuXEu, OeWSr, Eu>30ijO, (1222 fibm) containing a 
fiuorite layer has hem pftpst$td the dittct rt^im of 
the compodeatt metal 03tkles at 1273 K in oxygoi atmo* 
^>here [129]. 

ff^-pres£ure ceramic synthesis has been emplo^^ 
to {ffcpare leitd cupfales oC the 1212 type £130, 131], In 
orctor to pi^tr Pba.jOio.5Sr,Y^ 5Qio.jCo70i-,, 
sintering is earrkd out at 1213 K for 15 h under an 
oxygen pr^sure of 100 bar fi^lowed by £a$t co^g to 
373 K. The sampks i^i^ned from hig^pressute 
oxygen treatzneat show h^ier XtS thm these f^ooESsed 
at i bar ^resstfans irf €%]n^ Sutisttoi^4»i Y 1^ o^h^ 
rare earths has been p<Ki^sffi4e fc^ %ll^xi^ge^-pi^ 
stire method pil]. >UI the rare^ea^ s^Mtlx^ 
pounds are supocondtictmg w^ %s in the S^'W K 
range. The 7^ decreases with increase In ^ stze of tht 
rare eardi. In table 5 we summ^inze the pondi^o^ for 
the ^nthf^ ofthe viaitotis le^d^spralc^ 1^ fhecmmk 
methodL 



2.7 Electr ffiB Hl <q> e d siy ^ 

AH tlK? cupratjQ disused ^ uo^ am bole 
dtictdrs. Syntti^ of efectroiHloiped oiprate sup&r^Q- 
ductocs of tte type tMi^Mw(^4^^M ftn Hd, Pr. 
Sin, Ed: M » Gi^ ThX possessing tfie F ^tnxstm^ h 
genHcr^ aetievtd lyy ^ ber^^uir m^b0d tl32^1^}* 
The ocmdtti^ of syi^icisb Birt mo^ s^ir^geot stnce the 



Tittle Si Conditions for the synthesis ot lead cuprates by (he oeramk: method. 



Conditions 



Compmrnd 


Starting materia 


Temp.OQ 


Time 


Gas 


Comrawts 


7aW) 


Ret, 






1143 








78 




















PbO.PbO^;CaOgt. 


1223 


12^ h 




Sealed 90M tabes 


78 






















PtiO, $rC0s« YsO» . 


107$ 


15 h 


«k 












1173 


2h 


air 










^m 








78 








Idea 


6h 




220(2 ina|orpluise+ 
























lors 


5h 








(123J 


CuO 


1573 


2h 


Oa 






l^tO.SiCOs.YA* 


1t23 


tOh 


air 




50 


[«4J 




CaCO,»Oi!0 


1273 


1h 


o» 


t2i2ma^p^ttse'i' 














for) 






1243 


3ti 




1212ifia|orpttasa-fr 


47 




Cuj|^^ matrix 












im 






1108-1223 


1-1© h 




Ev«i$tMted «{^ tubes 


100 


Y^ivCoOa . Cu^O, CuO 


1106-12!^ 








80 


(lag 






t-IOti 




Evacuated tufa^ 




$rCuOa*Y;^,C«aCuO 


















t123 


ion 


air 




25 




GeOa.CuO 


ms 


lb 











10 



ccmtelit m tfce cop^e. I^dr thi$ reason, samples after 
cakhiatiGii aud sintcrijjg at 1323 K in air (for 24 h) arc 
annealed in a rcdticing atmosphere (typically Ar, Nj or 
dilute Hjt) at 1173 K to achieve superconductivity. 
Samples pr^red in this manner show a negative tem- 
perature coefficient of resistance above 7^ in the R~T 
curvtt; the resistivity drop at is also not sharp. An 
alternative synthetic route involves the reaction of 
pn&-reac^ NdCcO^ ^ mat^al with the required 
amounts <rf Nd^Oa and CuO at 1 253 K for a minimum 
period of 48 h in flowing oxygen [135]. The siampfes arc 
then rapidly quenched from 1253 K in ah argon aun<>- 
sphere to achieve superconductivity. This procedure 
eliminates the slow diifusion of Ge throughout the 
Nd^iGuO^-^ host and gives uniform concentrations of 
cerium and oxygen. Samples obtained from this route 
show a sharp transition at 2t K. 

Superconductivity with a 7; of 25 K is induced by 
doping fluorine for oxygen in Nd2Gu04 . This has been 
aceomirfished by taking NdFj as one of the initial reac- 
tants [1363- Suteirtution of either Qa or In for copper 
ro non-superconduciing Nd2-,Ce,Cu04,a also induces 
superconductivity [1 37^ 1 38]. 

Ii)^te4ayer cuprates 

EHs^ycry of superconductivity in cuprates containing 
iniinite CuOj layers has been of great importance in 
understanding the phenomenon. Very high pressures 
have be<&n employed for obtaining the infinite^layer cup^ 
rates. Both holc^opcd (e.g. Ca,.^r,CuOj) and 
^tron^oped (Sr, .^Nd^CuOj) infinite-layer cuprate 
supercofidttc^ors with a maximuro T; of 210K have 
been reported [139-142]. Infinite-layered cuprates of 
the type (Ba, Sr)GuO:i, (Ca, SrjCuO, are synthesized in 
an oxidizing atmosphere uiider high hydrostiatic ptt&- 
sure [139, 140, 142]. Electron^oped Sro.s^Ndo.MCuOj 
is also prepared under high hydrostatic pressures [141]. 
Metal nitrates are genially used as the starting 
materials since carbonates of Ba, Sr and Ca have high 
decomposition temperatures* After decomposing the 
metal nitrates at around 873-1 123 K in air, the product 
is subjected to high pressure to obtain the supercon- 
<N^iiig fliases. Sro.jftNdo.r4euOj , which supercpnduc- 
at 40 K, is made under a hydrostatic pressure of 
25 kbar at 1273 K. Superconducting {Ca, Sr)CuO, is 
F^pared ai 1273 K under 6<3Pa ptcsst^rc. Deficient of 
St and Ga as wcH as the oxidi;dng atmosphere make 
this phase superconducting, and the oxidizing atmo- 
^bere is provided by heating a capsule containing 
KQO^ along with the sample. This cuprate has a T. 
Sonset)of no K. 

^- CoprecipitaHon and precursor methods 

^^precipitation involves the separation of a solid con- 
^^^ng various ionic specif chemically bound to one 



of GTj^iiflftEie 6t mm W 
wdl defined stok*feineiry to m mm 

ions is obtained only when the fcAowing coioditions arc 
satisfied. 

(i) The prcdjHtaling agent is a multivalent organic 
compound which can coordinate with more than pi^ 
metal ion, and the precipttation rate is fast 

(ii) The solid precipitating out of the solution should 
be really inspIuWe in the mother liquor. 

The anions generally prefm^ed (ot copred{»lation of 
oxidic materials are ca^natts^ oxalates, citrates etc. 
The same is true of high-?; cuprates. Tte jstctpitates in 
some instances could be g&nuine precursors or spHd 
solutions (5, 6]. It is well known that precursor solid 
solutions drastically bring down diflfusiod d[is[tanGes for 
the cations and facilitate ructions in the soGd state. We 
shall not distinguish s^ecursor solid soluti<His.pred|»- 
lated from solutions from other preotrsors in this 
discussion. 

The precipitates (carbonate, oxalate etc) are heated 
at appropriate temperatures in a ^ttabte; aUnc^erc to 
obtain the desired cuprite. Some of the advkntag^ of 
the copredpiiation teduuqUe oyer the ceramic method 
arc an homogeneous distr3>uti0n of cofet^r^is^ a 
decrease in the reacti<m temp<»^atures ajsd the dura- 
tion of annealing, a higher d^ty and a loi^ parole 
size of the final product The ni^or drawbate^ 
route is the control over the ^o^iomelFy crf^ the fih^d 
product. 

3.L Laj^^^CoO^ 

Sr and Cii in La^ -j^SriGuQ^ ^re neadi^ €^predi»^ 
tated as caibonates [1 1, 12, 143]. For tfsS tfe 
required quantities of vaurious iiiti^^ 
solved together in distilled water Alter0itfvd^» Aie cor- 
responding oxides are disserved in hlHtric ai^ to give a 
nitrate solution and the pH <rf the scrfutiHE>n is a#U5ted 
to 7r^ by the addition of KOH solMt^n. A solution of 
KiCOj of appropriate strength k then sh^vly added 
under stirring to give a light blue pred}»tate wfaieh is 
thoroughly washed. The prectpitaic is dried at 42& K 
and calcined at 1070 K for 8 h in air The resuitmg 
Nack powder is ground and peltetized arid siritercd at 
J270 K for 16 h in air to obtain monophasic 
l^i.«5Sro.i5Cu04» superconducting at 35 K. 

Instead of as carbonate, the nwjtal ions are afeo 
readOy precipitated as oxalate 1^ the ad<^ton crf^ either 
oxalic acid or pota^ium oxalate to the solution of 
metal nitrates [J U 12, 144, 1453. The precipitated 
oxaJatc is then decompose to obtain the cuprate This 
method has certain disadvantages: 

(i) La"* * in the presence of an alkali metal oxalate 
first yields lanthanum oxalate which hirthcr reacts with 
the precipitating agent to give a double salt Control of 
sloichiometry therefore becomes diflicult. leading to 
multiphasic products. 



11 



o nf n nav vt ttf 




(ii) The relative solubilities of some of the oxalates 
also pose difTicuhies. For example. SrC204 is nearly 
four times more soluble than SrCOj . 

3^ YBajCoaOt 

YBa^CujO^ and related 123 compounds can be 
obtained via coprecipitation of the component metals 
(from a nitrate solution) as a formate [146. 147], acetate 
[148], oxalate [12, 149-156), hyponitrite [157] or 
hydroxycarbonate [158, 159]. Some bt these precipi- 
tates eould be genuine precursor compounds as is 
indeed the case with the hyponitrite. 

In oxalate coprecipitation [12, 149-152]. oxalic add 
solution of ai^opriale concentration is added to an 
aqueous solution of mixture of nitrates of Y, Ba aiid Cu 
and the pH of the soNtion is adjusted to 7.5 (by dilute 
NHjX The pale green slurry thus formed is digested for 
1 h, filtered and dried. The oxalate is converted to 
orthorhombic YBajCujO^-, by heating at 1053 K in 
air for 5 days followed by oxygenation at 723 K. This 
proecdure, even though successful in making supercon- 
ducting YBajCUjO^-* in small particulate form, often 
rest^s in undesirable st6ichk>metry because of the mod- 
erate solubility of bariiim o^talaie. Futthcrmorc^ rare- 
earth tons in the presence of arhmbmum oxalate ©vc a 
dmiblc!^! with the excess oxaliie which competes with 
the p^jMtation of copper and barium oxalates. These 
xiifTrc^iities cstn be overcome cither by taking a knowii 
excess {wt%) of barium and copper or by using tri- 
ctbylammoaium oxalate as the precipitant in aqeuous 
ethanol medium [153-155]. The alcoholic medium 
decreases tl» solubility of barium oxalate and the pH of 
the soiotion is controlled in sir w. 

A bctm method of bomogepeous coprecipitotiort of 
oxatales fa that <^ Liu et al [156] usin^ tirc^ aiJid oxalic 
add Urea, on heating, is hydrdyi^ liberatiftg GO2 
aod NHii and thus gradually adjusting the pH 
throughout Ibe solution. The CO3 hbcrated controls the 
bumping of the solution during digestion. The oxalate 
copredpitation route is widely described ih the liter- 
ature. The reactive powders obtained by ihc oxalate 
copredpitation method decrease the sintering tem- 
perature. The formation of BaCOj in the intcniwdiate 
{sdcmating step makes it difficult to obtain 
YBa^Ctt JO7 - , in pure form. 

Coinplele avoidance of the fonnattoa erf BaCOj 
during the synthesis is possibfe using the hyponitrite 
[157]. The hyponitrite precursor is obtained 
froiui a nitrate solution of Y, Ba and Cu ions by the 
addition gC an aqueous Na^NaOa solution, Tl^ prcdpt- 
tate is converted Into superconducting YBajCu^Qi-* 
by heating at around 973 K in an argon atmosphere, 
followed by oxygen annealing at 673 IL Although thb 
route provides a convenient means of obtaining the 123 
cuprate at niuch lower tempdatures than wkh other 
methods, there is a possibility of contamination of alkali 
metal ions during the course the iH:edpitatioa 

YBa2Cu307 can also be pxtpzttd by the hydroxy- 
carbonate method £158, 159]. Here, KOH and KjCOj 



are employed to precipitate copper as the hydroxide 
and Y and Ba as the carbonates in the pH range of 7-^. 
By employing NaOH and NajCOj, complete predpi- 
tation as hydroxycarbonate is attained at a pH ^ 13. 
The product from the above two procedures is homo- 
geneous, showing sharp onset of superoonducliviiy at 
92 K. The possibility of contamination by alkali metal 
ions cannot, however, be avoided. 

33, VBa»Cu40, 

YBaiCu^Ofl can be prepared by the oxalate route [160] 
wherdn the solution of Y, Ba and Cu nitrates in water 
is added dropwisc into oxailic add-triethylaminc solu- 
tion under stirring. Complete precipilauon of Y, Ba and 
Cu with the desired sloicJiicKnetry of 1 :2: 4 is achieved 
in the pH ran^ of 9.3-113. The predpitated oxalam 
are filtered and dried in air at 393 K. the solid obtained 
is then heated in the form of pellets at 1078 K in 
flowing oxygen for 2-4 days. The product after quen- 
ching in air shows the 124 phase as the ma^or product 
with a T^of 79K. 

An altcTBative copredpitation route for the $yntbcsSs 
of YBa2Cu408 is the method of Chen ei al [141] m 
which the aqueous nitrate solution of the oonstkuenl 
metal ions is mixed with j5-hydroxyqt»nptinc4ri. 
ethylamine solution. The precipitated oxinc fa filteired, 
washed, dried and sintered at 108? K in oxy^n 3 
days to jield |Aas6-pure YBa^thaj^Qs showing a I; <rf 
80 K. Ethytenediaminctetraacettcadd [161] as wdl as 
carbonate routes tl62] have also been taiaploycd for ihti 
preparation of YBa2CU40B . CoprccipHtapon using trf- 
ethylainmoniuTiS oxalate basr been t;cj^<Mt<fd for substi- 
tuting Sr in place of Ba in YB^jCft^Os [163]^ 



XA. Bitsmudi cuprates 

Very few copiedpilalioia studies have been carried out 
on the p«pa^ti6n Of bfatnuth cuprates. One reason 
may tx^ that desfMie the gofed saiti^ homogetldiy gen* 
erally obtained thmugh sohition n»tte>ds, the cbenjistry 
of bismuth cupraie$ fa rat^ complex: It fa not that 
easy lo find compounds erf aB the con|titi«»t me^ tons 
soluble in a ccHoimon sotvott; ?ontr^g I** stc*^te 
t%iy in Oeso cuprates fa di^ctttt m the co^ecij^t^^ 
tion proceduie. Paryiemcare, bisrouA mtmie^ wMch fa 
often used ^ one of the stattii« materfatte, decom{K>s^ 
in crfd water to a basic nitrate pfed^tete as pven by 

BKNOj)j(s)-^Bi** +JNO; 

Bi^* + 3NOJ ^ in^O rt BKOH)2N05(s) ^ 

This proMem can be ovcJcorae to so^ extent by jM^e- 
paring the nitrate ^lution of bismuth in nitric^ a^Sd or 
by starting wi& ^smujth acetate instead etf the mttm, 

Bidentate l^ads sudi as the ox^Jate are: Uimi to 
react more rapidly than multidentate Hgands sudi as 
citric add [164-1741 in the copredf^ta^on process. 
Com|4cxes of oxdBc acid are also ©ore stable than 




BiC204orSrG,04. 

A stiai^tforward oxalate oc^rcdjHtatkHi is 
ai^ieved dksotving the acetates 1^ Sr a&d Ca 
in g^dal acetic add and then adding excess oxalk add 
10 the solution [1^1 The oxalaU prcdj^tate ts dried 
and decon^>oscd at around 1073 K in air and processed 
In the 1103^1 123 K range for periods ranging from 24 b 
to 4 days, depending on the starting composition. The 
n » 2 (2122) membo^ obuuned by this ^ocedure ^ws 
2cfo resistai^ at 83 K. In another procedure reported 
by Zhang et ol [1651 ^ ^ Sr/Ca/Co nitrate solo- 
tkms are mixed in the reqoired molar ratia Into this 
s<^ntion is pottred a s<toti<Hi of l^smath idtatc pro- 
pped m i»tiic add along with oxaltc add. The com- 
plete prec^tatfon occnrs at a pH of around 5 (attained 
by tf^ addition of aqueous NaOH). This process 
involves the posstbiHty of contatnination of sodium 
ions; this has been drcmovented by using h^CH^^OH 
to adjust the pH the solution [166] and complete 
l^edfHtation of tt^ oxidates occurs at a pH 12l All 
these procedures, however, produce mixed-phase 
samples. 

For the prci^ration of the monophasic lead-doped 
n at 3 monber (2223X oxakte coftfedi^iatton has been 
found eSeetive [167-174]. In the procedure reported by 
Ck^g ef izl [HiX the mdlar ratio of the chdating 
agjbnt (oxahc add^ and the nitrate anions (fircm the 
meta! nitrate soluticuis) is fixed at OS and the pM^ 
2H$UStod by NH4OH sohition. at which complete pre- 
dpitaik>n occurs is 6.7. 1^ i^^oduct from this m^hod« 
Bi» ,»l1>o.«$r20i2Co,Oy» after sintering at 1133 K in air 
for 72 hv shows a Te of UD IC 

Coprecipttation as oxalates 10 prepare the lead- 
doped « = 3 member (2223) has been achieved from an 
e!(hyfene glycol medium ming tnetbylammontum 
oxsfote aiKi oxalic add [172]. A more easily conlroUed 
and reprddiKit^ oxafaitc ^predpttation |»^occdure 
appears to be thai (^Shd et irf [173] where in a mixture 
of trieihylamine and oxalic add is emj^oycd. The 
advanta^ of using tiiethylamine is that it has a Ugher 
ba^ty and a lower comptexiog abOity towards OHlf) 
than has ammon^ CocM^ of the stoicfaiometry of 
the ^al product is ibci^ore belter obtained with thU 
procedure; preci^taticHi occurs in the pH range l.S-12 
The copred|»taied oxalates stiHered at 1 133 K in air for 
a minimum period of 72 h give monophasic 
®»i^Ptloi<SriCaiCu3Q»o with a of 110 K. It is pos^ 
sft^ to av<»d a^usUii^ the pfl in the coprec^>ttatk>n of 
oxalates [174], The procedure inv<^ves copredpitating 
the oxalates from dilute acelatc solutions instead of 
ftxm mts^te solutions. The oxalates are then converted 
to neady phase-purt Bii.«Pbo.4SraGa2Gn30io {T^ of 
106 K) by sanltdng ai 1123 K m atr for 1 60 h. 

Carbonate corpredpiiation has also been carried 
out for the synthesis of superconducting bismuth cup- 
rates t^75. 176], but the mcihod does noi ywld mono- 
phasic products. 




aqioeous s<^^:^ as ' o3dM^ #V^^ 
bohty of thalfium oxsiMueu Sowe^^ ikmS»A 
Gritzner [177] have found that caoii^^lele copfee^fita- 
tioo as oxalates can be achieved staining with thal- 
lium acetate m gtacial acetic ackl medium. In the 
procedure repcHted for fi» preparatkni of the n « 3 
member (2223X itoidiioiiietric amounts of diaffiuzn 
acetate, CaCOj, BaCOj and copper swetate are dis- 
solved in water containing giadal acetic add. Tltf solu- 
ticm containing aB the catioas is then added to a 
solution of oxiedic add (exces^ under sttrxxng. The pto^ 
dpiutc, after cMgesticHi for 1 li« is fitteied, washed ^d 
dried. The oxalates are heated in the fenn of peflets 
(wrapped m g^ fd^ at around 1173 K for 6 min in an 
oxygest atinosplieteL The product after annc a ft^ in the 
sanie atznosptoe slk>ws £223 as d» major f^ase with a 



X6. Lead citprales 

Carbonate copcectpitadon is foui^ to be sats&ctory 
for tl» synthesis of represenutive s^inb^s ctf super* 
conducting lead cuprates [128] of 2213 ^ 1212 
types, namdy PbiSr2Y4^,C%jfCtt30»^, ifld 
Pb(^,Sro.,SriY^3Ca<,,5Cu207.,. Gk^)redi»teUiott as 
carbonates has been achie^ by oddijo^ the nitrate 
st^utk>n <£ tfie ccw^huent ^letd Itm^ to an sqbeous 
soluiJon of sodiimi carbcmate^^ cxqes^ tmler coiK^t 
stirring. The carbonate predpitate thus pbtabied is 
washed and dried The dec<»n|K3sed powdo^^ is heatpd in 
the form <^ pellets aroiJuid nS3 K. in a sidta^ ^ikh 
sphere. PbiSraCa^jYo.jCnjOs^, obtaii»d by tiiis 
method after heating for 4 h in nitrogen cot?(tainii|g J% 
O2 ^owed 2213 as the major pbsro (T^ - 74 E) w^ 
impurities sndi as YjO^. GO- The 1212 |*ase 
ot^if^ alter heating in oxygen at 11J3 R to 12h 
^wed a broad tfa^i^^ viA a T.if^$sm} <rf 1«0 K. 
This method has the advantage of he^ng caher 
than the ntiulti»ep i^^eedvto fe«irf«5d in the c^hcr 
inetbods. 



4. SeHiel process - 

The sd-gel process is em(^oyed in order to get homo- 
geneous mixing d[ cations on an atonic sCdH $0 that 
tlw state fiiactton occurs to csMUf^eti^ is a short 
dme and at the lowest posdble tempemtttte. The term 
fiol often refers to a suspension or dtsp^on of <fecretc 
coJfoldal particles, Yt^le a rqpiresents a ex^oi^Bil or 
polymeric sofid amtaining a fluid component ^*ic* has 
the intmial network structure wherdn both the solid 
and the fiuid con^nents are highly dispell In the 
sol-gel process a conceutratod sol ^ the reactant otitfes 
or hydroxides is omverted to a semi-ng^d gd by remo- 
ving the solvent The dry gel is healed at an appropriate 



13 



c N H mo etaj 



temperature to obtain the product Most of the reao 
tioAS m the soi-^ process occur via hydrolysis and 
polycondcDsatioti. 

Two dilTeretit routes for the sol-gc! proce^ arc 
usually described in the literature for the synthesis of 
hJgh-^T^ cufH^te superconductors: 

0 Via xnolecutar precursors <e.g. n^tal alkoxides) in 
organic medtum; 

(ii) Via ionic prccu^ors in aqueous mediuin (dtrate 
gd {M^ocess). 

The purity^ nucrostructure and physical properties 
of the ^oduGt are controlled by varying the preoirsor, 
soivent, pH» firii^ temperatures and atmosfrfiere of heat 
treatment, 

4.1. ZM CnpMtes 

SupetccNiductlng 214 expounds are prepared both 
by means of organometaUk precursor aiul by the 
dtrate gel pfocess [II]. Lanthanum 2»4-pesitanc 
dionatc» barium 2,4-pentane dionate and cojppcr (II) 
ethyl l^xanc^te arc mixed at ro<Hn teiiq>erature t» the 
appropriate ratios tn metboxyethanoi medhmi to obtain 
the orgaTOm«t;aI}ic precursor. AAer ^gorous sdrriiig at 
roiHxi temperature^ the ptec^rsor ffi h oonvolod to 
mcofc^^aae La,.^»ao.j&<>* (% » K) by firing at 
S73 K m oxy^c^ 

In the dtrate process, a mtxtuns citric add and 
ethyietie g^rvxd k ^Ided to the sdutira coi^atmng the 
required quantitks of metal mtratei The re»ihing sohi* 
tjon is v^e^^Misly sticted and heated acotod 193 K. 
EHirkig dkb ptKC^ oxides tutn^en resulting 
in a vkoous gel The g/^ h decomposed ^ 673 K in air 
and the ie»iltsng ^ack powder b then ^ven Uie neces- 
sary heat treatment to obtsun the superconducting 
oxide. 

In tiMB c^ (tf yBajCuj07.j^ the a^oxide 
are bc^ my ^cpemave and <lifiEk»it to otoiiL la nddi- 
^<m* the solubl^ of copper alkoxides is very low m 
ofgank sdvents and yttritim aftoxides are readily 
bydrolysed even by a trace of water. Deqslte these 
cuhies, Si^)erconductii^ YEaj^CuiO^.j has been pre- 
partd tek^ aOiogddes 1157, 179-181]. A sin^ leai^ 
i&vdving Y(QCIfKfe2))« ^^pCHMex), and CutN&u,) 
in THF in an aifon ateosplttre giits the 
ofgHs^mmllic pftcursor £1573. Tl^e p ttc gis 6r po^^der, 
after removal ^ the sotvott, is finlered at 9B K in 
flowing aificMQ to obtain tetrftg^oal YBa^C^^j^^, Fd- 
)o«^g osjrg^isiUoii at 673 the fH'odtict ^ws a % of 
$S K. S^jcreonifoct&ig pr opcr ti e a hai^ been tra^ved 

using »4)utoxi^ of Ba and Cu in butanol 
sotveot [179]. 

Aftetna^vis^. methoxyethoxides of yttrmm» barium 
and copper have been used as p iec nrsor s in 
mcthoxye&am^-methyMh^lcctDae-^oloen^ sc^voit 
mixture to prepare YBaaOi^O^., £1805. In of the 
preparaticws, O^O^ (stable in ethanol) or cof^ 



acetylacetonate (soluble in toluene) is used along with 
the alkoxid^ of yttrium md barium (o ovocomc the 
probten of low solul»lity o^per alkoxides [182, 
183]. Organometallic precursors involving prp^oi^tes 
[153] and neodeconates [184] have also been used for 
preparing YBa^Cu^O^ ^ ^ . 

Modified sol-gd nKthpds which do not involve the 
metal alkoxide precursors have been employed by many 
workers. Thus, Nagano and Greenblatt [185] have 
employed metal nitrates dbsolved m ethane glyc<^ 
After rdluxing around 353 K under vigorous stirrings a 
bluish green colloidal gd is obtained. The gel is con* 
verted into orthorhombic YBajCu^O^^^ by heating to 
1223 K in flowing oxygen. Pred{aiatHig all the titfee 
ions as hydroxides abo results is Ime eotkidal (j^r^des 
of the starting materials [186-^188]. the {^ecfphation is 
ges^mBy carried out by the addition of NH^OH 066% 
mCH^OH [187] or Eg^OHh [1^] to a sc^t^on of 
metal littrates (pH rang)e 7^ Thi^ hydroaddes are 
ckcomposed around 1223 K in bxygesi to give 
YBa^Cu^O^ showmg a i; of 93 K. 

YBajCuaO,^, has been prepared hy the citrate gd 
process [189-193]. En Ous method 1 g equsvaleat oi 
citric add is added to ea^ equivalent of the 
metal The pH iot the solution is ad|»sted to around 6 
^^ithor by NH^OH or by ediyiaa^dbmiiK> Evapcnr^^ 
pf the solvait fwat^ aroupd 3:^ K,fcsaltsin ai^j^bcoti$ 
dark blue gd* the gel is lEte^pompospd and the powder 
smtmd in Uie fom of peSm at 1173 K in ox]^ to 
oUain orthorbomHc YBslJCo^Oi^^ (7;» 91K]l By 
tlm method, oHtaSm bomc^seneous powders (particle 
size -^OJ ;an) are obtamed. Tbe ^udal step in fhk 
process is the «<yustment of the pH whidi controls the 
stoicbiometty of the finiM f^oduct Tim ^xvimkm has 
been ovenxmie by disper^ Ibe cerate metal i<m com- 
plexes in a solvent mixture of ^hyJ^e g^fori imd water 
tt94.i9$]. 

Problems such as the Ibnnation of hs^^ di»ring 
!^ calanatiofi Sm^iiEm and cc^iljMaimatMm of 
aBcali mietaJ ions hi the final prodttcl are aye&led in the 
^c^-^l fooccss. FmSbtmoxt, perfect bcmiosa^ is 
c^tamed bdm caJdnackm. 1^ sol-gel process i(e^ 
eitntte process) iias the advamt^ over tbt (Kber 
methods su that the gel can be used toit making thick 
and thin supaoc»jducting ffims^ fibres etc vAuxh have 
ledmological tmpOTtanoe [1^, I8X I8t^ 1^19^. 

The sol^^ method o&n a good altemative to the 
c^amic method for ^thess. <tf supt^o^ucting 
YBa^Cu^Oa. The fi^lowo^- prooadure has been med 
to prepare YBaaC^O* at 1 atm oxygen pessm% 
[199]. ApfKTopriate quantises of Y(« -OC^>,, 
Ba(s - OC4H^ and €u<s - OBu)j m butann^yfone 
mixture are lefiiaed in aa aigon atmosphere at 343 K 
for a period of 30 h. Tbe Sne powder after the v%orous 
reaction is freed frcun the solvou ai»i drkd. The powtto 
is heated in the fc»in of pdkts at 1033 K in fiowuig 
oxygen to obtain superconducting V^aCu^O^, 



osed as tfee source of in ^ prtj^' '^]- 

In thp iDodtfied dtiate gd proctw prepare 
VBaiCu»0» [201, 202], 1 g equivaJent of citric add is 
added for each gram cquivaknl of the metal and the pH 
of the solutiOB is adjusted to ~ 5.5 by the addition of 
ethyteocdianunc. The resulting dear sohition is evapo- 
rated to yield a viscous purple gel. The decomposed gd 
is sintered in Bowing oxygen for 3-5 days at 1088 K to 
obtain neariy roonophasic YBajCu^Og (T.*66K). 
Kakibana et d [203] have rqx»ned the preparation of 
YBajOuO, using a precursor obtained from dtrate 
metal ion eomptexes uniformly dispersed in a solvent 
mixture of ethylene glycol and water. This method 
yields phase-pure YBajCu*©, (T, ~ 79 K) and elimi- 
nates the need to adjust the pH. 

4.4. Blsinntli cuprates 

There have been very few reports of the preparation of 
biMnUth^basrf caprate supetcondoctors by the dkoxy 
sol-gd method [2041 Some of 4he difficulties arise 
because the rdevant bismuth/lead alkoxides arc not 
readily available: it is also not easy to get a coinmon 
organk; solvent to dissolve the various metal alkoxides 
simultaneously. Dhalle « al [204] have, however, 
attempted to synthesize the lead-doped n = 3 member 
(2223) osHig organometallic precursors involving proi»- 
onates. Tl» stardng materials were taken in the foriii of 
nitratis and converted into propionates by die ad^Uon 
of an excKS of 100% ^opyl aksohol. This step was fol- 
lowed tgr the addition of ammoni wn hydroxide awl ^th- 
yliaie glyarf to inareasc the aJkoxy anion concentration, 
thos in tuat increasing the viscoaty of the solution. All 
the solutionis were mixrf li^ther and dried at 353 K. 
The nain after calduation at 1123 K in air and sinter- 
ing at 1 118 K gave a mixture of the n = 3 and n = 2 
members. 

A amirte sol-gd method involving the addnion of 
daute ammonia to an aqwous solution containmg 
mtfates of Bl, tt and acetates of Ca. Cu and Pb (until 
the pH of the soiution reached around 5.5) has ?Sso 
been employed to prepare bismuth cuptatcs [2)5, 2(^ 
Tfe ^ soltt^a aft^ concentrating at around 343 K 
a vkscwBS gel. The gd is d©»mposed and the 
powder sintered at arouiid 1128 K in air. The product 
from this procedure is multii*asic showing a 7, of 
104 K. The simplidty of the method and the formation 
of the « = 3 phase in a short time makes it somewhat 
superior to the conventional ceramic route. The modi- 
fied dtrate gd process has been emj^oyed to prepare 
the « « 2 member (2212) in pure form with a T, of 78 K 
[193]. 

4.5. Lead cuprites 

Tht modified citrate gd process has been successfully 
employed by Mahesh et al [207] for the synthesis of 
lead cuprates of the 2213 or 1212 type. In a typical pro- 
cedure, a mixture of citric acid ahd ethylene glycol in 



b wncditfated'at 373 ^^O"** to f^t a #SeOUS gel 



The gd after decomporiW ^ 

pdlets in the temperature ran^ <rf 1073^1 IB K either 
in N, containing 1% Oj or in an oxygen atmosphere. 
PbiSr,Yo.,Cao.5Cu,0,*, obtained from ^ocms 
shows a sharp superconducting transition at 70 K. The 
1212 cnprate also shows a sharp transition at 60 K. 
This process is superior to the ceramic procedure for 
synthesizing superconducting lead cuprates. 

5. AHcall flux malhod 

Strong alkaKne media, other in the form <rf solid car- 
bonate fluxes, molten hydroxides or highly concentrated 
alkali solutions can be employed for the synthesis of 
higb-Tt cuprate superconductors. The alkali flux 
method lakes advantage of both the moderate tem- 
peratures of the mohea media (453-r67J lC) as wdl as of 
the add-basc diaractc«*«»« of molten bydiroxiiks to 
simultaneously predpitale oxides or oxide fwecursofS 
such as hydroxides or peroxides of the consti^ent 
metals. The method stabilizes higher oxidatfeP states of 
the metal by prov*dii« an oxidizing atinosphere. 

Employing fiised alkali hydroxides. Ham et al \7Xm 
have synthesized superconducting Laj-^MiCuO* 
(M==K or Na or vacancy) at relativehf low tem- 
peratures (470-570 K). In this method, stoidiiOmelric 
quaBtities of U,Os and QiO are added to a iftOlten 
mixture containing KOH and NaOH C"» ^ a^w- 
fanaldy 1 : 1 ratio) in a Teflon <iudWc arid heated Jrt 
around 570 K in air for fO&li. The 1:1 mi»ttffe ^ 
KOH and NaOM rtdts at 440 K and since the iffl:all 
hydroxides generally contain some watisr, the mdt is 
addic and can readily diwolve oxides sudi as UiOj 
and GuO. The Hack crystals obtait»«l feom laic reaction 
(after washing away the excess hydroxide with water) 
show a T. of 35 K. Since the reaction is carrfed out_m 
alkali hydroxides, incorporation of Na*^ or K for 
La? * in the iatticfe of lAaGwO^ cannot be rded It 
should be noted that snpereonduetiitg aflcah-doped 
LaXuO* is oorraaBy prepared at higher 
in seated gold tubes [205^. Receipitty. d*^« ^ 
bromite oxidation has been eraptoycd to 
UXuO*+, with a T. Of 44 K [ZIOJ. 

Supereonductmg YBa,Cu,0, {% ~ 88 iC)J»as m 
been prepared using the fa&tA eute<*ic of soditim ^ 
potassium hydroxides in a similar manner to that 
described above [211]. The problem of contaromaiJOB 
of alkaU metals in the preparation «f 
been overcome by using the Ba<OH), flux [2 1} The 
procedure involves heating a rt»ixt«rej»ntainlng stoi- 
chiometric amountt of Y(NOs),.6HzO, Ba^O»), and 
Cu(NO^, . 3H,0 in an open ceramic crudbl? at around 
1023 K in air for a short time (about 10 tniii) and then 
slowly cooling the melt to room temperature. Sujce 
BafOH), has two hydration states, one rodtmg at 
351 K and the other at 681 K. the lower-mdUng 
hydrate acts as the solvent for the nitrates of copper 

15 



C U n ela/ 




and yttrium while the high-mdung hydrate serves as the 
mcdiuzn for intimate mixing of the rcactanls. The pre- 
cipitate obtained from the mdt, af^er washing with 
water, is sintered in air at around 1 1 73 K followed by 
oxygenation at 773 K. This method yields an orthor- 
hombtc YBa2Cu^07 phase (with little CuO impurity) 
showing a T; of 92 K. 

The flux method diminates the need for mechanical 
grinding and introduction of carbon-containing anions^ 
whidi is <rften encountered in the «>!ution routes. Fur- 
thermore, the method is effkicnt and cost-effective. 

6. Combustion method 

Although many of IIk solution routes discussed earlier 
yield homogeneous products, the (processes Involved are 
quitfi cc»Dplex. Qmbustkm synthesis or seff^ 
propagatii^ h^gb^ten^^erature s^tbesis fSK^ first 
devd<^ped by Mctzbanov aitd Borovlti^aya [212]^ pro- 
vides a simile and rapid meatis of preparing inorganic 
materials, many <ff whidi are tecbnologieally impoitant 
Combustion s^tbcsis is based on the prindple that the 
heat energy libraated by many exothermic Don-€atal3rttc 
solid-solid or $oItd-ga$ reactions can setf*propagate 
throughout the $ample at a certain rate. Tliis process 
can theri^ore occur in a sarrow zcme whidi separates 
the sta^g substams and teactioii pfo^iK^ 

Self-propagating combustioii' has been em|^oyed 
itoeiUly in this laboratpcy to syntbe^ ijr»»nt^$ <rf 
almost an families <^ cupiate supoco&ductoi^ (eatoept 
for the thaOiuin cupratcs) [213]. The method involves 
the addition <^ an approjHiate fuel to a solution con- 
taining the metal nitrates in the proper st<»chk»ne(ry. 
The ratio of tte melal nitrates to the fuei is sudi that 
when the solution ts dried at arouiKl 423 the solid 
residue undergoes flash cooibustlon* giving an ash con- 
taining the mixture of oxides is tl» form of very fine 
partides (^jtide ^xt OJy4XS /im)L The 9$h b then given 
IP^per bc^l treatment otnler the iedipi ^trntsfp^^ to 
pbtaia the cupmte* The smtatfi partide ^ oT the ash 
&cffitates tbe re^tk^ between the metal o^i^ due to 
sm^kBer ^^U^on distances between the caticms. Fa^ 
such as urea [213, 1\4% ^ftm [213, 21^ mi tetra- 
tormd tnazine CTFTA) [2t6j are genmlly employed 
ibr synthesizing cnprate ^upercoodnctors. Ultta&ie par- 
tides d copper metal can also act as an intemal fud 
whocin the combustion is mitialed by flashing a Uiser 
beam for a short tii» [217). Seme of the cv^pMt super- 
cemduct<»rs wbidi have been p tcp aic d [2133 by this 
route include Ui^^JStJOaO^ (i; = 35 IQ, YBa,Cu,07 
(T, - 90 YBa,Cu40t (7; = » KX KiO^iCuA 
(Te-SSKX FbxSr,Yo.5Cai>^jQa (Te«60K) and 
Nd J .^Ofc^QiO^ (Te - * KjL 

i 

7, Other memods 

in addition to the various synthdk methods discussed 
thitherto, a few other n^tbods such as spray dtying 
Pl^2211 freeze drying [186^ 222, 223], use of metallic 
precursors [224. 225] and eSectrochemic^ methods 




[226^ 227] have also been employed for the preparation 
of cuprate superconductors in buft form. In spray 
drying, a solution conUtning the metallic constituents, 
usually in the form of nitrates, is sprayed in the form 
of fine droi>let$ into a hot chamber, the solvent 
ev^K^-ates instantaneotisly, leaving bdiind an 
intimate mixture of the reactants which on heating at 
the desired temperature in a suitable atmosphere yidds 
the cuprate. Some of the superconducting cuprates pre- 
pared by this method indode YBajCujO, (7; = 91 K) 
[218], YBajCu^Og (T^^SIK) [219] and 
Bi,.^Pbo.4SriCajCu30,o (T. « 101 K) [22Q, 221 J In 
freeze drying, the reactants (in a common sdvent) are 
frozen by iitunerang to liquid muogen. The solvent is 
removed at low pressures to obtain the iiutial re^itants 
in flne powder form« and these are then processed at on 
apfH-opnate lempeniture. For exami^ YBdiOi^O^ 
(7;«E7K) [IMl YBa,OuO» (T, = 79 K) [222] and 
Bit.^Pbo^Sr, jCa^CttjOyft; = !01 K> p23] tevc been 
prepared by this method. 

MietaUk j^^cursors have been used m ihe prcp^ 
aration of 123 and 247 oi^tes [22< 225). Far 
cxampk^ oxidizing an Ei^Ba-'^!^ aQoy aroimd 1170 K 
gives superconducting ErBajCu^O-, with a 7; of 87 K 
[224]. I^mtiarly YbjBa^C^Ots has been obtained l>y 
heating m afio^ <x>iiq)0;^tkm of Yb^MtjeCui fut^ 33 
wt% of stlyerV under 1 fttm imtl^MMiS % [£2i^ 

Making use of dec^UipGNrhk;^ oxidation, 
LaaOaO*^^ with a oC 44 K h«s bust jH^red at 
room tdnpeiratmer wldcii k < tfbei w ise po^^ 
use of high oxygen p^rssuKs [226,227]. 



8. Oxyoen fK>n*«toichl0metry 

Oxygen stoichiometry p&ys a oiujal role in determin- 
ing the si^ierccmductmg properties ci mzny ci the cup* 
xat^ Thus» 3toidik»nfctzk La^CnO^ is an ii^tdator» 
isdiile an ^cyg&n*exoes$ material pi^epared under hi^ 
oxygen pcessiires shows st>pero<Miduccivity with i T^ e^ 
Silt tiSi. The same holds lor tlie next merhber eC the 
hxmK^c^us fiimSy, Ia^- J^jP^^^ ""^^ ^ sq(>er* 
conducting only w&en tbw is an ojg^gea i^xo&ss [17J. 
The excess oxygen donates hiEAes in these two systons. 
In the case <rf YBa^CUsOT-j. oxygen can be easSy 
reiiM>ved givtag rise to tetti^cmal not^psupen^ndttcting 
YBajCujO^. Tte YBajCu^O^ n^tmd can be pre* 
pared \3y tiling YBa^CnaOt in an t^pm atnit^i^ere 
at 973 K for extended periods of &ne £22ff|* tbe tam- 
tioB or with dacy|)en s^crid^Ene^ is km/m 
[229» llOi, When i rcaditi 03, there is an intergrowth 
of YBaiCtosO* nnd YBa^^O, witd at this con^iosi* 

position is di^adned by qucridilng ^sfO material, 
heated in a nitrogen atmc^iere at 743 K [231], Simi* 
larly« by qncndung YBa^Du^O^ at 783 K in air, 
YBaaOijOi^T (showing a T; -^WK) is jatpared 
[231]. the t; of 90 K is found only when S^02. 
YBajCu^Oe is readily oxidized back to YBa^CUjO^, It 
may be noted that this oxidation-reduction process in 



YBa^aO^ 90 

YBajCu^Oe* 80 

BlaCaiSfaCUaOg 90 

TJCajBabCUaO*^,* 115 

TlaBdjCuOe* 90 

tljCsSajCUaO, 110 

TI,Ca;^aCu30,o 125 



Mda.^Ce.CiKD^ 30 
Ga, ^jOiOa 40-110 



Ceramic*. so<-9et. co4nbU8lk>n» «>procflpjtaik)n 
Ceramic (high 6, j^esMira)^ 
Cersmic pressura)* allifiJ Wo, hypobroiiyte* 

Cemnic (anmaRng In OJ*. scrf-^sl^, cof»recipHaikm*, 

Ceramic {hJQh pressure), ceramic (with Ne^Oa)* 

eaH7el\ copredpliaHdn* 
Geramk; {afr-K|uanch}* eoH>«**» combustion. 

m«tt b^as^ rcMe* 
Ceramic^. aoH^ ■''PMto 
Ceramic «md6d Ag/Au n^)* 
Cemmic (sealed As/Au fi^r 
Ceramte (»ealetf Ag/Au tube)* 
Ceramte ($eale<J A<^Au twbe)* 
Ceramic {sealed Ag/Au tube)* 
Cerwnic (sealed A^Au t^)* 
Ceramic (low O, partial pcosswe).* 

sd^* (low O2 ptftlal 

pressure) 
Ceramic (ftowTng O^)* 
Ceramic {low O, parttot pressure)* 
Coprec^Mlstion (low p, pafM prBSSure)* 
Ceramic (high presaoires)* 
Ceramto (Nd^ pressures}* 



* Hecgnunended methods are imffcat^d by asteri^. 

• 0^ rare-eaf^ oc^npound^ c4 Ws type are ate6 prepared ty similar memods. OkygeA anfteallns Is done betew m« 
or«MmoitdtlO'^»lrftgoi^tf >aft^^ 

^ Sr anaft»0ues or coffipeums^ wim ^Beren^ 



YBajGujO?-* is of topochemical character. The other 
a09k^gou$ larc-earth 123 cMf»ratcs also behave in iei 
S9i!|9ar way whh respect to the yariation of S wHh % 

YjB^CaiPis-, a ^tide ran^ cf pjq^cfl stoichi- 
omcay (0^^ 5 ^ 1) C2i3]. Tbc maximum 1; of 90 K is 
adde^ wlwit * is close to zero» and when ^ reaches 
nmty &e mateiia} diows a I; of 30 K ; ttorc is 00 stnic- 
tqial phast traasiticni accompanyiiig the yarktkm In 
a?tyi^ stc^ofiietry* Usually, tkHh yttrium 124 and 
247 ci^iEites and thdr rare-earth anatbgutrs, |wrepared 
by the oeramiG method under 1 ^Un oxygen pressure^ 
sfe6w j dose to imo. 

j^^tb curies of tb^ type WjCCa, Srl,», 
stre bc$t f^tcp^red ^ qucpchtng the 
smptes in air or by annea^ng In a Bilrog^ a&m)S|>he!rt 
at apia^c^^iate fcemp!?rjUiu^ £55, 234]. Hating th^ 
sam;^ in an o%f&^ tsmac^^^ k m good« possibly 
because t^ exu^a oky^eti may add oft to the l^O 
laym. In the case df fhe teadnckHM it»3 si>ember 
ittiS^ prepafti^ the samples under low partial pres- 
sures of oxygen is found to indneaie the vohimc fraction 
of the superccHiductiag |*ase [235. 2360- The n ^ I 
niMbcr, M^jCtiOe^, shows metallic behavkHir when 
ftcare is excess oxyg»i C237J By anncsafing in a redudng 
atmosf^icre <Ar or N,), the txocss oxygen can be 
rcanoved to it^\k€t superconductivity; 

Oxy^ stoichiom^y has a dramatic influence 00 
Ihe sup^conducting pr^H'iSi^tks of thalHam cupratcs {94, 
iW, 10^, For cxamjMe, ibaJllum cupf^tes of 

Ite TICa^.iBajCu^Oj^^j faro3y» derivatives of the 



TICa,,,Sr2Cu,Oi,+3 fomily and TliBajCuO^ <^ 
have exoKs oxygen when prepared in seiled tubealL By 
anneaKng these sami^ m a rediwipg aUnoafi^^ 
diuie H^^ Ni <»r v^cofmi M s^p^ppnm H i mp tt^ ^i u ^ 
the excess o^xygea is n»niaYed to isnktqs SD|cipe»»ftao 
tivtty in some cases [10«, I0?» Mac^^iEig «t lo^ 
oxygen partial pr^t^s or in a reducing fitoos^pfteie 
also fecreases the of sonm of the si^^^ndu^g 
ihalHum cupratcs to vali»^ 4carea$u^ ^ 

oxygen OHU^t 239-246]. Thf^ yamt^ are 
cleaHy related to the bole co9i^trafiG0 wheire the 
number of hoks decreases by removing excess oxy£^ 
thereby giving the o^Himal concentration required for 
maximal 7^ [247]^ 

In lead o^tes of the Pb2Sr^La, €^Cu^O»+, 
<22I3) type, mm^fl^ tltt oxygcto o^t«it it the 
material by annealing in an oxy^ &tiitt«c^JseJ* 03^1^ 
the Pb^ * and Cu* * without affeptiag the CuQi A©ets» 
governs the superpofKhictiviiy in fMs mate^ 
[243]. Though thb system shows a wide range rf 
oxygen stokfaioitietTy (assodated whh a strocta^ 
phase iransstioo from <tfUioriiombtc to temig^fos^ 
symmetryX inaximum % is observed for any gi^ com- 
petition where in S i$ close to xcro [249]. &m»pies wiOi 
d 0 arc thciefi>rc f^e^aied 1^ axmeai}faig ra a mMgeani 
almosj^re cootaimag hltk oxygen. The lead 1212 e»p- 
raics, on the other hand, are best prepared in b IU^H 
oxygen atmosphere The samples obtained aSer the 
oxygen treatment are irften n<)t supeGr?GQC»h^^ 
ihCTe is an oxyglftn cxiDCSi. The saa^to ate q[i««^ in 
air at around 1073 K in wder to aeliiw sapcrcottdu<> 
tiviiy [250]- 



17 



e N B ef «/ 



SupercotiductiAg properties of the clcctron-dopcd 
sapcrcooduciors, Nd^.^Ce^CuO*,*. arc scnsiiivc co 
the oxygen content The as-fw^red samples which arc 
semkonducting have oxygen conicni greater than four 
Samples with oxygen content kss than four arc 
obtained by annealing in a reducing atmosiAcrc fNj. 
Ar or dilute Hj) at around 1173 K. Maintaining the 
oxygen sioichiometry a( less than four b esscnltal tor 
havmg an oxidation stale of Cu less than 2+ in this 
material C25I]- 

9. Condadlng rwrtartcs 

In the earlier sections we presented deuils of the pre- 
parative methods for the synthesis of various familKS of 
cujwatc superconductors. In addition, we also examined 
the advantages airf disadvantages of the dfflereni 
iB^hods. SiiKx more than one method of synthesis has 
beea ot^<^ f<^ prcparaig any ^vcn cu^te^ it 
beG«»^ iiecBssary to make the rigirt choke irf^m^hod 
Id any giVen satuatkm. Iti order to assist in making sn0k 
a ^$oic^ we have tabulated in table 6 the hnportant 
preparative methods employed to synthesize some <rf 
the r^t«scotative cuprates, where the recommended 
i£H£tbod$ are aJ^ ix^icated. 

Acfcnowled^nent 

the atnlK^ thank the vaiiou$ sl&si^ crpedafly t^c 
National Superconductivity Research Board, Umversity 
Grants Commisaon and the US National Science 
Foandatloa for support of the research r^ated to 
cspv^tc superconductors. 



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BRIEF ATTACHMENT AC 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479,810 
Filed: June?. 1995 



Date: March 14. 2005 
Docket: YO987-074BZ 



Group Art Unit: 1751 
Examiner: M. Kopec 



For NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE. METHODS FOR THEIR USE AND PREPARATION 

Commissioner for Patents 

P.O. Box 1450 

Alexandria. VA 22313-1450 



In response to the Office Action dated July 28, 2004, please consider the 



The attachments refenred to herein A to Z and AA are in the FIRST 
SUPPLEMENTAL AMENDMENT. The Attachments AB to AG are attached herein. 

Please charge any fee necessary to enter this paper and any previous paper to 
deposit account 09-0468. 



THIRD SUPPLEMENTAL AMENDMENT 



following: 




Dr. Daniel P. Morris. Esq 
Reg. No. 32,053 
(914) 945-3217 



IBM CORPORATION 
Intellectual Property Law Depi 
P.O. Box 218 

Yorictown Heights, New York 10598 



ATTACHMENT AC 



XI 



|2i- 



51 



Si 





J2 "^t » 



I «^ ? 

ft; Sc; 



^1 



00 Oi 



?3 I 
HO 




r-j V* t** 




fflGH TEMPERATURE SUPERCONDUCTORS 
C. N. R Rao and A. K. Raychaudhuri 



The following tables give properties of a number of high temperature superconductors. Table I lists the crystal structure (space group and lattice 
constants) and the critical transition temperature T^. for the more important high temperature superconductors so for studied Table 2 gives energy gap, 
critical current density, and penetration depth in tfw superconducting state. Table 3 gives electrical and themial properties of some of these materials 
in the normal state. The tables were prepared in November 1992 and updated in November 1994. 



1. Ginsburg, D.M., Ed., Physical Properties of High-Temperature Superconductors, Vols. 1— III, Worid Scientific. Singapore, 1989—1992. 

2. Rao. C.N.R., Ed., Chemistry of High-Temperature Superconductors, Worid Scientific, Singapore, 1991. 

3. %\iSickt\iorA,}^.,TheCRC Material Science and Engineer! 1992. 98— 99 and 122— 123. 

4. l^&\&,^.,B^M<itenaisandCrystdlographicAspectsofHTc'Superc 

5. Malik, S.K. and Shah, S.S., Ed., Physical and Material Properties of High Temperature Superconductors, Nova Science Publ., Commack, 
N.Y., 1994. 

6. Chmaissem, O. et al., Physica, C230, 23 1—238, 1994. 

7. Antipov, E.V. et al, Physica, C215, 1— 10, 1993. 



REFERENCES 



Table 1 



Structural Parameters and Approximate Values of High-Temperature Superconductors 



Material 



Structure 



TJK (maximum value) 



TljCaBazCuiOg 

TljCaiBazCujOio 

TI(BaLa)Cu65 

Tl(SrU)Cu05 

aWboJSrjCuOs 

TlCaBa2Cu207 

(TlojPbo.5)CaSr2Cu207 

TlSrjYo^CaosCujO, 

TlCajBazCuiOa 

(TlojPbo^)Sr2Ca2Cuj09 

TlBa2(Lai.,Cej2Cu209 

PbzSrjLao^Cao^CujOg 

Pb2(Sr,U)2Cu206 

(Pb,Cu)Sr2{La,Ca)Cu207 

(Pb,Cu)(Sr,Eu)(Eu,Ce)Cu20, 

Nd2,,Ce^Cu04 

Cai.^r,Cu02 

Sr,.,Nd,Cu02 

Bao.6Ko.4BiOj 

RbjCsCjo 

NdBaaCujO? 



BiiCaSrjCujOs 
Bi2Ca2Sr2Cu30to 
Bi2Sr2(lJi,.,Ce,)2Cu20,o 
Tl2Ba2Cu06 



YBajCu^O, 
YBaiCu^Og 
YzBa^CuTOis 
Bi2Sr2Cu06 



La2Cu04+5 

La2.^r^Ba^jCu04 

LajCau^Sr^CujOfi 



Bmab;a = 5.355,A = 5.401,c= I3.I5A 
l4/nunm; a = 3.779. c = 13.23 A 
I4/mmm: a = 3.825. c = 19.42 A 
Pmmm; a = 3.82 1 . A = 3.885. c = 1 1 .676 A 
Ammm; a = 3.84, b = 3.87. c = 27.24 A 
Ammm; a = 3.851, 6 = 3.869. c = 50^9 A 
Amaa; a = 5.362. b = 5.374. c = 24.622 A 
Ajaa; a = 5.409. b = 5.420, c = 30,93 A 
A2aa; a = 5.39, b = 5.40. c = 37 A 
P4/mmm; a = 3.888, c = 17.28 A 
A2aa; a = 5.468, b = 5.472. c = 23.238 A; 

14/mmm; a = 3.866. c = 23.239 A 
!4/mmm; a = 3.855. c = 29.3 1 8 A 
14/mmm; a = 3.85, c = 35.9 A 
P4/mmni; a = 3.83, c = 9.55 A 
P4/mmm; a = 3.7. c = 9 A 
P4/mmm; a = 3.738. c = 9.01 A 
P4/mmm; a = 3.856. c = 12.754 A 
P4/mmm; a = 3.80, c = 12.05 A 
P4/mmm; a = 3,80, c = 12.10 A 
P4/mmm;a = 3.853.c= 15.913 A 
P4/mmm; a = 3.8 1 . c = 1 5.23 A 
I4/ramm; a 3,8, c = 29.5 A 
Cmmm; a = 5.435, b = 5.463. c = 1 5.817 A 
P22,2; a = 5.333, b = 5.421, c = 12.609 A 
P4/mmm; a = 3,820, c = 1 1 .826 A 
I4/mmra; a ^ 3.837. c = 29.01 A 
14/mmm; a = 3,95. c= 12,07 A 
P4/mmm; a = 3.902. c = 3.35 A 
P4/mmm; a = 3.942, c = 3,393 A 
Pm3m; a = 4.287 A 



39 
35 
60 
93 
80 
93 
10 
92 

no 

25 



92 
119 
128 
40 
40 
40 
103 
90 
90 
110 
120 
40 
70 
32 
50 
25 
30 
110 
40 
31 
31 
58 



a= 14.493 A 
Pmmm; a = 3.878, i> = 3.913, c = 1 1 ,753 



12-87 




BRIEF ATTACHMENT AD 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorzetal. 
Serial No.: 08/479.810 
Filed: June?, 1995 



Date: March 14. 2005 
Docket: YO987-074BZ 
Group Art Unit: 1751 
Examiner: M. Kopec 



For NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE. METHODS FOR THEIR USE AND PREPARATION 

Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



In response to the Office Action dated July 28, 2004, please consider the 



The attachments refen-ed to herein A to Z and AA are in the FIRST 
SUPPLEMENTAL AMENDMENT. The Attachments AB to AG are attached herein. 

Please charge any fee necessary to enter this paper and any previous paper to 
deposit account 09-0468. 



THIRD SUPPLEMENTAL AMENDMENT 



fdiowing: 




Dr. Daniel P. Morris, Esq 
Reg. No. 32.053 
(914) 945-3217 



IBM CORPORATION 
Intellectual Property Law Dept. 
P.O. Box 218 

YoiWown Heights. New Yori< 10598 



ATTACHMENT AD 



Theory of 
Superconductivity 



By 

M« von LAUE 

Kaiser-Wilhclm-Institut fur phystkalische und HlektroOiemie 
Berlin— Dahlem 

Translated by 

LOTHAA METER 

University of Chicago, Chicago, Illinois 

and 

WILLIAM BAM) 

The State CoU^e of Washington. Pullman, Washington 




ACADEMIC PRESS INC., PUBLISHERS 
New York, 1952 




Chapter i 



fig -so Q 



am 



am 



am 



Hi, 



Fiindamento] Facts 
(a) Superconductivity was distovered in 1911 by Kamerlingh-Onnes> 
He was the first to liquefy helium and so to produce temperatures below 
10*^ K. With this new technique he was able to observe the continued 
decrease of the electrical resistance of metals with decreasing temperature. 
With mercury, in contrast to other metals, he was astonished to find that 
the resistance completely vani^ed, almost discontinuously, at about 4.2® K 
(Fig. Today superconductivity is 

known in 18 other metals (see Table 
whereas in others, e. g.; gold and 
bismuth, the conductivity remains nor- 
mal far below even 1<* K. Many alloys 
_ aiid compounds ' can also become super- 
' conducting, in particular the frequently 
. used niobium nitride which has a tran- 
sition temperature as high as 20** K. 
However, among these latter substances 
hysteresis phenomena mentioned in the 
fev-'Tntroduction" are so much more strongly 
V evident that in testing the present theorj'^ 
we prefer to employ only the "good" 
superconductors, i. e., the pure elements, 

^ .g:. . In the ideal case the resistance vanishes 
conipletely and discontinuously at a tran- 
sition temperature T,. Actually the resi- 
stande-temperature curve does fall more 
sharply the more the specimen is like a 
single crystal and the smaller the mea- 
suring current used. ^ Because the drop 
^. always occurs in a> measurable tempera- 
-^^ture* range, the experimental definition 
of -the transition temperature is to some 
4s;extent arbitrary. The temperature at : 
: o whidi the direct-current reastance reaches one half of the value it had 
^ just before the drop is generally given as the transition temperature, because 
this can be measured accurately. However, a high-frequency investigation 
to be described in Chap. 16 (f) indicates that the foot of the curve where 



(LOSQ 



0M2S 



Fig. 1 — 1- Appearance of supercon- 
ductivity in mercury according to 
H. Kamcrlingh-Onncs (1911). The 
ordinate is the resistance R', .R^ 
the resistance of solid mercury 
extrapolated to 0* C, is 60 ohms. 



*H. Kamerlingh-Onncs, C<wnm««i. Uiden, 120b, 122h. 124f. (1911). 



BRIEF ATTACHMENT AE 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479,810 
Filed: June?, 1995 



Group Art Unit: 1751 
Examiner: M. Kopec 



Date: March 14. 2005 
Docket: YO987-074BZ 



For NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 

Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



In response to the Office Action dated July 28. 2004, please consider the 



The attachments referred to herein A to Z and AA are in the FIRST 
SUPPLEMENTAL AMENDMENT. The Attachments AS to AG are attached herein. 

Please charge any fee necessary to enter this paper and any previous paper to 
deposit account 09-0468. 



THIRD SUPPLEMENTAL AMENDMENT 



Sin 



following: 




Dr. Daniel P. Moms, Esq 
Reg. No. 32,053 
(914) 945-3217 



IBM CORPORATION 
Intellectual Property Law Dept 
P.O. Box 218 

YoiWown Heights. New Yort^ 10598 



ATTACHMENT AE 




Europllsches Patentamt 
European Patent Office 
Office europ^ des brevets 



0 Publication number; 



0 275 343 

Al 



® EUROPEAN PATENT APPLICATION 

© Application number: 87100961.9 ® int CI/ H01L 39/12 

@ Date of filing: 23.01.87 



® Date of publication of application: 
27.07.88 Bulletin 88/30 

@ Designated Contracting States: 

AT BE CH DE ES FR QR IT U LU NL SE 



® Appficant: International Business Machines 
Corporation 
Old Orchard Road 
Armonk, N.Y. 10504(US) 

@ Inventor: Bednorz, Johannes Qeorg, Or, 
Sonnenbergstrasse 47 
CH-8134 Adllswil(CH) 
Inventor: MUller, Carl Alexander, Prof.Dr.. 
Haldenstrasse 54 
CH-890d Hedfnaen(CH) 
Inventor: Takashige, MasaakI, Or, 
Rotfarbweg 1 
CH-8803 Rtischllkon(CH) 

0 Representative: Rudack, QUnter O., Olpl-lng. 
IBM Corporation SMumerstrasse 4 
CH-8803 RUschllkon(CH) 



® New superconductive compounds of the K2NIF4 structural type having a high transition 
temperature, and method foe fabricating same. 



@ The superconductive compounds are oxides of 
the general fomiula REa,«AExTM.04^ , wherein RE is 
a rare earth, AE is a member of the group of alkaline 
earths or a combinatron of at least two member of 
that group, and TM is a transitkjn metal, and wherein 
X < 0.3 and 0,1 ^ y S0.5. The method for making 
these compounds involves the steps of copredpitat- 
ing aqueous solutk^ns of the respective nitrates of 
the constituents and adding the copredpitate to ox- 
alic add. decomposing the predpitate and causing a 
2 solid-state reaction at a temperature between 500 
^and 1200'C for between one and eight hours, for- 
COming pellets of the powdered product at high pres- 
J^ure, sintering the pellets at a temperature between 
*^500 and 1000*C for between one half and three 
W hours, and subjecting the pellets to an additional 
annealing treatment at a temperature twtween 500 
and 1200'C for between one haft and five hours in a 
O protected atmosphere permitting the adjustment of 
l^the oxygen content of the final product. 
Ul 



Xerox Copy Centra 



0 275 343 



NEW SUPERCONDUCTIVE COMPOUNDS OF THE K^NIF. STRUCTURAL TYPE HAVING A HIGH TRANSITION 
TEMPERATURE, AND METHOD FOR FABRICATING SAME 



Reld of the Invention 

The invention relates to a new class of super- 
conductors, in particular to components of the 
K2NIF4 type of structure having superconductor 
properties below a relatively high transition tem- 
perature, and to a method for manufacturing those 
connpounds. 



Background of the Invention 

Superconductivity is usually defined as the 
complete loss of electrical resistance of a material /s 
at a well-defined temperature. It is known to occur 
in many materials: Alxmt a quarter of the elements 
and over 1000 alloys and components have been 
found to be superconductors. Superconductivity is 
considered a property of the metallic state of the 20 
material, in that all known superconductors are 
metallic under the conditions that cause them to 
superconduct. A few normally non-metalfic materi- 
als, for example, become superconductive under 
very high pressure, the pressure converting them 25 
to metals before they become superconductors. 

Superconductors are very attractive for the 
generation and energy-saving transport of electrical 
power over long distances, as materials for forming 
the coils of strong magnets for use in plasma and 30 
nuclear physics, in nuclear resonance medical di- 
agnosis, and in connection with the magnetic levita- 
tion of fast trains. Power generation by thermonu- 
clear fusion, for example, will require very large 
magnetic fields which can only be provided by as 
superconducting magnets. Certainly, superconduc- 
tors will also find application in computers and 
high-speed signal processing and data communica- 
tion. 

While the advantages of superconductors are 40 
quite obvious, the common disadvantage of all 
superconductive materials so far known lies in their 
very low transition temperature (usually called the 
critical temperature Tc) which is typically on the 
order of a few degrees Kelvin. The element wim 45 
the highest Tcis niobium (9^ K). and the highest 
known Tc is about 23 K for NBjGe at ambient 
pressure. 

Accordingly, most known superconductors re- 
quire liquid hefium for cooling and this, in tum. so 
requires an elaborate technology and as a matter 
of principle involves a considerable investment in 
cost and energy. 

It is, therefore, an object of the present inven- 



tion to propose compositions for high-Tc supercon- 
ductors and a manufacturing method for producing 
compounds which exhibit such a high critical tem- 
perature tfiat cooling with liquid helium is obviated 
so as to considerably reduce the cost involved and 
to save energy. 

The present invention proposes to use com- 
pounds having a layer-type structure of the kind 
known from potassium nickel fluoride K2NiFi. This 
structure is in particular present in oxides of the 
general composition RE2TM.0i, wherein RE stands 
for tiie rare earths (lanthanides) and TM stands for 
the so-called transition metals. It is a characteristic 
of tfie present invention that in tiie compounds in 
question ttie RE portion is partially substituted by 
one member of the alkaline earth group of metals, 
or by a combination of ttie members of this alkaline 
earth group, and that the oxygen content is at a 
deficit 

For example, one such compound that meets 
the description given above is lanthanum copper 
oxide La^OuOj in which tiie ianthanum -which be- 
longs to tiie IIIB group of elements-is in part substi- 
tuted by one member of tfie neighboring IIA group 
of elements, viz. by one of tiie alkaline earth metals 
(or by a combination of the memljers of the IIA 
group), e.g., by barium. Also, tfie oxygen content of 
tfie compound is incomplete such that the com- 
pound will have ttie general composition Laj. 
xBaxCu04^ . wherein x 5 0.3 and y < 0.5. 

Anotiier example for a compound meeting the 
general fonnula given above is lanthanum nickel 
oxide wherein the lanttianum is partially substituted 
by strontium, yielding ttie general formula IBz. 
KSrxNi04.y . Still another example is cerium nickel 
oxide wherein ttie cerium is partially substituted by 
calcium, resulting In Ge2.xCaxNi04.y. 

The following description will mainly refer to 
barium as a partial replacement for the lanttianum 
in a LazCuO* compound because it is ttie Ba-La- 
Cu-0 system which is. at least at present the best 
understood system of all possible. Some com- 
pounds of ttie Ba-La-Cu-0 system have been de- 
scribed by C. Michel and B. Raveau in Rev. Chim. 
Min. 21 (1984) 407. and by C. Michel. L Er-Rakho 
and B. Raveau in Mat. Res. Bull.. Vol. 20. (1985) 
667-671. They did. however, not find nor try to find, 
superconductivity. 

Experiments conducted in connection witti the 
present invention have revealed that high-Tc super- 
conductivity is present in compounds where the 
rare earth is partisdly replaced by any one or more 
of ttie other members of the same IIA group of 
elements, i.e. tiie other alkaline eartti metals. Ac- 



0 275 343 W 4 



tually, the Tc of LazCuO*^ with Sr2 is higher and is 
superconductivity-induced diamagnetism larger 
than that found with Ba^ and Ca^ . 

As a matter of fact, only a small number of 
oxides is known to exhibit superconductivity, 
among them the U-Ti-O system with onsets of 
superconductivity as high as 13,7 K. as reported by 
D.C. Johnston, H. Prakash, W.H. Zachariasen and 
R. Visvanathan in Mat. Res, Bull. 8 (1973) 777. 
Other known superconductive oxides include Nb- 
doped SrTiCb and BaPb,.K8lx03 . reported respec- 
tively by A, Saratoff and G. Binnig in Physics 108B 
(1981) 1335. and by A.W. Sleight J.L Glllson and 
F.E. Bierstedt in Solid State Commun. 17 (1976) 
27. 

The X-ray analysis conducted by Johnston et 
al. revealed the presence in their U-Ti-O system of 
three different crystallographic phases, one of 
them, with a spinel structure, showing the high 
critical temperature. The Ba-La-Cu-0 system, too. 
exhibits a number of crystallographic phases, 
namely with mixed-valent copper constituents 
which have itinerant electronic states between non- 
Jahn-Teller Cu3 and Jahn-Teiler Cu^ ions. 

This applies likewise to systems where nickel 
is used in place of copper, with Ni^ being the 
Jahn-Teller constituent and Ni^ being the non- 
Jahn-Teller constituent 

The existence of Jahn-Teller polarons is con- 
ducting crystals was postulated theoretically by 
K.H. Hoeck. H. Nickisch and H. Thomas in Helv. 
Phys. Acta 56 (1983) 237. Polarons have large 
electron-phonon interactions and. therefore, are fa- 
vorable to the occurranc© of superconductivity at 
high critical temperatures. 

Generally, the Ba-La-Cu-O system, when sub- 
jected to X-ray analysis reveales three individual 
crystallographic phases, viz. 

- a first layer-type perovsWte-iike phase, related to 
the KaNiFi structure, with the general composition 
La2.KBaKCu04^. with X^ and ySO; 

- a second, non-conducting CuO phase: and 

- a third, nearly cubic perovskite phase of the 
general composition Lai^Ba^CuOs^ which appears 
to be independent of the exact starting composi- 
tion. 

as has been reported in the paper by J.Q. Bednorz 
and K.A. MQIIer in Z. Phys. B - Condensed Matter 
64 (1986) 189-193. Of these three phases the first 
one appears to be responsible for the high-T© 
superconductivity, the critical temperature showing 
a dependence on the barium concentration in that 
phase. Ot^viously. the Ba^ substitution causes a 
mixed-valent state of Cu^ and Cu^ to preserve 
charge neutrality. It is assumed that the oxygen 
deficiency, y, is the same in the doped and un- 
doped crystallites. 

Both LazCuO* and LaCuOj are metallic conduc- 



tors at high temperatures in the absence of barium. 
Actually, both are metals like LaNi03. Despite their 
metallic character, the Ba-La-Cu-O type materials 
are ceramics, as are the other compounds of the 

5 REzTM.Oi type, and their manufacture more or less 
follows the known principles of ceramic fabrication. 
The preparation of a Ba-La-Cu-O compound, for 
example, in accordance with the present invention 
typically involves the following manufacturing 

w steps: 

• Preparing aqueous solutions of the respective 
nitrates of barium, lanthanum and copper and 
coprecipitation therof in their appropriate ratios. 

- Adding the coprecipitate to oxalic acid and for- 
15 ming an intimate mixture of the respective oxalates. 

- Decomposing the precipitate and causing a solid- 
state reaction by heating the precipitate to a tem- 
perature between 500 and 1200-C for one to eight 
hours. 

20 ' Pressing the resulting product at a pressure of 
about 4 kbar to form pellets. 
. Re-heating the pellets to a temperature between 
500 and 900*C for one half to three hours for 
sintering. 

2S It will be evident to those skilled in the art tfiat 
if the partial substitution of the lanttianum by stron- 
tium or calcium is desired, tiie particular nitrate 
thereof will have to be used in place of the barium 
nitrate of the example described above. Also, if the 

30 copper of this example is to be replaced by an- 
other transition metal, the nitrate tiiereof will obvi- 
ously have to be employed. 

Experiments have shown that the partial con- 
tents of the individual compounds in the starting 

35 composition play an important role in tiie formation 
of the phases present in the final product. While, as 
mentioned above, tiie final Ba-La-Cu-O system ob- 
tained generally contains the said three phases, 
witti the second phase being present only to a very 

40 small amount, the partial substitution of lanthanum 
by strontium or calcium (and perhaps beryllium) 
will result in only one phase existing in the final 
Laa-xSr^CuOi^ or l^-xCaxCuO*^, respectively, pro- 
vided X < 0.3. 

45 With a ratio of 1:1 for the respective (Ba, La) 
and Cu contents, one may expect tine said tiiree 
phases to occur in the final product. Setting aside 
tiie said second phase, i.e. the CuO phase, whose 
amount is negligible, the relative volume amounts 

50 of tiie otiier two phases are dependent on the 
barium contents in the La2.xBaxCu04^ complex. At 
me 1:1 ratio and with an x = 0.02, the onset of a 
localization transition is observed, i.e.. the resistiv- 
ity increases with decreasing temperature, and 

55 there is no superconductivity, i 

With x = 0.1 at the same 1:1 ratio, there is a 
resistivity drop at ttie very high critical temperature 
of 35 K. 



3 



0 275 343 



With a (BaXa) versus Cu ratio of 2:1 in the 
starting composition, the composition of the 
LasCuOAiBa phase, which was assumed to be re- 
sponsible for the serconductivity. is imitated, with 
the result that now only two phases are present, 
the CuO phase not existing. With a barium content 
of X = 0.15. the resistivity drop occurs at Tc = 26 
K. 

The method for preparing the Ba-La-Cu-0 
complex involves two heat treatments for the 
precipitate at an elevated temperature for several 
hours. In the experiments carried out in connection 
with the present invention it was found that best 
results were obtained at SOO^C for a decomposition 
and reaction period of 5 hours, and again at 900'C 
for a sintering period of one hour. These values 
apply to a ratio 1:1 composition as well as to a 2:1 
composition. 

For the ratio 2:1 composition, a somewhat 
higher temperature is permissible owing to the 
melting point of the composition being higher in the 
absence of excess copper oxide. Yet it is not 
possible by high-temperature treatment to obtain a 
one-phase compound. 

Measurements of the dc conductivity were con- 
ducted between 300 and 42 K. For barium-doped 
samples, for example, with x < 0.3, at current 
densities of 0.5 A/cm^. a high-temperature metallic 
behavior with an increase in resistivity at low tem- 
peratures was found. At still lower temperatures, a 
sharp drop in resistivity (>90%) occurred which for 
higher current densities became partially sup- 
pressed. This characteristic drop was studied as a 
function of the annealing conditions, i.e. tempera- 
ture and oxygen partial pressure. For samples an- 
nealed in air. the transition from itinerant to lo- 
calized behavior was not found to be very pro- 
nounced, annealing in a slightly reducing atmo- 
sphere, however, led to an increase in resistivity 
and a more pronounced localization effect At the 
same time, the onset of the resistivity drop was 
shifted towards higher values of the critical tem- 
perature. Longer annealing times, however, com- 
pletely destroy the superconductivity. 

Cooling the samples from room temperature, 
the resistivity data first show a metal-like decrease. 
At low temperatures, a change to an increase oc- 
curs in the case of Ca compounds and for the Ba- 
substituted samples. This increase is followed by a 
resistivity drop, showing the onset of superconduc- 
tivity at 2Zt2 K and 33±2 K for the Ca and Ba 
compounds, respectively. In the Sr compound, the 
resistivity remains metallic down to the resistivity 
drop at 40tl K. The presence of localization ef- 
fects, however, depends strongly on alkaline-earth 
ion concentration and sample preparation, that is to 
say, annealing conditions and also on the density 
which have to be optimized. All samples with low 



concentrations of Ca. Sr, and Ba show a strong 
tendency to localization before the resistivity drop 
occur. 

Apparently, the onset of the superconductivity. 

5 i.e the value of the critical temperature Tc, is de- 
pendent among other parameters, on the oxygen 
content of the final compound. It seems that a 
certain oxygen deficiency is necessary for the ma- 
terial to have a high-Tc behavior. In accordance 

10 with the present invention, the method described 
afcxDve for making the La2Cu04:Ba complex is com- 
plemented by an annealing step during which the 
oxygen content of the final product can be ad- 
justed. Of course, what was said in connection with 

1$ the formation of the La2CuOd:Ba compound, like- 
wise applies to other compounds of the general 
formula REzTM.OirAE. such as. e.g. NdaNiOicSr. 

In the cases where a heat treatment for de- 
composition and reaction and/or for sintering was 

20 performed at a relatively k>w temperature, i.e. at no 
more than 950**C, the final product is subjected to 
an annealing step at about 900"C for about one 
hour in a reducing atmosphere. It is assumed tiiat 
tiie net effect of ttiis annealing step is a removal of 

25 oxygen atoms from certain locations in the matrix 
of tfie RE2TM.O4 complex, thus creating a distortion 
in its crystalline structure. The O2 partial pressure 
for annealing in tiiis case may be between 10 ^ 
and 105 bar. 

30 In those cases where a relatively high tempera- 
ture (i.e. above 950 'C) was employed for the heat 
treatment, it might be advantageous to perform the 
annealing step in a slightly oxidizing atmosphere. 
This would make up for an assumed exaggerated 

35 removal of oxygen atoms from the system owing to 
the high temperature and resulting in a too severe 
distortion of tfie system's crystalline structure. 

Resistivity and susceptibility measurements, as 
a function of temperature, of Sr^ and Ca^ -doped 

40 La2Cu04.y ceramics show the same general ten- 
dency as the Ba? -doped samples: A drop in re- 
sistivity p(T). and a crossover to diamagnetism at a 
slightiy tower temperature. The samples containing 
Sr2 actually yielded a higher onset than those 

45 containing Ba^ and Ca^ . Furtiiermore, tfie dia- 
magnetic susceptibility is about Uiree times as 
large as for the Ba samples. As the ionic radius of 
Sr2 nearly matches tfie one of La^ . it seems that 
tiie size effect does not cause the occurrence of 

50 superconductivity. On tiie conti^. it is ratiier ad- 
verse, as tiie data on Ba^ and Ca^ indicate. 

The highest Tc s for each of tiie dopant ions 
investigated occur for those concentrations where, 
at room temperature, ttie Re2.xTMx04-y structure is 

55 close to the orthortiombic-tetragonal structural 
phase transition which may be related to the sub- 
stantial electron-phonon interaction enhanced by 
ttie substitution. The alkaline-earth substitution of 



4 



027S343 



the rare earth metal is clearly important and quite 
likely creates TM ions with no Sg Jahn-Teller or- 
bitais. Therefore, the absence of these J.-T. or- 
bitals, that is, J.-T. holes near the Fermi energy 
probably plays an important role for the Tc en- 
hancement 



Claims 

1 ) Superconductive compound of the REaTM.Oi 
type having a transition temperature above 28 K, 
wherein the rare earth (RE) is partially substituted 
by one or more members of the alkaline earth 
groups of elements (AE). and wherein the oxygen 
content is adjusted such that the resulting crystal 
structure is distorted and comprises a phase of the 
general composition RE2.«AEkTM.04^ . wherein TM 
represents a transition metal, and x < 0.3 dnd y < 
0.5. 

2) Compound in accordance with claim 1, 
wherein the rare earth (RE) is lanthanum and the 
transition metal (TM) is copper. 

3) Compound in accordar^ce with claim 1, 
wherein the rare earth is cerium and the transition 
metal is nickel. 

4) Compound in accordance with claim 1. 
wherein the rare earth is lanthanum and the transi- 
tion metal is nickel. 

5) Compound in accordance with claim 1. 
wherein bex\um is used as a partial substitute for 
the rare earth, with x < 0.3 and 0.1 2 y 2 0.5. 

6) Compound in accordance with claim 1. 
wherein calcium is used as a partial substitute for 
the rare earth, with x < 0.3 and 0.1 ^ y ^ 0.5. 

7) (impound in accordance with claim 1. 
wherein strontium is used as a partial substitute for 
the rare earth, with x < 0.3 and 0.1 i y S 0.5. 

8) Compound in accordance with claim 1, 
wherein the rare earth is lanthanum Bn6 the transi- 
tion metal is chromium. 

9) Cksmpound is accordance with claim 1, 
wherein the rare earth is neodymium and the tran- 
sition metal is copper. 

10) Method for making superconductive com- 
pounds of the RE2TM.O4 type, with RE being a rare 
earth, TM being a transition metal, the compounds 
having a transition temperature above 26 K, com- 
prising the steps of: 

- preparing aqueous solutions of the nitrates of the 
rare earth and transition metal constituents and of 
one or more of the alkaline earth metals and 
coprecipitation thereof in their appropriate ratios; 

- adding the coprecipitate to oxalic acid and for- 
ming an intimate mixture of tiie respective oxalates: 
• decomposing tiie precipitate and causing a solid- 
state reaction by heating the precipitate to a tem- 
perature between 500 and 1200'*C for a period of 



time t>etween one and eight hours: 

• allowing the resultant powder product to cool: 

- pressing the powder at a pressure of between 2 
and 10 kt)ar to form pellets; 

5 - re-adjusting the temperature of ttie pellets to a 
value between 500 and 1000"C for a period of time 
t)etween one half and tiiree hours for sintering; 

- subjecting the pellets to an additional annealing 
treatment at a temperature between 500 and 

10 1200*C for a period of time between one half and 
5 hours in a protected atmosphere pennitting the 
adjustment of the oxygen content of tiie final prod- 
uct which has a final composition of the form REj. 
kTM.04^, wherein x < 0.3 and 0.1 < y < 0.5. 

IS 11) Method in accordance with claim 10. 
wherein tt)e protected atmosphere is pure oxygen. 

12) Method in accordance with claim 10. 
wherein the protected atmosphere is a reducing 
atmosphere with an oxygen partial pressure be- 

20 tween 10 ' and 10 ^ bar. 

13) Mettiod in accordance with claim 10. 
wherein the decomposition step is performed at a 
temperature of 900 "0 for 5 hours, and wherein the 
annealing step is performed at a temperature of 

25 900* C for one hour in a reducing atmosphere with 
an oxygen partial pressure between 10 ^ and 10^ 
bar. 

14) Mettiod in accordance with claim 10. 
wherein lanthanum is used as the rare eartin and 

30 copper is used as tiie transition metal, and wherein 
barium is used to partially substitute for tiie ian- 
ttianum. with x < 0.2. wherein tiie decomposition 
step is performed at a temperature of 900'C for 5 
hours, and wherein the annealing step is performed 

35 in a reducing atmosphere with an oxygen partial 
pressure on the order of 10^ bar and at a tem- 
perature of 900**C for one hour. 

15) Mettwd in accordance with claim 10. 
wherein lanthanum is used as tiie rare earth and 

40 nickel is used as the transition metal, and wherein 
barium is used to partially substitute for tiie lan- 
tiianum, with x < 0.2. wherein tiie decomposition 
•step is performed at a temperature of 900 'C for 5 
hours, and wherein tiie annealing step is performed 

45 in a reducing atmosphere witti an oxygen partial 
pressure on the order of 10 ^ bar and at a tem- 
perature of 900^0 for one hour. 

16) Method in accordance witti claim 10. 
wherein lanttianurh is used as tiie rare eartfi and 

50 copper Is used as the transition metal, and wherein 
calcium is used to partially substitute for ttie lan- 
thanum, with X < 02. wherein tiie decomposition 
step is performed at a temperature of 900" C for 5 
hours, and wherein tiie annealing step is performed 

55 in a reducing atmosphere witti an oxygen partial 
pressure on tiie order of 10 ^ bar and at a tem- 
perature of 900'C for one hour. 



5 



0 275 343 



17) Method in accordance with clainr^ 10. 
wherein lanthanum is used as the rare earth and 
copper is used as the transition metal, and wherein 
strontium is used to partially substitute for the 
lanthanum, with x < 0.2, wherein the decomposition 5 
step is perfonmed at a temperature of 900*'C for 5 
hours, and wherein the annealing step is performed 

in a reducing atmosphere with an oxygen partial 
pressure on the order of 10^ bar and at a tem« 
perature of 900'C for one hour. io 

18) Method in accordance with claim 10, 
wherein cerium is used as the rare earth and nickel 
is used as the transition metal and wherein t>arium 
is used to partially substitute for the cerium, with x 

< 0.2. wherein the decomposition step is per- rs 
formed at a temperature of 900°C for 5 hours, and 
wherein the annealing step is performed in a re- 
ducing atmosphere with an oxygen partial pressure 
on the order of 10 ^ bar and at a temperature of 
900 * C for one hour.. 20 



75 



30 



35 



40 



45 



50 



55 



6 



BRIEF ATTACHMENT AF 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479.810 
Filed: June?, 1995 



Group Art Unit: 1751 
Examiner: M. Kopec 



Date: March 14, 2005 
Docket: YO987-074BZ 



For NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 

Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



In response to the Office Action dated July 28, 2004, please consider the 



The attachments referred to herein A to Z and AA are in the FIRST 
SUPPLEMENTAL AMENDMENT. The Attachments AB to AG are attached herein. 

Please charge any fee necessary to enter this paper and any previous paper to 
deposit account 09-0468. 



THIRD SUPPLEMENTAL AMENDMENT 



Sir 



following: 




Dr. Daniel P. Morris, Esq 
Reg. No. 32,053 
(914) 945-3217 



IBM CORPORATION 
Intellectual Property Law Dept. 
P.O. Box 218 

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ATTACHMENT AF 



COPPER OXIDE 
SUPERCONDUCTORS 



Charles P. Poole, Jr. 
TimirDatta 
Horacio A. Farach 



H'ilh help from 

M. M. Rigney 
C. R. Sanders 

Department of Physics and Astronomy 
University of South Carolina 
Columbia, South Carolina 




WILEY 

A Wilcy-Interscience Publkalion 
JOHN WILEY & SONS 

New York • Chichester • Brisbane • Toronto • Singapore 




Copyright © 1988 by John Wiley & Sons. Inc. ^ 

All rights reserved. Published simultaneously in Canada. [ 

Reproduction or translation of any pan of this work t 

beyond that permitted by Section 107 or 108 of the V 

1976 United States Copyright Act without the permission * 
of the copyright owner is unlawful. Requests for 

permission or further information should be addressed to ^ 

the Permissions Depanmeni, John Wiley & Sons Inc ^ 

d 

Lsbrao^ oj Congress Cataloging in Puhtication Data: a 
Poole. Charles P. 

Copper oxide superconductors / Charles P. Poole, Jr.. Timir Da.ia ci 
and Horacio A. Farach: with help from M. M. Rigncv and C. H. Sanders r 
p- cm. ^ 

e; 

"A Wilcy-Inicrscicncc publication." 

Bibliography: p. 1 
Includes index. 

W 

I- Copper oxide superconductors. I. Datia. Timir. 11. Farach " 
Horacio A. 111. Title. 

OC6U.98.C64P66 1988 

539.6 ' 23-dc 1 9 88-1 8569 C J P N< 
ISBN 0-471-62342-3 pj 

Printed in the United States of America 

10 9 8 7 6 5 4 3 2 I 



2_ 



METHODS OF PREPARATION 61 



CuO 



iSrCaCu07-6 (a) 
luminum-doped 
iple calcined at 
and ig) calcined 



the same tem- 

the early work 
I out with thin 
paration tech- 
ich samples, 
n, and others 
:entative tech- 

•ulk supercon- 
h as thin films 
ys of checking 
or subsolidus 
Fig. V-2 con- 
l-point oxides 
^(Ba3Cu04), 
)7), along the 
ig green phase 
n the interior 
urth, Kuzzz, 
). Compounds 
workers. The 
so), and then 



BaO 




YzCuzOs 



Ba3Y409 BaY204 



YOii 



Compound 


Slowly cooled 




lo room temperature 


123- YBaaCuaOe^+i 


O7 


143- YBa4Cu308i+6 


O9 


385- Y3BaeCu50,7.5+4 


O18 


152- YBasCuzOas+i 


Os 


211 - YzBaCuOs 




Ba2Cu03+4 


O33 



Fig. V-2, Ternary phase diagram of the YjOa-BaO-CuO system at 950**C. The green 
phase [YjBaCuOs, (211)] the superconducting phase [YBaiCujO;.*, (123)], and three 
other compounds are shown in the interior of the diagram (DeLee). 



B. IVIETHODS OF PREPARATION 

In this section three methods of preparation will be described, namely, the solid 
state, the coprecipitation. and the sol-gel techniques (Hatfi). The widely used 
solid-state technique permits off-the-shelf chemicals to be directly calcined into 
superconductors, and it requires little familiarity with the subtle physicochemi- 
cal processes involved in the transformation of a mixture of compounds into a 
superconductor. The coprecipitation technique mixes the constituents on an 
atomic scale and forms fine powders, but it requires careful control of the pH 
and some familiarity with analytical chemistry. The sol-gel procedure requires 
more competence in analytical procedures. 

In the solid-state reaction technique one starts with oxygen-rich compounds 
of the desired components such as oxides, nitrates, or carbonates of Ba, Bi, La, 
Sr, Tl, Y, or other elements. Sometimes nitrates are formed first by dissolving 
oxides in nitric acid and decomposing the solution at 500°C before calcination 



8 



a 



62 



PREPARATION AND CHARACTERIZATION OF SAMPLES 



been dried, cilS tagc^ nThTsot /, f """"""'^ "^^ 

vantage of (his method a. ""^f"'"'-'""'' procedure. A dkad- 

tfct is concerTerL Sfat it ' ™, " "l' « """^ri* 

teed ,or vVTor::,McLaf Httfll ""^ P'" 

900-C for 15 hr. During this taTthrvRfr rT "O""" 

8«n Y,BaCuO. phas! fo e da^t gr! YBa Cu ' "i^r 

:S:^tr;;rert;erx~^^^^^^^^^^^ 

0«en,a..hL.,^.hrr-^f~-^^^^^ 



conducting 
sintered foi 
at -3^C/r 
perature is 
conductor i 
quenching, 
sand blasti 
another ox; 
serve the si 
An exan 
metric amo 
ing them in 
dares sever 
same temp 
shows the 
curve. 

WARNINi 

precaution: 
the high-qt 
ides in air • 
powdered, 
utes in flow 
perature fS 

Alien 
mat ion on 
Pharmacol 
antidote fe 
cusses case 



C. ADDIl 

This sectio 
the prepar; 

In one t 
were calcin 
compressic 
(Graha). I 
llOO^C SI 
for YBa* a 
distinct frc 

Anothei 
or Yb. Ba 
tained sub 



ADDITIONAL COMMENTS ON PREPARATION 63 



:ired atomic 
)cess. Then 
xtended pe- 
be repeated 
material at 
The process 
wn to room 
ntering in a 
ass, but for 
erial pellet- 
lid-state re- 
iki, Hatan, 
)epp, Polle, 
Vuzz3). 
employed a 
the desired 
; extruding, 

calcination 
;ela, Bedno, 
n an atomic 
formity can 
cipitate has 
re. A disad- 
erials scien- 
rocedures. 
al technique 
Cu, and Y 
ire gelled by 
:ts the nitric 
IS been per- 

ination pro- 
stle or a ball 
or materials 
:. Care must 
chemicals to 

.g., Gran2). 
/gen around 
lor from the 
d. Then the 
its purity. If 
: is repeated, 
ly it is semi- 



conducting or even nonconducting. After pelletizing at >10^ psi the pellet is 
sintered for several hours at =900°C in flowing oxygen and then slowly cooled 
at -3°C/min down to room temperature. Slow cooling from the elevated tem- 
perature is important for producing the low-temperature orthorhombic super- 
conductor phase. The tetragonal nonsuperconducting phase may be obtained by 
quenching The pellet may be used as is or it may be cut into suitable sizes by 
sand blasting, with a diamond saw, or with an arc. After vigorous machmmg 
another oxygen anneal (450°C, 1 hr, slow cool down) is often required to pre- 
serve the superconducting properties. 

An example of preparing a Bi-based superconductor involves mixing gravi- 
metric amounts of high-purity BhO„ SvCO,, C^CO,, and CuO powders, calcin- 
ing them in air at 750-890°C, regrinding them, and then repeating these proce, 
dures several times. Then pellets of the calcined product were sintered at the 
same temperature and quenched to room temperature (ChuzS). Figure V-1 
shows the effect of sample treatment on the resistance versus temperature 
curve. 

WARNING- As was mentioned above, thallium is a toxic material and proper 
precautions must be taken when working with it. It is useful to start by preparing 
the high-quality precursor compound BaCujO, or Ba/:u30s by reactmg the ox- 
ides in air at 925''C for 24 hr. Then appropriate amounts of TI2O3 are added, 
powdered, and pelletized. The pellet is then heated to 880-910° C for a few min- 
utes inflowing oxygen, and at the onset of melting it is quenched to room tem- 

Allen Hermann has suggested consulting the following references for infor- 
mation on thallium poisoning and antidotes thereto: H. Heydlanf. Euro. J. 
Pharmacol 6 340 (1969). which discusses thallium poisoning and describes the 
antidote ferric cyanoferrate. and Int. J. Pharmacol. 10. / (1974). which dis- 
cusses cases of thallium intoxication treated with Prussian Blue. 



C. ADDITIONAL COMMENTS ON PREPARATION 

This section will treat some additional methods which have been employed for 
the preparation of samples. . * 

In one experiment coprecipitated nitrates of La. Sr. Cu, and Na carbonate 
were calcined for 2 hr at 825°C, pressed into pellets, and then subjected to shock 
compression of = 20 GPa at an estimated peak temperature of =1000 C 
(Graha). The best superconductivity was observed after 1 hr of air exposure at 
1100°C. Shock compression fabrication has also been reported (Murrz, Murrl) 
for YBa* and other rare-earth derivatives. This process produced "monoliths, 
distinct from the usual composites. 

Another technique involved the formation of a precursor alloy of Eu, Ba. Ui 
or Yb, Ba, Cu by rapid solidification, with the superconducting materials ob- 
tained subsequently by oxidation (Halda). A novel method involved preparing 



M 

i 

I 

5 

s 



64 PREPARATION AND CHARACTERIZATION OF SAMPLES 



the superconductors from molten Ba-Cu oxides and solid rare-earth-containing 
materials. In principle this process may be better controlled and complicated 
shapes can be molded or cast (Herma). 

Pulsed current densities of 300-400 A /cm^ with rise times of 0.6 ^sec at room 
temperature were used to convert the weakly semiconducting phase of YBaCuO 
to the stable metallic phase (Djure, Djurl). 

A claim was made that thermal cycling from cryogenic temperatures to 240 K 
raised the of YBa* and YBaCuO-F (with some F substituting for O) to 159 K. 
Cycling above 140 K lowered T^. This cycling process could possibly change the 
density of twins and thereby enhance T^, 

A freeze-drying technique was reported as producing sintered materials ho- 
mogeneous in composition and small in porosity (Stras). The low-temperature 
firing of oxalates {T < 780°C) has also been reported as producing a homogene- 
ous material of small grain size (Manth). 

Both Bi and Pb act as fluxes during the sintering process (Kilco). Bismuth 
substitution appears to reduce the normal state resistivity by about an order of 
magnitude without affecting the superconducting properties. 

A convenient method of separating the superconducting particles from a pow- 
dered mixture using magnetic levitation has been reported (Barso). This may be 
used to select the superconducting fraction after each calcination process. 

D. FILMS 

The new ceramic oxide superconductors presently lack mechanical properties 
such as ductility which are needed for high-current applications like magnet wire 
fabrication (Jinzz-Jinz3) and power transmission. To circumvent some of these 
deficiencies for microelectronic applications one can prepare thin films on suit- 
able substrates. Some devices such as Josephson junctions require thin super- 
conducting films. Many workers have discussed the preparation and properties 
of LaSrCuO- (e.g., Adach, Delim, Kawas, Koinu, Matsu, Nagat, Naito, Teral) 
and YBaCuO- (e.g., Burbi, Charz, Evett, Gurvi, Hause, Hongz, Inamz, Kwozz, 
Kwozl, Manki, Scheu, Somek. Wuzz4) type films. 

Almost every conceivable thin-film deposition technique such as electron 
beam evaporation, molecular beam epitaxy, sputtering, magnetron, laser abla- 
tion, screening, and spraying has been tried with the copper oxide system. Some 
of these techniques require expensive, elaborate apparatus, although descrip- 
tions of simple thin-film deposition systems are also available (e.g., see Koinl). 
Some representative examples of deposition procedures will be discussed. 

Epitaxial films of YBajCujOy-^ on (100) SrTiOs were produced using three 
separate electron beam sources (e.g., Chaud, Chaul, Laibo). The deposition 
was done in lO-^'-lO"^ torr O2 with a substrate temperature of 400*^0. The de- 
posited films were atomically amorphous with a broad X-ray peak. The epitaxial 
ordering was achieved upon annealing in O2 at 900°C with the orthorhombic c 
axis essentially perpendicular to the plane. 



High-quality 
beam to evapori 
torr (Hammo, C 
ited film in oxyg 
TSO'^C for 1 hr, 
furnace. 

Superconduc 
rangement (Ma 
was Ar or an Ar 
10"^ torr and, v 
Zr02-9% Y2O3 
films. The film? 
gen annealing. ! 
erties dependec 
conditions, con 
Films of dys] 
beam epitaxy (1 
cess was monitc 
copper was ino 
amorphous Ba ; 
high-temperatt 
Films of Y,. 
ness of 500 A 
ited on SrTiOj 
pellet of YBaCi 
The evaporatio 
6 Hz, =^30 ns€ 
heated to 450*^* 
they appeared ; 
oxygen anneak 
hours. Standai 
perconductivit; 
tivity achieved 
LaSr* (Moorj) 
Films were • 
and Cu in lay 
200'*C and 10 
layers to diffu; 
ducting compc 
conductivity v, 
Y2O3, and Ba< 
Some 5000- 
vacuum dc-m 
was 0.2 A /set 
strate distanc* 



^^^^^^^^ 



FILMS 65 



rth-containing 
d complicated 

.6 /isec at room 
iseof YBaCuO 

atures to 240 K 
or O) to 159 K. 
ibly change the 

i materials ho- 
iw-temperature 
ig a homogene- 

:ilco). Bismuth 
out an order of 

:lesfromapow- 
o). This may be 
m process. 



nical properties 
ike magnet wire 
it some of these 
in films on suit- 
uire thin super- 
1 and properties 
t, Naito, Teral) 
Inamz, Kwozz, 

uch as electron 
tron, laser abla- 
de system. Some 
though descrip- 
;.g., see Koinl). 
discussed, 
iced using three 
The deposition 
400°C. The de- 
ik. The epitaxial 
orthorhombic c 



High-quality superconducting films were obtained using a multiple electron 
beam to evaporate metallic sources in a flow of molecular oxygen at 4-5 X 10 
torr (Hammo, Ohzzz). The deposition rate was 10 A/sec. To annealthe depos- 
ited film in oxygen it was heated for 3-6 hr in a flow of oxygen at 650 C, raised to 
750°C for 1 hr, then to 850°C for 1 hr, and finally slowly cooled down in the 

'"'su^i^rconducting films were prepared using a double ion beam sputtering ar- 
rangement (Madak). The target beam was Ar at 40 mA. and the substrate beam 
was Ar or an Ar-Oj mixture at 10-500 eV and 2 mA. The base pressure was 5 X 
10-' torr and. with the gas. 4 X 10"" torr. The best substrate materials such as 
Zr02-9% Y2O3 did not appreciably interact, diffuse, or change the deposited 
films The films were - 1 iim thick and were rendered superconductmg by oxy- 
gen annealing. Zero resistance was attained at 88 K. The superconducting prop- 
erties depended upon the ion beam energy, substrate temperature, annealing 
conditions, composition, and the extent of poisoning from the substrate 

Films of dysprosium barium copper oxide were grown (Webbz) by molecular 
beam epitaxy (MBE) using a Varian 360 MBE system, and the nudeation pro- 
cess was monitored by reflection high-energy electron diffraction (RHEED). The 
copper was incompletely oxidized in metallic microcrystals growing in a sea of 
amorphous Ba and Dy . After deposition superconducting films were obtained by 
high-temperature oxygen annealing. , . . , u 

Films of Y, ,Ba, sCuaO.., approximately 3300 A thick with a surface rough- 
ness of 500 A were prepared (Dijkk, Inamz, Wuzz4). These films were depos^ 
ited on SrTi03, sapphire, and vitron carbon by evaporation ^om a single bulk 
pellet of YBaCuO 1 cm diameter and 0.2 cm thick at a pressure of 5 X 10 torr. 
The evaporation was produced by several thousand pulses of laser irradiation (3- 
6 Hz -30 nsec width, 1 J/pulse, 2 J/cm^). For best results the substrate was 
heated to 450°C. As deposited thin films were well bonded to the substrate and 
they appeared shiny dark brown and were electrically insulating. The films were 
oxygen annealed at 900°C for 1 hr and then slowly cooled over a period of several 
hours, standard four-probe resistivity measurements indicated the onset of su- 
perconductivity around 95 K and, for a (100) SrTiOa substrate, with zero resis- 
tivity achieved near 85 K. The laser ablation technique was also employed for 
USr* (Moorj) and YBa« (Naral). v u r» 

Films were obtained from sandwiched multilayers by depositing Y2O3. Bau, 
and Cu in layers (Nasta. Tsaur) on ZrOz. MgO, and sapphire substrates at 
200'>C and 10"* torr. Oxygen treatment for 1-2 hr at «850°C permitted the 
layers to diffuse, homogenize, and oxygenate, and thereby form the supercon- 
ducting compound (Baozz). Films on Ni have also been reported in which super- 
conductivity was obtained by a diffusion process involving the Cu substrate, 
Y2O3. and BaC03 composite (Tachi). 

Some 5000- A thick films of YBaCuO have been deposited using an ultrahigh 
vacuum dc-magnetron getter-sputter deposition system. The deposition rate 
was 0.2 A /sec. the substrate temperature was 1050°C. and the target-to-sub- 
strate distance was 12 cm. The scattering was done in an Ar-Oj atmosphere. 



66 



PREPARATION AND CHARACTERIZATION OF SAMPLES 



The x-ray and electron microscope examinations indicated some variation 
among the substrates arranged on the heater. Inhomogeneities were observed 
even within the film made on a single substrate. As deposited the films were 
oxygen deficient, and annealing produced suitable compositions. The reversible 
oxygen incorporation was monitored by the systematic splitting of the strongest 
X-ray peaks. The oxygen diffusion coefficient at eOO^C was 10" 's mVsec and the 
activation energies for desorption and absorption were 1.1 and 1 7 eV respec 
S/p ^'^^^"^ temperature was 99 K with complete superconduction 
at 40 K. Exposure to water inhibited the superconductor (Barns, Kishi, Yanzz) 
A device structure with a Y^Oj barrier has also been studied (Blami) 

Another work showed that films produced by dc magnetron sputtering are 
copperdeficent if the substrate-to-target distance is large or if the substrate is at 
an elevated temperature (Leez5). 

Superconducting YBaCuO thin films with a large surface area ( = 5 cm X 
5 cm) were grown on AhO„ sapphire, and MgO up to a 500°C substrate temper- 
ature by magnetron and diode techniques. Rutherford back scattering (RBS) 
indicated a uniform composition across magnetron-deposited film areas with di- 
ameters up to 5 cm, and the diode film composition homogeneity was even bet- 
ter but over a smaller area («2.5 cm diameter). The as-deposited films were 
annealed in oxygen at different temperatures and exposure times. Prolonged 
high-temperature annealing (>850°C) increased the impurity phase. The high- 
rii n k ^ ""l '^"^^ °' composition, with the maximum film copper 
.1 ; I .^o^ ^" '^'''""'^y °' YBa* thin films a rapid heat- 

ing to about 900°C in flowing helium followed by slow cool down in flowing oxy- 
gen was recommended (David). ^ ^ 
The post-deposition anneal cycle was avoided by producing the films in a 

Shrrr'^rr?"" "^^P^^""^" P'^^^^ ^"volving rapid thermal annealing 
(Lathr). Smooth films were obtained on zirconia and SrTiO, substrates. Screen 
printing of oxide superconducting films is also possible (Budha, Fuzzl) and 
simple spray deposition has been reported (Gupta). Films have also been made 
ZZ aqueous-alcoholic 

(Ric^l 1 r'*'' f ^^^^P'^' --tic acid 

(R eel), and sol-gels (Kraml) have all been reported. These processes are poten- 
tially important for commercial superconducting coatings on silicon (Kraml) 

(Gu^a'T ') '^^'^^ ^"P*^>' - MgO 



E. SINGLE CRYSTALS 



best way to u 
crystals. Unl 
anisotropy a 
twinning pro 
gle crystals. 

A numbe 
X-ray diffra< 
(e.g., Crabt, 
and micro- R 
scribe how s 
Crystal Gray 
Millimete 
oxide flux ( 
Taka4. Zhoi 
contaminatit 
a hot press ( 
(Satoz). 

Small sinj 
der which w 
sphere and 1 
tare also pre 
melting a st 
followed by 
A gold cr 
(1X2X0. 
was heated i 
400°Cat25' 
on the surfa 
the crucible 
A detailei 
crystal by th 
1:3 and 2:t 
multistep te 
found at tht 
crucibles. P 
crucibles wt 
ported. A s 
DyBa* as Is 



larllll P'^'P^'^'Z^^''^^ superconductors are averages over components 
Lmn e P^'^^"''^"'^'" '"^^ ^""^ P'anes. In addition, for orthorhombic 
samples there is an averaging over properties that differ for the a and b direc- 
hons in this plane. This in-plane anisotropy is especially pronounced for the 
YBa* 123 structure in which the Cu-O-Gu-O chains lie along the b axis The 



F. ALIGNI 

Clearly higl 
of siipercon 



ALIGNED GRAINS 67 



some variation 
: were observed 

the films were 
. The reversible 
of the strongest 

m^/ sec and the 
1.7 eV, respec- 
aperconduction 

Kishi, Yanzz). 
lami). 

I sputtering are 
e substrate is at 

rea ( ^ 5 cm X 
bstrate temper- 
:attering (RBS) 
m areas with di- 
:y was even bet- 
;ited films were 
mes. Prolonged 
hase. The high- 
I Tc film copper 
ns a rapid heat- 
i in flowing oxy- 

\ the films in a 
rmal annealing 
Dstrates. Screen 
la, Fuzzl), and 
also been made 
leous-alcoholic 
ilute acetic acid 
esses are poten- 
ilicon (Kraml), 
i), and on MgO 



best way to understand these materials is through experiments on perfect single 
crystals. Unfortunately, untwinned YBa* crystals are not available so the a,b 
anisotropy cannot be resolved. Tetragonal superconductors should not have this 
twinning problem. In this work twinned monocrystals will be referred to as sin- 
gle crystals. 

A number of experiments have been carried out on monocrystals such as 
X-ray diffraction (e.g., Borde, Hazen, Lepag, Siegr, Onoda), magnetic studies 
(e.g., Crabt, Schnl, Worth), mechanical measurements (e.g., Cookz, Dinge), 
and micro-Raman spectroscopy (e.g., Hemle). In this section we will briefly de- 
scribe how such crystals are made. The December 1987 issue of the Journal of 
Crystal Growth was devoted to superconductors. 

Millimeter-size (LaujrSrjr)2Cu04 single crystals were grown in a molten copper 
oxide flux (Kawal). Another basic technique employs other fluxes (Haned, 
Taka4, Zhoul), namely, PbFj, B2O3, PbO, PbOi, with the risk of possible Pb 
contamination. LaSr* crystals were also grown by the solid phase reaction using 
a hot press of pellets (Iwazu) and rapid quenching of a nonstoichiometric melt 
(Satoz). 

Small single crystals of YBa2Cu307_5 have been prepared from a sintered pow- 
der which was formed into a pellet and then heated, first in a reducing atmo- 
sphere and then in an oxidizing one at 925°C. Annealing a stoichiometric mix- 
ture also produced monocrystals (Liuzz). Millimeter-size crystals were grown by 
melting a stoichiometric mixture of YBa2Cu307.j plus excess CuO at IISO^C 
followed by holding at 9(X)*^C for 4 days (Damen, see also Final). 

A gold crucible on a gold or alumina sheet was used to obtain free-standing 
(1 X 2 X 0. 1 mm) single crystals of YBa* (Kaise, Kaisl, Holtz). A charge of 2 g 
was heated in air at 200°C/hr and held at 975*^0 for 1 .5 hr, then it was cooled to 
4(X)'^C at 25*^C/hr. The molten charge creeps and forms single crystals and twins 
on the surfaces. The larger crystals formed in the space between the bottom of 
the crucible and the gold support sheet. 

A detailed account has appeared of the preparation of a 123 compound single 
crystal by the flux method (Zhoul). The flux mole ratio Ba02 : CuO was between 
1:3 and 2:5, and the nutrient Y2O3 : Ba02 : CuO mole ratios were 0.5:2:3. A 
multistep temperature process was employed. Black single crystals of YBa* were 
found at the bottom and at the edge between the wall and the bottom of the 
crucibles. Platinum crucibles seemed to contaminate the samples so alumina 
crucibles were recommended. Crystals as large as 2 X 2 X 0.3 mm^ were re- 
ported. A similar technique was used to produce single crystals of YBa* and 
DyBa* as large as 4 mm (Schnl). 



/er components 
•r orthorhombic 
t a and b direc- 
lounced for the 
the b axis. The 



F. ALIGNED GRAINS 

Clearly high-quality single crystals are important for understanding the physics 
of superconductors. However, much useful information about anisotropics can 



68 PREPARATION AND CHARACTERIZATION OF SAMPLES 

be obtained by studying the properties of aligned grains, which are much easier 
to fabricate. 

A superconducting sample can be initially a collection of randomly oriented 
grams, but various techniques can be used to partially orient these grains so that 
the c axis lies preferentially in a particular direction. For example uniaxial com- 
pression tends to orient compacted grains, with compressed 90-Aim particles ex- 
hibiting more alignment than compressed 10-Atm particles (Glowa). Epoxy- 
embedded grains have been aligned under the influence of an applied magnetic 
field and pressure (Arend). 

X-ray and magnetic measurements have been reported on aligned crystalline 
grains of YBa* (Farrl). Optical studies have also been made on aligned grains. 
The critical current density for samples cut parallel to the compression axis of 
such grains was nearly isotropic with respect to the direction of an applied mag- 
netic field, and it was a factor of 6 smaller than that for the samples cut perpen- 
dicular to this axis (Glowa). 



G. REACTIVITY 

The oxide superconductors are not inert materials, but rather they are sensitive 
to exposure to certain gases and to surface contact with particular materials. 
Great care must be exercised to avoid contamination from water vapor and car- 
bon dioxide in the atmosphere. In addition these materials are catalytic to oxy- 
genation reactions, and these factors result in the occurrence of various chemical 
and other interactions, especially at elevated temperatures. The granular and 
porous nature of the materials has an accelerating effect on such reactions. 

Samples of YBaCuO may degrade in a matter of days when exposed to an 
ordinary ambient atmosphere; they react readily with liquid water, acids, and 
electrolytes, and moderately with basic solutions. The reaction with water 
(Barns, Kishi, Yanzz) produces nonsuperconducting cuprates. The effects of ac- 
etone and other organics (McAnd) have been determined, and stable carboxyl 
groups have been found in the YBaCuO lattice (Parmi). 

Hydrogen enters the YBaCuO lattice at elevated temperatures and forms a 
solid solution. Low concentrations have very little effect and high concentrations 
degrade the superconducting properties (Berni. Reill. Yang3). The effects of ex- 
posure to oxygen at elevated temperature and oxidation have been discussed sev- 
eral places m this review (e.g.. Blend, Engle, Tara3). 

The foregoing evidence for the reactivity of the oxide superconductors makes 
it necessary to consider methods of passivation or protecting them from long- 
term degradation. An epoxy coating was found to provide some protection 
(Bams). Coating the surface with metals can be deleterious since metals such as 
Fe (Gaozl, Hillz, Weave) and Ti (Meyel) react with the surface of LaSrCuO or 
YBaCuO. There is evidence for the passivation of the surface of LaSr* with gold 
(Meyer). * 



H. THER] 

Thermogra 
pie during 
oxygen con 
an oxidizir 
procedures 
the method 
John4, Lee 
ferential tl 
procedures 



I. CHECK 

After a san 
conductor, 
mine whetl 
supercondi 
ity sample, 
the magne 
sharp, higl 
-IMtt.TI 
of the susc 
the fractioi 

In addit 
chemical c( 
tion is dedi 
material. ( 
XPS. elect 
probe that 
investigato 
tent is muc 
back-scatt< 
tents, and 

The stru 
ily checkec 
constants a 
or orthorh< 
indicate a \ 
for LaSr* ( 
used to coi 



CHECKS ON QUALITY 69 



:h easier 

Driented 
s so that 
ial corn- 
icles ex- 
Epoxy- 
rtagnetic 

ystalline 
1 grains. 
1 axis of 
ed mag- 
perpen- 



H. THERMOGRAVIMETRIC ANALYSIS 



Thermogravimetnc analysis (TGA) consists of monitoring the weight of a sam- 
pie during a heating or cooling cycle. For example, one might determine the 
oxygen content of a superconducting material by measuring its weight change in 
an oxidizmg (O, or air) or reducing (e.g., 4% H, in Ar) atmosphere. Typical 
procedures consist of heating or cooling at 20-C/min. The relative accuracy of 
he method is about 0.005 (Ongzl). Many workers (e.g.. Beye3, Hauck, Huanl 
John4, Leez7, Maruc, Ohish, Ongzl, Tara7, Zhuzz) are now using TGA or dif' 
ferential thermal analysis (DTA) routinely during their sample preparation 
procedures. r t- r 



sensitive 
laterials. 
and car- 
c to oxy- 
chemical 
ular and 
tions. 
;ed to an 
:ids, and 
th water 
cts of ac- 
carboxyl 

1 forms a 
ntrations 
:cts of ex- 
issed sev- 
ers makes 
om iong- 
rotection 
Is such as 
>rCuO or 
with gold 



I. CHECKS ON QUALITY 

After a sample has been prepared it is necessary to check its quality as a super- 
conductor Most investigators employ the four-probe resistivity check to deter- 
mme whether it superconducts. and at what temperature it transforms to the 
superconductmg state. A sharp, high transition is an indicator of a high-qual- 
.ty sample. Another widely used quality control method is the determination of 
the magnetic susceptibility of the specimen. Good quality is indicated by a 
sjiarp. high transition with both the flux exclusion and flux expulsion close to 

1/4t. This IS, in a sense, a more fundamental check on quality since the value 
of the susceptibility far below the transition temperature is a good indicator of 
the fraction of the sample that is superconducting (see Section III-D) 

In addition to its superconducting properties, it is also of interest to know the 
chemical composition and the structure of the specimen. The nominal composi- 
tion is deduced from the relative proportions of the various cations in the starting 
matenal. Chemical analysis and some more sophisticated techniques such as 
XPS, electrospectroscopic chemical analysis (ESCA). and an electron micro- 
probe that IS favorable for low-atomic-weight elements are applicable here Most 
investigators only report the cation concentrations in the specimen. Oxygen con- 
tent is much more difficult to determine, but is important to know. Rutherford 
back-scattering experiments (Johnl, Wuzzl, Wuzz4) can provide oxygen con- 
tents, and metallography characterizes grain sizes. 

"ITie structures of the oxide superconductors described in Chapter VI are eas- 
ily checked by the X-ray powder pattern mbthod. Many articles list the lattice 
constants a, b,c of samples and mention whether they are tetragonal {a = b:^c) 
or orthorhombic (a « 6 ^ c). Narrow lines and the absence of spurious signals 

or """P'"- '^yP'"^' ^-'■^y diffraction powder patterns 

for LaSr* (Skelt) and YBa* presented in Figs. V-3 and V-4. respectively, may be 
used to compare with patterns obtained from freshly prepared samples 



70 PREPAThI lON AND CHARACTERIZATION OF SAMpISs 



C 
0 

u 

N 
T 

S 





20 



ANGLE IDEG) 

Fig. V.3. Room-temperature (upper curve) and 24-K (lower curve) X- 
powder patterns of (Lao.925Bao.o75)2Cu04 (Skelt). 



ray diffraction 



J. RESIS 

A measur 
temperati 
becomes 
sharp dro 
to apply a 
such a tw 
Most resi 
described 
method (1 
silver gla2 
portance i 
port Jc m 
The sp 
in a suital 
probe con 
and out c 
between t 
conductin 
with the c 
ment volt; 



I- 



> 

to 

UJ 




CO 

o 



20 30 



CO 

Sjk ill l§ - 

40 50 60 70 



40 50 
2 e (DEG) 



Fig. V-4 Room-temperature X-ray diffraction powder pattern of YBa^CuaOy. (Provided 
by C. Almasan, J. Estrada, and W. E. Sharp.) 





RESISTIVITY MEASUREMENT 71 



-ray diffraction 



J. RESISTIVITY MEASUREMENT 



A measurement of the resistance R{T) or resistivity p{T) of a material versus the 
temperature is the principal technique employed to determine when a material 
becomes superconducting. The transition temperature manifests itself by a 
sharp drop in resistivity to zero. The simplest way to make this measurement is 
to apply a voltage across the sample and measure the current flow through it, but 
such a two-probe method (Baszy) is not very satisfactory, and is seldom used. 
Most resistivity determinations are made with the four-probe technique to be 
described below, although more sophisticated arrangements such as a six-probe 
method (Kirsc) can also be used. The fabrication of low-resistance contacts by 
silver glazing has been reported (Vand2). These researchers pointed out the im- 
portance of a low-contact resistance (p < 10 fiQ/mrn^ at 77 K) for making trans- 
port Jc measurements. 

The specimen resistance as a function of temperature is generally determined 
in a suitable cryostat by attaching leads or electrodes to it in the standard four- 
probe configuration. Two leads or probes carry a known constant current / into 
and out of the specimen, and the other two leads measure the potential drop 
between two equipotential surfaces resulting from the current flow. For super- 
conducting specimens the leads are often arranged in a linear configuration, 
with the contacts for the input current on the ends, and those for the measure- 
ment voltage near the center. 



M 

I 

& 



ft 



2 



U3O7. (Provided 



i 



BRIEF ATTACHMENT AG 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In fe Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479.810 
Filed: June 7. 1995 



Date: March 14. 2005 
Docket: YO987-074BZ 
Group Art Unit: 1751 
Examiner: M. Kopec 



For NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 

Commissioner for Patents 
P.O. Box 1450 
Alexandria. VA 22313-1450 



In response to the Office Action dated July 28, 2004, please consider the 



The attachments referred to herein A to Z and AA are in the FIRST 
SUPPLEMENTAL AMENDMENT. The Attachments AB to AG are attached herein. 

Please charge any fee necessary to enter this paper and any previous paper to 
deposit account 09-0468. 



THIRD SUPPLEMENTAL AMENDMENT 



Sir 



following: 




Dr. Daniel P. Moms, Esq 
Reg. No. 32.053 
(914)945-3217 



IBM CORPORATION 
Intellectual Property Law Dept. 
P.O. Box 21 8 

YofWown Heights. New York 10598 



ATTACHMENT AG 



:ONDUCTIVITY 



:ts 



ERCONDUCTIVITY 



The New Superconductors 



>NDUCTIVITY 



Frank J. Owens 



Army Armament Research Engineering and Development Center 
Picatinny. New Jersey 

and Hunter College of the City University of New York 
New York, New York 



and 

Charles P. Poole, Jr. 

Institute of Superconductivity 
University of South Carolina 
Columbia. South Carolina 



on order will bring delivery of 
d only upon actual shipment. 



Plenum Press • New York and London 



On file 



Library of Congress Cataloging-in-Publication Data 



ISBN 0-306-45453-X 

© 1996 Plenum Press, New York 

A Division of Plenum Publishing Corporation 

233 Spring Street, New York. N. Y. 10013 

1098765432 1 

All rights reserved 

^n?fol°nr^' ""^^ ^ reproduced, stored in a retrieval system, or transmitted in 
fil H no mechanical, photocopying, microfilming, 

recording, or othenftfise. without written pemtission from the Pubfisher 

Printed in the United Slates of America 



98 CHAPTER 8 



Table 8, L Progress in Raising the Superconducting Transition Temperature 
Since the Discovery of Cuprates in 1986 



Material 




Year 


Ba;^La5_xCu509 


30-35 


1986 


(Lao.9Bao.i)2Cu404_, (at I-GPa pressure)*' 


52 


1986 


YBasCujOr.^ 


95 


1987 


Bi2Sr2Ca2Cu30|o 


110 


1988 


Tl2Ba2Ca2Cu30io 


125 


1988 


Tl2Ba2Ca2Cu30,o (at 7-GPa pressure) 


131 


1993 


HgBa2C:a2Cu308+„ 


133 


1993 


HgBa2Ca2Cu30,o (at 30-GPa pressure) 


147 


1994 



""A pressure of 1 GPa is about 10,000 atm. 



While this increase in itself is an amazing result, a high-transition tempera- 
ture is not the only property required to make new compounds useful for applica- 
tions. For example if materials are to be used as wires in magnets, they must be 
malleable and ductile rather than brittle; in addition they must have high critical 
currents in large magnetic fields. Critical currents as high as those in niobium-tin 
have not yet been achieved in forms of the new materials that can easily be made 
into wires, although there are reports of comparable values in thin films on various 
substrates. 

The Holy Grail that is being sought is a transition temperature much above 
room temperature. We say much above because devices must operate significantly 
below the transition so that the critical current and critical magnetic field B, 
are sufficiently high. Very close to the transition temperature, the critical magnetic 
field is usually quite small, but we see from Figs. 3.4 and 3.5 that and J, 
continuously increase as the temperature is lowered below T^, We need an operating 
temperature far below the critical surface in Fig. 3.15 so that both and are 
sufficiently large for the desired application. 

83, LAYERED STRUCTURE OF THE CUPRATES 

All cuprate superconductors have the layered structure shown in Fig. 8.1: The 
flow of supercurrent takes place in conduction layers, and binding layers support 
and hold together the conduction layers. Conduction layers contain copper-oxide 
(CUO2) planes of the type shown in Fig. 8.2; each copper ion (Cu^*) is surrounded 
by four oxygen ions (O^'). These planes are held together in the structure by calcium 
(Ca^*) ions located between diem, as indicated in Fig. 8.3. An exception to this is 
the yttrium compound in which the intervening ions are the element yttrium (Y ) 
instead of calcium. These CUO2 planes are very close to being flat. In the normal 
state above conduction electrons released by copper atoms move about on these 




figure 8.h Layering sche 
layers for different sequent 
for several cuprates. 



figure 8.2. Arrangement 
in a CUO2 plane of the cor 



CHAPTERS 



f^EW HICH-TEMPERATURE SUPERCONDUCTORS 



99 



Transition Temperature 
n 1986 



Year 

1986 
1986 
1987 
1988 
1988 
1993 
1993 
1994 



C 



BINDING LAYERS 



CONDUCTION LAYERS WITH CuO^ 



BINDING LAYERS 



CONDUCTION LAYERS with CuO^ 



t, a high-transition tempera- 
npounds useful for applica- 
s in magnets, they must be 
ley must have high critical 
igh as those in niobium-tin 
als that can easily be made 
ues in thin films on various 

n temperature much above 
: must operate significantly 
d critical magnetic field 
•ature, the critical magnetic 
.4 and 3.5 that B, and J, 
w Tp. We need an operating 
so that both and are 



BINDING LAYERS 



CONDUCTION LAYERS WITH CuO^, 



BINDING LAYERS 



Figure 6, 1 . Layering scheme of the cuprate superconductors, figure 8.3 shows details of the conduction 
layers for different sequences of copper oxide planes, and Fig. 8.4 presents details of the binding layers 
for several cuprates. 



f5 

ure shown in Fig. 8.1 : The 
ind binding layers support 
yers contain copper-oxide 
;r ion (Cu^*) is surrounded 
in the structure by calcium 
.3. An exception to this is 
the element yttrium (Y^) 
) being flat. In the normal 
toms move about on these 



figure 6.2. Arrangement of copper and oxygen atoms 
in a CUO2 plane of the conduction layer. 



OXYGEN COPPER 

I / 
I / 

• o • o • o 

o o o 

• o • o • o 
000 

• o • o • o 



o 
o 



CHAPTERS 

CUO2 

Conduction layer with one copper oxide plane 



CuO;j 
Ca 
CUO2 



Conduction layer with two copper oxide planes 



_ CuOa 
_ Y 
_ CuO^ 




Conduction layer of yttrium compound with two copper oxide planes 
CuO. { 



Ca 



CUO2 
Ca 
CuOa 



Conduction layer with three copper oxide planes 

f igure 8.3. Conduction layers of the various cuprate superconductors showing sequences of CUO2 and 
Ca (or Y) planes in the conduction layers of Fig. 8.1. 

CUO2 planes carrying electric current. In the superconducting state below T^, these 
same electrons form the Cooper pairs that cany the supercunent in the planes. 

Each particular cuprate compound has its own specific binding layer consisting 
mainly of sublayers of metal oxides MO, where M is a metal atom; Fig. 8.4 gives 
the sequences of these sublayers for the principal cuprate compounds. These 
binding layers are sometimes called charge reservoir layers because they contain 




Neodyn 



Y 



Bismu' 



Thalli 



Mercu 

f''gure8.4. Sequence; 
"letal ions. The parent! 




CHAPTERS 



r oxide plane 



r oxide planes 



two copper oxide planes 



jer oxide planes 

:tors showing sequences of CuO^ and 



•nducting state below Tc, these 
supercunent in the planes. 
»ecific binding layer consisting 
is a metal atom; Fig. 8.4 gives 
J cuprate compounds. These 
iV layers because they contain 



Lao 
LaO 



Lanthanum Superconductor La^CuO^ 



NdO 
NdO 



Neodymium (electron) Superconductor Nd^CuO* 




yttrium Superconductor YBa^Cu^O^ 



SrO 
Bio 
Bio 
SrO 



Bismuth superconductor Bi2SraCa„.iCu„0^4 



BaO 
TIO 
TIO 
BaO 



Thallium Superconductor Tl2Ba2Ca„.iCu„0a„^4 




Mercury Superconductor HgBa^Can.iCu^Oa^^a 

figure 8.4. Sequences of MO sublayers in the binding layers of Fig. 8. K where M stands for various 
metal ions. The parentheses around the oxygen atom O in the lowest panel indicates partial occupancy. 



CHAPTERS 

of randomly oriented grains. In 
he cunent flow capability of 



La,_^,Sr^)2Cu04 are hole-type 
^rium-copper oxide, (Nd,_^ 
trons rather than holes. The 
have trivalent positive ions: 

(8.6) 
(8.7) 

itium (Sr^^) and cerium (Ce**X 



jCu04) 



I2CUO4) 



(8.8) 



(8.9) 



one extra electron to form an 
rontium subtracts one electron, 
rperconductor is hole-like. Any 
mt both of these examples of 
lar, but not identical structures; 
:ause most experiments are not 



VCTURES 

ferred to as ceramics, they are 
irovskite refers to the particular 
;ral perovskite, calcium titanate 
:) parts of the lanthanum com- 
perovskite. with Cu present in 
lot shown in Fig. 8.9) positions, 
Similarities between these two 
:all La2Cu04 a perovskite-type 



^^HICH-TEMPERATURE SUPERCONDUCTORS 



109 



TITANIUM 



OXYGEN- 




figure 8.9. Sketch of the cubic unit cell of the mineral Perovskite, CaTi03, showing titanium at the 
vertices and oxygen in the middle of the edges. Calcium, not shown, is in the center of the cube. 



In contrast the ceramic designation is not based on structural grounds but on 
the similarity of the cuprate-superconducting compound and ceramic manufactur- 
ing process. For example La-Sr-Cu-0 is made by heating mixtures of lanthanum 
oxide, strontium carbonate, and copper oxide in air at 9(X)-1000 for 20 hours. 
Proportions of atoms in the initial mixture should be the same as in the end product, 
and for the compound (Lao9Sro.i)2Cu04 the ratio La:Sr:Cu is 1.8:0.2:1. Materials 
are usually ground to a fine mixture before heating; after heating in air, they are 
cooled, pressed into pellets, and reheated from 900- 1 000 **C for several more hours. 

We see in Fig. 8.10 that the superconductor (La|_,Srj2Cu04 has only one 
copper oxide plane in its conduction layer and each copper ion is surrounded by 




pervoskite 
like 



conduction layer 



binding layer 



conduction layer 

binding layer 

conduction layer 
a 

%ure 8J0. Atom positions in the tetragonal unit cell of the La2Cu04 compound. When strontium is 
substituted for lanthanum in the superconducting compound (La|_jjSr^)2Cu04 it replaces lanthanum in 
«»ne of the La sites. 



Cu- 



110 



CHAPTERS 



f^E\A/ HIGH-TE/^ 



six neighboring oxygen ions; these form an 8-sided figure called an octahedron, as 
shown. The CuOg complex of one copper and six oxygens is present in all cuprate 
superconductors that have a single CuOz plane in their conduction layer. Figure 
8. 11 shows atom arrangements in the mercury compound HgBajCaiCujOio, which 
has three such planes in its conduction layer, hi the upper and lower planes, copper 
ions have five neighboring oxygens forming a CuOj group with the shape of a 
pyramid, as shown. The middle cc^per ions have only four nearby oxygens, forming 
what is called a square planar group CUO4. If we consider removing the central 
copper oxide plane and one calcium layer from Fig. 8. 1 1 , we generate the two-plane 
structure in which all copper ions form CUO5 pyramids. These structural details 
may somehow constitute important factors in determining why cuprates are such 
good superconductors. 



YTTRIL 

The disco 
the initial rq)0] 
Muller (see F; 
compoundYB; 
niuogen, as sh* 
between the re: 
Wu of the Uni> 



ac 



r 



BINDING 
LAYER 



r 



CONDUCTION 
l^YER 



r 



BINDING 
LAYER 




E 
o 

a 
a 



O.C 



0.C 



O.C 



O.C 



0.( 



Figure 8.1 h Atom positions in four unit ceUs of the superconducting compound HgBa2Ca2Cu308+i 
whidi has = 1 33 K. The copper ions of Uie upper CuOj plane are hidden by Uie pyramids, and some 
partially occupied oxygen sites in the mercury Hg plane are not shown. 



ffgurea.rz Firs 
BednorzandK. A 



BRIEF ATTACHMENT AH 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479,810 
Filed: June 7, 1995 



Group Art Unit: 1751 
Examiner: M. Kopec 



Date: March 1, 2004 



Docket: YO987-074BZ 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



FIFTH SUPPLEMENTAL AMENDMENT 



Sir: 



In response to the Office Action dated February 4, 2000: 



ATTACHMENT 16 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
J. Bednorz et al. 



Date: December 15, 1998 



Serial No, 08/303,561 



Group Art Unit: 1105 



Filed: September 9, 1994 



Examiner: M. Kopec 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, AND METHODS FOR THEIR USE AND PREPARATION 



I, David B. Mitzi, being duly sworn, do hereby depose and state: 

That I received a B. S. E. degree in Electrical Engineering/Engineering Physics (1985) from 
Princeton University and a PhD. degree, in Applied Physics (1990) from Stanford University, 
California. 

That I have worked as a research staflf member in Solid State Chemistry at the Thomas Watson 
Research Center of the International Business Machines Corporation in Yorktown Heights, NY 
from 1990 to the present. 

That I have worked in the fabrication of and characterization of high temperature superconductor 
and related materials from 1990 to the present. 

That I have reviewed the above-identified patent application and that I have reviewed the 
above-identified patent application and acknowledge that it represents the work of Bednorz and 



AFFIDAVIT UNDER 37 C.F.R. 1.132 



Commissioner of Patents and Trademarks 
Washington, D. C. 20231 



Sir: 



YO987-074BY 



Muller, which is generally recognized as the first discovery of superconductivity above 26**K and 
that subsequent developments in this field have been based on this work. 

That all the high temperature superconductors which have been developed based on the work of 
Bednorz and Muller behave in a similar manner, conduct current in a similar manner and have 
similar magnetic properties. 

That once a person of skill in the art knows of a specific transition metal oxide composition which 
is superconducting above 26°K, such a person of skill in the art, using the techniques described in 
the above-identified patent application, which includes all knows principles of ceramic fabrication 
known at the time the application was filed, can make the transition metal oxide compositions 
encomposed by the claims in the above identified application, without undue experimentation or 
without requiring ingenuity beyond that expected of a person of skill in the art. This is why the 
work of Bednorz and Muller was reproduced so quickly a&or their discovery and why so much 
additional work was done in this field within a short period of their discovery. 

The general principles of ceramic science referred to by Bednorz and Mueller in their patent 
apphcation can be found in many books and articles published before their discovery. An 
exemplary list of books describing the general principles of ceramic fabrication are: 

1) Introduction to Ceramics, Kingery et al.. Second Edition, John Wiley & Sons, 
1976, in particular pages 5-20, 269-319, 381-447 and 448-513, a copy of which is with 
the Affidavit of Thomas Shaw submitted December 15, 1998. 

2) Polar Dielectrics and Their Applications, Burfoot et al.. University of California Press, 
1979, in particular pages 13-33, a copy of which is with the Affidavit of Thomas Shaw 
submitted December 15, 1998. 

3) Ceramic Processing Before Firing, Onoda et al., John Wiley & Sons, 1978, the entire 
book, a copy of which is with the Affidavit of Thomas Shaw submitted December 15, 

1998. 



YO987-074BY 



• 



4) Structure, Properties and Preparation of Perovskite-Type Compounds, F.S. Glasso 
Pergamon Press, 1969, in particular pages 159-186, a copy of which is with the Affidavit 
of Thomas Shaw submitted December 15, 1998. 



An exemplary list of articles applying their general principles of ceramic fabrication to the types of 
materials described in applicants' specification are (these references are cited on applicant's 1449 
form submitted August 5, 1987 and in PTO Form 892 in Paper # 20, Examiner's action dated 
August 8, 1990): 



1) Oxygen Defect K2NiF4 - Type Oxides: The Compounds Laz-x SrxCuO^-x^*, Nguyen et 
al.. Journal of Solid State Chemistry 39, 120-1^^81). 

2) The Oxygen Defect Perovskite BaLa4 Cu5<Di3.4, A Metallic Conductor , C. Michel et 
al., Mat. Res. Bull, Vol. 20, pp. 667-671, 1985. 

3) Oxygen intercalation in mixed valence copper oxides related to the perovskite, C. 
Nfichel et al;. Revue de Chemie minerale, p. 407, 1984. 



4) Thermal Behaviour of Compositions in the Systems x BaTiOa + (1-x) Ba(Lno.5 Bo 5) O3. 
V.S. Chincholkar et al. Therm. Anal. 6th, Vol. 2., p. 251-6, 1980. 




Sworn to beforejue 




Notary Public 



DANIEL P, MORRIS 
NOTARY PUBUC Stato of New York 
No. 4666676 

Qualified in Westchester County x;;^^ 
Commission Expires March 16, 19Jl2f^ 



David B. Mitzi 



^ i^J^ day of 



YO987-074BY 



BRIEF ATTACHMENT Al 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479,810 



Date: March 1 , 2004 



Docket: YO987-074BZ 



Filed: June 7, 1995 



Group Art Unit: 1751 
Examiner: M. Kopec 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria. VA 22313-1450 



FIFTH SUPPLEMENTAL AMENDMENT 



Sir: 



In response to the Office Action dated February 4, 2000: 



ATTACHMENT 17 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of . u , i < i qor 

J. BednTrz et al. Date: December 15. 1998 

Serial No. 08/303.561 Group Art Unit: 1 105 

Filed: September 9, 1994 Examiner: M. Kopec 

For NEW SUPERCONDUCTIVB COMPOUNDS HAVING fflGHTT^SITI^^^ 
xiMPERATURE. AND METOODS FOR THEm USE AND PREPARATION 



AT7FmAVTTUN r>P^tl7CFR. 1.132 

Commissioner of Patents and Trademarks 
Washington, D. C. 20231 



Sir: 

I, Timothy Dinger, being duly sworn, do hereby depose and state: 

That I received a B. S. degree in Ceramic Engineering (1981) from New York State College of 
Ceramics, Alfred University, an M. S. degree (1983) and a PhD. degree (1986), both in Material 
Science from the University of California at Berkley. 

That I have worked as a research staflf member in Material Science at the Thomas Watson 
Research Center of the International Business Machines Corporation in Yorktown Heights, NY 
from 1 986 to the present. 

That I have worked in the fabrication of and characterization of high temperature superconductor 
materials from 1987 to 1991. 

That I have reviewed the above-identified patent application and acknowledge that it represents 
the work of Bednorz and Muller, which is generally recognized as the first discovery of 



YO987-074BY 



superconductivity above 26TC and that subsequent developments in this field have been based on 
this work. 



That all the high temperature superconductors which have been developed based on the work of 
Bednorz and MuUer behave in a similar way, conduct current in a similar manner and have similar 
magnetic properties. 

That once a person of skUl in the art knows of a specific transition metal oxide composition which 
is superconducting above 26'K, such a person of skiU in the art, using the techniques described in 
the above-identified patent application, which includes all knows principles of ceramic fabrication 
known at the time the apphcation was filed, can make the transition metal oxide compositions 
encomposed by the claims in the above identified apphcation, without undue experimentation or 
without requiring ingenuity beyond that expected of a person of skill in the art. This is why the 
work of Bednorz and MuUer was reproduced so quickly after their discovery and why so much 
additional work was done in this field within a short period of their discovery. 

The general principles of ceramic science referred to by Bednorz and MueUer in their patent 
apphcation can be found in many books and articles pubUshed before their discovery. An 
exemplary list of books describing the general principles of ceramic fabrication are: 

1) Introduction to Ceramics, Kingeiy et al.. Second Edition, John Wiley & Sons, 
1976, in particular pages 5-20, 269-319, 381-447 and 448-513, a copy of which is with 
the AflRdavit of Thomas Shaw submitted December 15, 1998 

2) Polar Dielectrics and Their Applications, Burfoot et al.. University of California Press, 
1979, in particular pages 13-33, a copy of which is with the Affidavit of Thomas Shaw 
submitted December 15, 1998. 

3) Ceramic Processing Before Firing, Onoda et al., John Wiley & Sons, 1978, the entire 
book, a copy of which is with the Affidavit of Thomas Shaw submitted December 15, 
1998^ 



YO987-074BY 



4) Stnicture, Properties and Preparation of Perovsldte-Type Compounds, F.S. Glasso, 
Pergamon Press, 1969, in particular pages 159-186, a copy of which is with the Affidavit 
of Thomas Shaw submitted December 15, 1998. 



An exemplary list of articles applying their general principles of ceramic fabrication to the types of 
matOTals described in applicants* specification are (these references are cited on applicant's 1449 
form submitted August 5, 1987 and in PTO Form 892 in Paper # 20, Examiner's action dated 
Augusts, 1990): 

1) Oxygen Defect K2NiF4 - Type Oxides: The Compounds Lai^ SrxCu04.x/2+% Nguyen et 
al.. Journal of SoUd State Chemistry 39, 120-127 (1981). 

2) The Oxygen Defect Perovskite BaLa4 Cu5-0,34, A Metallic Conductor , C. MQchel et al., 
Mat. Res. Bull., Vol. 20, pp. 667-671, 1985. 

3) Oxygen intercalation in mixed valence copper oxides related to the perovskite, C. 
Michel et al.. Revue de Chemie minerale, p. 407, 1984. 

4) Thermal Behaviour of Compositions in the Systems x BaTiOa + (1-x) Ba(Lno.5 Bo s) O3. 
V.S. Chincholkar et al. Therm. Anal. 6th, Vol. 2., p. 251-6, 1980. 




Timothy Dinger 



Sworn to before me this 





Notary Public 




YO987-074BY 



BRIEF ATTACHMENT AK 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479,810 
Filed: June 7, 1 995 



Group Art Unit: 1751 
Examiner: M. Kopec 



Docket: YO987-074BZ 



Date: March 1 , 2004 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria. VA 22313-1450 



FIFTH SUPPLEMENTAL AMENDMENT 



In response to the Office Action dated February 4, 2000: 



ATTACHMENT 19 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



Applicants: J. Bednorz et al. 



Date: Decemb)er 15, 1998 



Serial No. 08/303,561 



Group Art Unit: 1105 



Filed: September 9, 1 994 



Examiner M. Kopec 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH 
TRANSITION TEMPERATURE. AND METHODS FOR THEIR 
USE AND PREPARATION 



The Commissioner of Patents and Trademarks 
Washington, D.C. 20231 



Sir: 

I, Thomas M. Shaw, being duly sworn, do hereby depose and state: 

I received a B.S. degree in Metallurgy from the University of Liverpool, Liverpool, 
England and a M.S. and PhD. degree in Materials Science (1981) from the University 
of California, Berkeley. 

I have worked as a postdoctoral researcher in the Material Science Department of 
Cornell University from 1981-1982. I worked at Rockwell International Science Center 
in Thousand Oaks, California from 1982-1984 as a ceramic scientist. I have worked as 
a research staff member in Ceramics Science at the Thomas J. Watson Research 

YO987-074BY 1 



AFFIDAVIT UNDER 37 CFR 1.132 



Center of the International Business Machines Corporation in Yorktown Heights, N.Y. 
from 1984 to the present. 

I have worked in the fabrication of and characterization of ceramic materials of various 
types, including superconductors and related materials from 1 984 to the present. 

Attached is a resume of my publications. I have reviewed the above-identified patent 
application and acknowledge that it represents the work of Bednorz and Mueller, which 
is generally recognized as the first discovery of superconductivity above 26°K and that 
subsequent developments in this field have been based on this work. 

That all the high temperature superconductors which have been developed based on 
the work of Bednorz and Mueller behave in a similar manner, conduct current in a 
similar manner and have similar magnetic properties. 

That once a person of skill in the art knows of a specific transition metal oxide 
composition which is superconducting above 26*K, such a person of skill in the art, 
using the techniques described in the above-identified patent application, which 
includes all known principles of ceramic fabrication known at the time the application 
was filed, can make the transition metal oxide compositions encompassed by the 
claims in the above-identified application, without undue experimentation or without 
requiring ingenuity beyond that expected of a person of skill in the art. This is why the 



YO987-074BY 



2 



work of Bednorz and Mueller was reproduced so quickly after their discovery and why 
so much additional work was done in this field within a short period of their discovery. 

The general principles of ceramic science referred to by Bednorz and Mueller in their 
patent application can be found in many books and articles published before their 
discovery. An exemplary list of books describing the general principles of ceramic 
fabrication are: 

1) Introduction to Ceramics, Kingery et a!.. Second Edition, John Wiley & Sons, 
1976, in particular pages 5-20, 269-319. 381-447 and 448-513, a copy of 
which is attached herewith, 

2) Polar Dielectrics and Their Applications, Burfoot et al.. University of California 
Press, 1979, in particular pages 13-33, a copy of which is attached herewith. 

3) Ceramic Processing Before Firing, Onoda et al., John Wiley & Sons, 1978, 
the entire book, a copy of which is attached herewith. 

4) Structure, Properties and Preparation of Perovskite-Type Compounds, 
F.S. Glasso, Pergamon Press, 1969, in particular pages 159-186, a copy of 
which is attached herewith. 

An exemplary list of articles applying their general principles of ceramic fabrication to 
the types of materials described in applicants' specification are (these references are 
cited on applicant's 1449 form submitted August 5, 1987 and in PTO Form 892 in 
Paper # 20, Examiner's action dated August 8, 1 990): 

1) Oxygen Defect K2NiF4 - Type Oxides: The Compounds La2.x SrxCu04-x/2+6. Nguyen et 
a!.. Journal of Solid State Chemistry 39, 120-127 (1981). 

2) The Oxygen Defect Perovskite BaLa4 CU5-O13.4. A Metallic Conductor . C. Michel et 
al., Mat. Res. Bull., Vol. 20, pp. 667-671, 1985. 



YO987-074BY 



3 



3) Oxygen intercalation in mixed valence copper oxides related to the perovskite, C. 
Michel et al., Revue de Chemie minerale, p. 407, 1984. 

4) Thermal Behaviour of Compositions in the Systems x BaTiOa + (1-x) Ba(Lno5 Bos) O3 

V.S. Chincholkar et al. Therm. Anal. 6th. Vol. 2., p. 251-6. 1980. 



Notary Public 



SANDRA M. EMMA 
Notary Public. Slate of New Yof Ic 

NO.01PO493529O 
Quartfied in V^festchester County 
Commission Expires July ^» J , uVt 




Thomas M. Shaw 



Sworn to before me this 




19?^. 




YO987-074BY 



4 



BRIEF ATTACHMENT AJ 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479,810 
Filed: June 7, 1995 



Group Art Unit: 1751 
Examiner: M. Kopec 



Docket: YO987-074BZ 



Date: March 1 , 2004 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



FIFTH SUPPLEMENTAL AMENDMENT 



Sir: 



In response to the Office Action dated February 4, 2000: 



ATTACHMENT 18 



FN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
J. Bednorz et al. 



Date: December 15, 1998 



Serial No. 08/303,561 



Group Art Unit: 1105 



Filed: September 9, 1994 



Examiner: M. Kopec 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, AND METHODS FOR THEIR USE AND PREPARATION 



I, Chang C. Tsuei, being duly sworn, do hereby depose and state: 

That I received a B. S. degree in Mechanical Engineering from National Taiwan University (1960) 
and M. S. and PhD. degrees, in Material Science (1963, 1966) respectively from Califr)mia 
Institute of Technology. 

That I have worked as a research staflf member and manager in the physics of superconducting, 
amorphous and structured matwials at the Thomas Watson Research Center of the International 
Business Machines Corporation in Yorktown Heights, New York from 1973 to the present. (See 
attached Exhibit A for other professional employment history.) 

That I have worked in the fabrication of and characterization of high temperature superconductor 
and related materials from 1973 to the present. 

That I have reviewed the above-identified patent application and acknowledge that it represents 
the work of Bednorz and Muller, which is generally recognized as the first discovery of 
YO987-074BY 



AFFIDAVrrUNDER 37 CF.R. 1.132 



Commissioner of Patents and Trademarks 
Washington, D. C. 20231 



Sir: 



superconductivity above l&^K and that subsequent developments in this field have been based on 
this work. 

That all the high temperature superconductors which have been developed based on the work of 
Bednorz and Muller behave in a similar manner, conduct current in a similar manner and have 
similar magnetic properties. 

That once a person of skill in the art knows of a specific transition metal oxide composition which 
is superconducting above 26°K, such a person of skill in the art, using the techniques described in 
the above-identified patent application, which includes all knows principles of ceramic fabrication 
known at the time the application was filed, can make the transition metal oxide compositions 
encomposed by the claims in the above identified application, without undue experimentation or 
without requiring ingenuity beyond that expected of a person of skill in the art. This is why the 
work of Bednorz and Muller was reproduced so quickly after their discovery and why so much 
additional work was done in this field within a short period of their discovery. 

The general principles of ceramic science referred to by Bednorz and Mueller in their patent 
application can be found in many books and articles published before their discovery. An 
exemplary list of books describing the general principles of ceramic fabrication are: 

1) Introduction to Ceramics, Kingery et al.. Second Edition, John WTUey & Sons, 
1976, in particular pages 5-20, 269-319, 381-447 and 448-513, a copy of which is with 
the Affidavit of Thomas Shaw submitted December 15, 1998. 

2) Polar Dielectrics and Their Applications, Burfoot et al., University of California Press, 
1979, in particular pages 13-33, a copy of which is v/ith the Affidavit of Thomas Shaw 
submitted December 15, 1998. 

3) Ceramic Processing Before Firing, Onoda et al., John Wiley & Sons, 1978, the entire 
book, a copy of which is with the Affidavit of Thomas Shaw submitted December 15, 
1998. 



YO987-074BY 



4) Structure, Properties and Preparation of Perovskite-Type Compounds, F.S. Glasso, 
Pergamon Press, 1969, in particular pages 159-186, a copy of which is with the Affidavit 
of Thomas Shaw submitted December 15, 1998. 



An exemplary list of articles applying their general principles of ceramic fabrication to the types of 
materials described in applicants' specification are (these references are cited on applicant's 1449 
form submitted August 5, 1987 and in PTO Form 892 in Paper # 20, Examiner's action dated 
August 8, 1990): 



1) Oxygen Defect K2NiF4 - Type Oxides: The Con^)ounds Laz-x SrxCu04.x«f, Nguyen et 
al., Journal of Solid State Chemistry 39, 120-127 (1981). 

2) The Oxygen Defect Perovskite BaLa4 Cus-0i3.4, A Metallic Conductor , C. Michel et al.. 
Mat. Res. Bull., Vol. 20, pp. 667-671, 1985. 

3) Oxygen intercalation in mixed valence copper oxides related to the perovskite, C. 
Michel et al.. Revue de Chemie minerale, p. 407, 1984. 

4) Thermal Behaviour of Compositions in the Systems x BaTiOj + (1-x) Ba(Lno.5 B0.5) 
O3.V.S. Chincholkar et al. Therm. Anal. 6th, Vol. 2., p. 251-6, 1980. 



Bv: ^^—-t^ ^ ^ 
Chang C. Tsuei 



Sworn to before me this 



dayof (\ilJl>OniM^ , 




7 

Notary Public 



SANDRA M. EMMA 
Notary Public, State of New York 

NO.01P04935290 
Oualified in Westchester Coontv 
Commission Expires July 5, £LuSi2 



YO987-074BY 



CHANG C. TSUEI 



Education 

California Institute of Technology, M S. (1963), Ph.D. (1966) 
National Taiwan University, B.S. (1960) 

Professional Employment 

1993 - present - Research Staff Member 
1983 - 1993 - Manager, Physics of Structured Materials 
1979 - 1983 - Manager, Physics of Amorphous Materials 
1974 - 1975 - Acting Manager, Superconductivity 
1973 - 1979 - Research Staff Member 



Harvard University: 1980 (Summer) 

Visiting Scholar in Applied Physics 

Stanford University: 1982 (Sept.) - 1983 (April) 
Visiting Scholar in Applied Physics 

California Institute of Technology 

1972 - 1973 - Senior Research Associate in Applied Physics 
1969 - 1972 - Senior Research Fellow in Materials Science 
1966 - 1969 - Research Fellow in Materials Science 

Exhibit A 



YO987-074BY 



BRIEF ATTACHMENT AK 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479,810 
Filed: June 7, 1995 



Group Art Unit: 1751 
Examiner: M. Kopec 



Date: March 1 , 2004 



Docket: YO987-074BZ 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



FIFTH SUPPLEMENTAL AMENDMENT 



In response to the Office Action dated February 4, 2000: 



ATTACHMENT 19 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



Applicants: J. Bednorz et al. 



Date: December 15, 1998 



Serial No. 08/303,561 



Group Art Unit: 1105 



Filed: September 9, 1 994 



Examiner M. Kopec 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH 
TRANSITION TEMPERATURE. AND METHODS FOR THEIR 
USE AND PREPARATION 



The Commissioner of Patents and Trademarks 
Washington, D.C. 20231 



Sir: 

I, Thomas M. Shaw, being duly sworn, do hereby depose and state: 

I received a B.S. degree in Metallurgy from the University of Liverpool, Liverpool, 
England and a M.S. and PhD. degree in Materials Science (1981) from the University 
of California, Berkeley. 

I have worked as a postdoctoral researcher in the Material Science Department of 
Cornell University from 1981-1982. I worked at Rockwell International Science Center 
in Thousand Oaks, California from 1982-1984 as a ceramic scientist. I have worked as 
a research staff member in Ceramics Science at the Thomas J. Watson Research 



AFFIDAVIT UNDER 37 CFR 1.132 



YO987-074BY 



1 



Center of the International Business Machines Corporation in Yorktown Heights, N.Y. 
from 1984 to the present. 

I have worked in the fabrication of and characterization of ceramic materials of various 
types. Including superconductors and related materials from 1984 to the present. 

Attached is a resume of my publications. I have reviewed the above-identified patent 
application and acknowledge that it represents the work of Bednorz and Mueller, which 
is generally recognized as the first discovery of superconductivity above 26°K and that 
subsequent developments in this field have been based on this work. 

That all the high temperature superconductors which have been developed based on 
the work of Bednorz and Mueller behave in a similar manner, conduct current in a 
similar manner and have similar magnetic properties. 

That once a person of skill in the art knows of a specific transition metal oxide 
composition which is superconducting above 26*K, such a person of skill in the art, 
using the techniques described in the above-identified patent application, which 
includes all known principles of ceramic fabrication known at the time the application 
was filed, can make the transition metal oxide compositions encompassed by the 
claims in the above-identified application, without undue experimentation or without 
requiring ingenuity beyond that expected of a person of skill in the art. This is why the 



YO987-074BY 



2 



work of Bednorz and Mueller was reproduced so quickly after their discovery and why 
so much additional work was done in this field within a short period of their discovery. 

The general principles of ceramic science referred to by Bednorz and Mueller in their 
patent application can be found in many books and articles published before their 
discovery. An exemplary list of books describing the general principles of ceramic 
fabrication are: 

1) Introduction to Ceramics, Kingery et al.. Second Edition, John Wiley & Sons. 
1976. in particular pages 5-20. 269-319. 381-447 and 448-513, a copy of 
which is attached herewith. 

2) Polar Dielectrics and Their Applications. Burfoot et al.. University of California 
Press. 1979. in particular pages 13-33. a copy of which is attached herewith. 

3) Ceramic Processing Before Firing. Onoda et al.. John Wiley & Sons, 1978, 
the entire book, a copy of which is attached herewith. 

4) Structure, Properties and Preparation of Perovskite-Type Compounds, 
F.S. Glasso, Pergamon Press. 1969. in particular pages 159-186, a copy of 
which is attached herewith. 

An exemplary list of articles applying their general principles of ceramic fabrication to 
the types of materials described in applicants' specification are (these references are 
cited on applicant's 1449 form submitted August 5, 1987 and in PTO Form 892 in 
Paper # 20. Examiner's action dated August 8. 1 990): 

1) Oxygen Defect K2NiF4 - Type Oxides: The Compounds La2.x SrxCu04.x/2+6. Nguyen et 
al.. Journal of Solid State Chemistry 39. 120-127 (1981). 

2) The Oxygen Defect Perovskite BaLa4 CU5-O13.4, A Metallic Conductor , C. Michel et 
al., Mat. Res. Bull.. Vol. 20. pp. 667-671, 1985. 



YO987-074BY 



3) Oxygen intercalation in mixed valence copper oxides related to the perovskite C 
Michel et al., Revue de Chemie minerale, p. 407, 1984. 

4) Thermal Behaviour of Compositions in the Systems x BaTiOa + (1-x) Ba(Lno5 Bos) O3 

V.S. Chincholkar et al. Therm. Anal. 6th, Vol. 2.. p. 251-6, 1980. 



Notary Public 



SANDRA M. EMMA 
Notary Pubric. State of New York 

No.OtP04935290 
Qualified in Westchester County 
Commission Expires July ^.dJmSL 




Thomas M. Shaw 



Sworn to before me this 





YO987-074BY 



4 



BRIEF ATTACHMENT AL 



i 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479,810 
Filed: June 7, 1995 



Group Art Unit: 1751 
Examiner: M. Kopec 



Docket: YO987-074BZ 



Date: March 1,2004 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE. METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



FIFTH SUPPLEMENTAL AMENDMENT 



Sir: 



In response to the Office Action dated February 4, 2000: 



ATTACHMENT 20 




IN THE UNITED STATES PATENT AND TRADEMARK QFFICF 



Applicants: J. Bednorz et al. 



Date: December 18, 1998 



Serial No. 08/303,561 



Group Art Unit: 1105 



Filed: September 9, 1 994 



Examiner: M. Kopec 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH 
TRANSITION TEMPERATURE. AND METHODS FOR THEIR 
USE AND PREPARATION 



The Commissioner of Patents and Trademarks 
Washington. D.C. 20231 



I, Peter R. Duncombe, being duly sworn, do hereby depose and state: 

I received a B.A. degree in Chemistry from the State University of New York at New 
Paltz, New Paltz, N.Y. and a M.S. degree in Chemical Engineering (1983) from the 
State University of New York at Buffalo, Buffalo. N.Y. 

I have worked as a graduate research assistant in the Chemical Engineering 
Department of SUNY at Buffalo from 1980-1983. I have worked as a chemical 
engineer in Ceramics Science at the Thomas J. Watsop Research Center of the 
International Business Machines Corporation in Yorktown Heights, N.Y. from 1984 to 
the present. 

YO987-074BY 1 



AFFIDAVIT UNDER 37 CFR 1.132 



I have worked in the fabrication of and characterization of ceramic materials of various 
types, including superconductors and related materials from 1984 to the present. 

Attached is a resume of my publications (Attachment A). 

I have reviewed the above-identified patent application and acknowledge that it 
represents the work of Bednorz and Mueller, which is generally recognized as the first 
discovery of superconductivity above 26°K and that subsequent developments in this 
field have been based on this work. 

That all the high temperature superconductors which have been developed based on 
the work of Bednorz and Mueller behave in a similar manner, conduct current in a 
similar manner and have similar magnetic properties. 

That once a person of skill in the art knows of a specific transition metal oxide 
composition which is superconducting above 26''K, such a person of skill in the art, 
using the techniques described in the above-identified patent application, which 
includes all known principles of ceramic fabrication known at the time the application 
was filed, can make the transition metal oxide compositions encompassed by the 
claims in the above-identified application, without undue experimentation or without 
requiring ingenuity beyond that expected of a person of skill in the art. This is why the 



YO987-074BY 



2 



work of Bednorz and Mueller was reproduced so quickly after their discovery and why 
so much additional work was done in this field within a short period of their discovery. 

The general principles of ceramic science referred to by Bednorz and Mueller in their 
patent application can be found in many books and articles published before their 
discovery. An exemplary list of books describing the general principles of ceramic 
fabrication are: 

1) Introduction to Ceramics. Kingery et al., Second Edition, John Wiley & Sons, 
1976, in particular pages 5-20, 269-319, 381-447 and 448-513, a copy of 
which is attached herewith. 

2) Polar Dielectrics and Their Applications, Burfoot et al., University of California 
Press, 1979, in particular pages 13-33, a copy of which is attached herewith. 

3) Ceramic Processing Before Firing, Onoda et al., John Wiley & Sons, 1978, 
the entire book, a copy of which is attached herewith. 

4) Structure, Properties and Preparation of Perovskite-Type Compounds, 
F.S. Glasso, Pergamon Press, 1969, in particular pages 159-181, a copy of 
which is attached herewith. 

An exemplary list of articles applying their general prindples of ceramic fabrication to 
the types of materials described in applicants' specification are (these references are 
cited on applicant's 1449 form submitted August 5. 1987 and in PTO Form 892 in 
Paper # 20, Examiner's action dated August 8. 1 990): 

1) Oxygen Defect KaNiF^ - Type Oxides: The Compounds La2.x SrxCu04.x/2+6, Nguyen et 
al.. Journal of Solid State Chemistry 39. 120-127 (1981). 

2) The Oxygen Defect Perovskite BaLa^ Cus-On.,. A Metallic Conductor , C. Michel et 
al.. Mat. Res. Bull.. Vol. 20, pp. 667-671. 1985. 



YO987-074BY 



3 



3) Oxygen intercalation in mixed valence copper oxides related to the perovskite, C. 
Michel et al., Revue de Chemie minerale. p. 407. 1984. 

4) Thermal Behaviour of Compositions in the Systems x BaTiOa + (1-x) Ba(Lno5 B05) O3 

V S. Chincholkar et al. Therm. Anal. 6th. Vol. 2., p. 251-^, 1980. 

I have recorded research notes relating to superconductor oxide (perovskite) 
compounds in technical notebook IV with entries from November 12, 1987 to June 14, 
1988 and in technical notebook V with entries continuing from June 7, 1 988 to May 2, 
1989. Complete copies of each of these notebooks are attached - Attachment B - Book 
IV and Attachment C - Book V. Below is a listing of some of the compounds I prepared 
and recorded in these notebooks according to the teaching as described in the 
Bednorz and Mueller patent application using the general principles of ceramic science 
as described in the books and articles listed above. 

In Book IV. YiBa2Cu30x batch CI pellet pressing, sintering notes and powder 
processing specifications start on page 2 and continue intermittently to pg. 40 (pg. 13 
has superconductive susceptibility ounces for pellet 9). Batch C2 YiBa2Cu303 detailed 
from pages 14 to 47. 

In Book V green phase (Y2BaCuOx) microstructural photomicrographs are logged on 
pages 15-17 with notes continuing to pg. 19. The perovskite superconductor BiSrCaCu 
oxide (Bi2.i5Sri.68Cai.7Cu208+5) and related perovskites Ca(2-x)SrxCuOx and Bi2Sr2CuOx 
synthesis notations start and continue through pg. 61 with microstructural 
photomicrographs. 



YO987-074BY 



4 



A series of YiBazCuaOx stoichiometric perturtsations to study compositional effects on 
2nd phase or grain boundary phases and their effect on conductivity (resistivity), 
sintering behavior etc., continue until the end of the book notes on the page dated May 
2, 1989 (page not numbered). These are typical perovskite synthetic procedures, 
microstructural photomicrographs, powder processing methods, characteristic 
susceptibility curve(s), sintering behavior and the like. Additional notes may be 
available in later notebooks. 



The undersigned affiant swears further that all statements made herein of his own 
knowledge are true and that all statements made on information and belief are believed 
to be true; and further that these statements were made with the knowledge that willful 
false statements and the like so made are punishable by fine or imprisonment, or both, 
under Section 1001 of Title 18 of the United States Code and that such willful false 
statements may jeopardize the validity of the application or patent issuing thereon. 




By:__li^L=Jb-JvU^ 




Peter R. Duncombe 



Swomio before me this 



/(P-^davof DnjdQ inJuA. 1 9 



Notary Public * " 

SANDRA M. EMMA 
Notary Public, State of New York 

NO.01PO4935290 
Quatified in Westchester Cmjntv 
Commission Expires July ^ (IffulJ 



YO987-074BY 



5 




ATTACHMENT A 



i 




1 . Compensation doping of BaO. /Sr0.3TiO3 thin films 
Copel, M Baniecki.JD Duncombe.PR Kotecki, D 
Laibowitz, R Neumayer, DA Shaw, TM 

APPLIED PHYSICS LETTERS V73 NI3 SEP 28 1998 PI 832- 1834 

2. Method for Forming Noble Metal Oxides and Structures Formed Thereof. June 1 998 
Duncombe, P. R. Hummel, J. P. Laibowitz, R. B. 

Neumayer, D. A. Saenger.K. L. Schrott.A. G. 
RC 98A 41575 



3. Growth of Bismuth Titanate Films By Chemical Vapor Deposition and Chemical Solution 
Deposition. March 1998. RC-21 124 "lunun 

Neumayer, D. A. Duncombe, P. R. Laibowitz, R. B. 
Shaw,T. Purtell, R. Grill, A. 

4. Dielectric relaxation of Ba0.7SrO.3TiO3 thin films from 1 mHz to 20 GHz Baniecki JD 
Laibowitz, RB Shaw, TM Duncombe, PR 

Neumayer, DA Kotecki, DE Shen, H Ma, QY 
APPLIED PHYSICS LETTERS V72 N4 JAN 26 1998 P498-500 

5. Contrasting magnetic and structural properties of two La manganites with the same 
doping levels 

McGuire, T.R. Duncombe, P.R. Gong, G.Q. Gupta, A. Li, X.W. Pickart S J Crow M L 
J. Appl. Phys. (USA) Vol.83. No.l 1 1 June 1998 P7076-8 

6. Effects of Annealing Conditions on Charge Loss Mechanisms in MOCVD (Ba0.7,Sr0.3)TiO3 
Thin Film Capacitors. 

Baniecki, J.D., Laibowitz, RB Shaw, TM Duncombe, PR Saenger, iCL Cabral C 
Kotecki, DE, Shen, H , Lian. J., Ma, QY 

7. Low Operating Voltage and High Mobility Field Effect Transistors Comproising Pentacene 
and Relatively High Dielectric Constant Insulators RC2 1 233(94806) 7/1 7/98 
Dimitrakopoulos, CD Purushothaman S , Kymissis L Callegari A. , Neumayer DA 
Duncombe PR, Laibowitz RB, Shaw JM ' / . 

8. Maximum Magnetorsistance in Granular Manganite/Insuiator System close to Percolation 
Threshold PACS 10/06/98 rcrcoiauon 

DK Petrov, L Krusin-Elbaum, JZ Sun, C Feild, & PR Duncombe 

9. Magnetorsistance and Hall Effect of Chromium Dioxide Epitaxial Thin Films 
X.W. Li, A. Gupta, T.R. McGuire, P.R. Duncombe, Gang Xiao 

10. Progress Report on High-k dielectric material: amorphous BST from solgel (09/98) 

P. Andry, D. Neumayer. P. Duncombe, C. Dimitrakopoulos, F. Libsch, A. Grill, R. WisniefT 



fTfTro^^t c from The IBM Total InformatiofT^Bi- 



ici/al Center 



MAIN I OTHER 
MENU I OPTIONS 



Personal Inventor History 

NamerDuncombe, P.R. Serial : 155139 LociRES YORKTOWN 

Patent Pts:36 TDB Pts : 1 Total Pts:37 Plateau Lvl : 3 

Plateau Date: 10/24/98 File Update : 11/02/98 

Awards Due : None 



Title: NOVEL METAL ALKOXYALKOXIDECARBOXYLATES AND USE TO FORM FILMS 

06/17/98 Opene d as Disci Y O89802 31 Status: Filed 

06/22/98 Disci Review ' " Action: File ' 

Q) 09/04/98 Filed as Docket Y0998254 in US Rating: 2 Pts:3 

Co- inventors : Neumayer, D.A. 

Title: SELECTIVE GROWTH OF FERROMAGNETIC FILMS FOR MAGNETIC MEMORY, STORAGE - BASED 
DEVICES, AND OTHER DEVICES 

06/17/98 Opened as Disci YO8980225 Status: Filed 

® 06/29/98 Disci Review Action: File " " 

10/15/98 Filed as Docket Y0998268 in US Rating: 2 Pts: 3 

Co-inventors: Guha, S. • Gupta, A. Bojarczuk, N.A. Karasinski, J.M. 

Title: BEOL DECOUPLING CAPACITOR MATERIALS 

01/28/98 Opened as Disci YO8980024 in US Status : Opened 

. 06/24/98 Disci Review Action: File 

Co-inventors: Rosenberg, R. Ning, T.H. Shaw, T.M. Edelstein, D.C. Neumayer, D-A. 

Laibowitz, R.B. ' ^ 

10/01/97 Opened as Disci YO8970512 in US Status : Opened 

09/16/98 Disci Review Action: File 

Title: CAPACITORS WITH AMORPHOUS DIELECTRICS AND IMPROVED DIELECTRIC PROPERTIES MADE 
USING SILICON SURFACES AS ELECTRODES 

06/06/97 Opened as Disci YO8970261 in US Status;Opened 
Co-inventors: Shaw, T.M. Neumayer, D.A. Laibowitz, R.B. 

Title: FABRICATION OF THIN FILM FIELD EFFECT TRANSISTOR COMPRISING AN ORGANIC 
SEMICONDUCTOR AND CHEMICAL SOLUTION DEPOSITED METAL OXIDE 
03/25/97 Opened as Disci YO8970113 Status: Filed 

03/25/97 Disci Review Action: File * 

03/25/97 Filed as Docket YO997083 in US Rating: 2 Pts -3 

^03/24/98 Filed as Docket YO997083 in J A' Rating: 2 

03/16/98 Filed as Docket YO997083 in TA Rating: 2 

"03/12/98 Filed as Docket YO997083 in KO * Rating: 2 

04/24/98 Last Office Action 

Co-inventors: Purushothaman, S. Dimitrakopoulos, CD. Furman, B.K. Neumayer, D.A. 
Laibowitz, R.B. 

Title: NOVEL ALKOXYALKOXIDES AND USE TO FORM FILMS 
10/30/96 Opened as Disci YO8960411 Status: Filed 

03/10/97 Disci Review Action: File 

01/30/98 Filed as Docket YO997069 in US Rating: 2 Pts:3 

Co - inventors : Neumayer, D.A. * - 



3 



11/3/98 2:40 PM 



Title: THIN- FILM FIELD -EFFECT TRANSISTOR WITH ORGANIC SEMICONDUCTOR REOUIRTMr to,, 
OPERATING VOLTAGES ^ 



® 



09/11/96 Opened as Disci YO8960358 
03/04/97 Disci Review 

03/25/97 Filed as Docket YO997057 in US 
03/12/98 Filed as Docket YO997057 in KO. 
04/10/98 Last Office Action 
Co- inventors: Purushothaman , S. Dimitrakopoulos , CD. 
Laibowitz, R.B. 



Status: Filed 
Action: File 
Rating: 2 
Rating: 2 



Pts:3 



Furman, B.K. Netimayer, D.A. 



(D 



Title: HIGH DIELECTRIC CONSTANT, BARIUM LANTHANUM TITANATE THIN Fllil CAPACTTHRQ pad 
RANDOM ACCESS ^v^^iUKb tOK 

06/20/96 Opened as Disci YO8960255 in US Status : Opened 

Co-inventors: Gupta, A. Shaw, T.M. Laibowitz, R.B. 

Title: METHOD FOR FORMING NOBLE METAL OXIDES AND STRUCTURES FORMED THEREOF 
10/30/95 Opened as Disci YO8950450 
11/12/96 Disci Review 

11/05/97 Filed as Docket Y0996239 in US 
10/20/98 Filed as Docket Y0996239 in JA 
07/30/98 Filed as Docket Y099 6239 in TA 
Co-inventors: Schrott, A.G. Saenger, K.: 
Laibowitz, R.B. 



Status: Filed 
Action: File 



Rating: 2 
Rating: 2 
Rating: 2 
Hummel, J. P. 



Pts:3 



Neumayer, D.A. 



Title: PEROXIDE ETCHANT PROCESS FOR PEROVSKITE-TYPE OXIDES 
10/23/95 Opened as Disci YO8950434 Status: Filed 

©08/08/97 Disci Review Action: File 

04/08/98 Filed as Docket Y0997256 in US Rating: 2 Pts:3 

Co-inventors: Rosenberg, R. Cooper, E.I. Laibowitz, R.B. 

Title: RF TRANSPONDER FOR METALLIC SURFACES 

08/02/95 Opened as Disci YO8950329 in US Status : Opened 

Co-inventors: Af zali -ardakani , A. Feild, C.A. Duan, D.W. Brady, M.J. 
Moskowitz, P. A. 

Title: METHOD FOR CLEANING THE SURFACE OF A DIELETRIC 

09/06/95 Opened as Disci FI8950292 Status: Filed 

09/06/95 Sent to Evaluator 

02/05/96 Evaluated Action : Search 

04/19/96 Disci Review Action: File 

12/06/96 Filed as Docket FI996047 in US Rating: 2 Pts-3 

11/29/97 Filed as Docket FI996047 in KO Rating: 2 

05/26/97 Filed as Docket FI996047 in TA Rating: 2 

06/11/98 Last Office Action 

Co-inventors: Kotecki, D.E. Wildman, H.S. Yu, C. Natzle, W. Laibowitz, R.B. 

Title: NANO PHASE FABRICATION OF COPPER-GLASS CERAMIC COMPOSITE VIAS IN CORDIERITE 
SUBSTRATES 

10/05/92 Opened as Disci YO8920907 in US Status : Published 

10/08/92 Sent to Evaluator 

12/17/92 Disci Review Action: Publish 

01/06/93 Mailed to Tech Disci Bulletin 09/02/93 Published Pts : 1 

Co-inventors: Kang, S.K. Shaw, T.M. Brady, M.J. 



Title: METHOD OF SINTERING ALUMINUM NITRODE 
11/06/92 Opened as Disci FI8920668 in US 
11/06/92 Sent to Evaluator 
12/18/92 Closed 

Co -inventors: Takamori, T. Shinde, S.L. 



Status: Closed 



Title: METHOD OF SINTERING ALUMINUM NITRIDE 



2 of 3 



1 1/3/98 2:40 PN 



11/06/92 Opened as 
11/06/92 Sent to Eva" 
12/18/92 Closed 
Co- inventors : Takamori , 



/axuator 



18920667 in US 



:iosed 



T. Shinde, S.L. 



Status: Filed 



Title: ALUMINUM NITRIDE BODY AND METHOD FOR FORMING SAID BODY UTILIZING 
SINTERING ADDITIVE 

08/13/92 Opened as Disci FI8920525 
08/17/92 Sent to Evaluator 
09/29/92 Evaluated Action : Search 

12/23/92 Disci Review Action: File 

05/10/95 Filed as Docket FI992168B in US Rating: 2 " *Pts:3 

05/28/96 Issued as Patent 5520878 in US 
Co - inventors : Takamori, T. Shinde, S.L. 



A VITREOUS 



Title: ALUMINUM NITRIDE BODY AND METHOD FOR FORMING SAID BODY UTILIZING 
SINTERING ADDITIVE 

08/13/92 Opened as Disci FI8920525 
08/17/92 Sent to Evaluator 
09/29/92 Evaluated 
12/23/92 Disci Review 

12/22/93 Filed as Docket FI992168A in US Rating: 2 Pts : 3 

01/09/96 Issued as Patent 5482903 in US 
Co -inventors: Takamori, T. Shinde, S.L. 



A VITREOUS 



Status: Filed 

Action: Search 

Action: File 
Rating: 2 



Title: GOLD DOPING OF YBA2CU307 - 8 AS A MEANS OF INCREASING TRANSPORT CRITICAL 
CURRENT DENSITY 

02/12/92 Opened as Disci YO8920161 in US Status:Closed 
02/14/92 Sent to Evaluator 
05/15/92 Closed 

Co-inventors: Daeumling, M. Shaw, T.M. 

Title: PROCESS FOR PRODUCING CERAMIC CIRCUIT STRUCTURES HAVING CONDUCTIVE VIAS 
07/19/89 Opened as Disci YO8890552 Status: Filed 

07/25/89 Sent to Evaluator 
08/10/89 Evaluated 
07/30/90 Disci Review 

12/17/92 Filed as Docket YO990091B in US Rating: 2 Pts: 3 

08/16/94 Issued as Patent 5337475 in US 
Co-inventors: Vallabhaneni, R.V. Giess, 



Action: Search 

Action: File 
Rating: 2 



Vanhise, J. A. 
Neisser, M.O. 



Aoude , F . Y . 
Park, J.M. 



E.A. 

Muller- landau, F. 



Farooq, S, 
Shaw, R.R, 



Cooper, E.I, Kim, 
Walker, G.F. Rita, 



Shaw, T.M. Brownlow, J,M. Kim, J. Knickerbocker, 



Y.H. 
R.A. 
S.H. 



Title: VIA PASTE COMPOSITIONS AND USE THEREOF TO FORM CONDUCTIVE VIAS IN CIRCUTTT7Fn 
CERAMIC SUBSTRATES 



Status: Filed 

Action: Search 

Action: File 
Rating: 2 



07/19/89 Opened as Disci YO8890552 
07/25/89 Sent to Evaluator 
08/10/89 Evaluated 
07/30/90 Disci Review 

03/20/91 Filed as Docket YO990091A in US Rating: 2 Pts ■ 3 

02/01/94 Issued as Patent 5283104 in US 
Co-inventors: Vallabhaneni, R.V. Giess, E.A. Farooq, S. Cooper, E.I. Kim, 
Vanhise, J. A. Aoude, F.Y. Muller - landau, F. Shaw, R.R. Walker, G F " Rita' 
Neisser, M.O. Park, J.M. Shaw, T.M. Brownlow, J.M. Kim, J. KAickerbocker ! 

Call your award coordinator, IPL department, or T/L 826-2680 for help. 



Y.H. 
R.A- 
S.H. 





vSEND 


1 

1 MENU 


1 OTHER 
1 OPTIONS 



3 of 3 



1 1/3/98 2:40 P 



Emp. Sen 155 




• T.R. McGuirc. A. Gupta. P.R. Duneombc. M. Rupp JZ. Sun RB «, . ^ .. 

• TJt McOuire. P.R. Duntombt. O.Q. Oo»s. A. Oupa X W Li i r, -ka . 

Manganatc Perovskitcs" to appear Appl. Phys. Lett Pen,end.cular Transport Devices Made Using Doped 

• J.Z. Sun, L. Kiusin-Elbaum, P.R. Duncombc A Guota A R r i o i„ • -o - 
Pcn,vskite Manganate Trilayer Junctions" A^L su^ion n/96 ^P"-'''"--'' Tunneling in Doped 

• T.R. McGuire, P.R. Duncombc. CQ. Gong, A. Guota. X W r i v ... 
Magnetoresistance Of LCMO/LSMO 67/3? Multilayt" APL sutmt^^^^^^ '""'"^'^ ^"P""^ * 

• R-B Laibowitz, T.M. Shaw, D.E Kotecki. S. Tiwari. A. Gupta A Grill & P R n 
App..^.s origin Pil^ori^dUntb.^^ 

' vi^Si7^'rmS^^^^^ ^"^'•^ ""•"^■•nS A Vitreous Sintering Additive" 

• vL^rsr:s;g\^^^^^^ ^pr fsstra^^^r- ^^'^ ^ 

• Ah Afeali-Ardakani.:Mike Brady. Dah-Weih Duan. Peter Duncombe Thnc p -.^ .m 
Transponder for Metallic Surfaces" Docket#:YOm-03r9 submr^'^J ""^ 

• D.E. Kotecki, R.B. Laibowitz, W. Natzle C Yu. H W.Mmon d d 

• D.A. Neumayer. P.R. Duncombe. R.B. Laibowitz. & A Grill n.i d 

International Symposium on Integrated Ferroelec^cs (IShJ^ LSi^Ll^! N M '° 

• A. Grill. R. Laibowitz. D. Beach, D Neumaver & P R n k 

Electrical Properties of PLT IBM RC 20402 (901 Ssj 3/5^5"*^"' "^^"^^ °" -^^^ Cystallization & 

• D.A. Neumayer. P.R. Duncombc. R.B. UibowitE & A Grill -Ffr^. r-r r. 

Sol-Gel Derived Bi4Ti30I2 Films" ISIF sobill^Son "^""^ '"^^'^^ °" Co^stallization of 

• CD. Dimitrakopoulos. P.R. Duncombe B K Furman R R i ,:k„ -. r^ v. 

■ ^S-T^"*^- °- ^-s-. AO. s..„„ ^^^^^ ^ 

• T. Shaw. R.B. Laibowitz, P.R. Duncombe & A. Gupta • Hich Dielccrrir rn„c, .0 , 

DRAM Structures" Disclosure U: yO898-0681 rateS File 1/96 in ^^^^^^^^^^^ T"''^"^<«-Based 

• P^e^lXr """^"""^ ^'-.e Films- VO896-04x. rated File 10/96 in ^ 



IBM Commit ments: To Win 

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22 5=«!B/WS^^»f2i*f!<* 

COHPS SCRIPT Al dac«d 87/12/02 14:32:2$ r«s« 1 



D«C« 
FroB 

To: 



2 &ecub«r 1987, 13:24:31 EST 

PLECKAT at YICrVMZ 

PSD 



T1i« laboratory results on your samples are: 



« CI 


T 

0.03 


Ba Cu 0 Cu«I, KP 
0.6B X 


f C2 


r 


78.1 t (V/V) 


# C3 


Ba . 


.. «6.9 I - 


ff C4 


Tl . 


- S7.3 X - / error du« to static electr. 

durinc welchinc of x«^UI/ 


# cs 


Ti . 
Sr . 


- 22.2 X . - 
. 49.4 X - . 


1 « 


Tl . 
Sr . 


, 24.2 X - 
VSO.4 X - 


# C7 


T 

0.34 


Ba Cu 0 Cu=l 
0.71- XC^ 


# C8 


T 

0.34 


Ba Cto O J - - 

0.71 — .-^ 


# C9 


T 

2.37 


Ba Ca 0 

1.10 X 




KKP 



Date 
Fcoa 

To: 



; 21 Octobar 1987, 10:45:18 EOT 
; PUCKAT at TCTVMZ 
PRO 

The laboratory results oo your saaples are: 



9 CI 


T 

0-35 


Ba 

0.72 


Cu 


0 
X 


Cu=l, 


ICP 


# Clf 


T 

0.33 


Ba 

0.70 


Cu 


6 

X 






ff cs 


T 

2.21 


Ba 

1.06 


Cu 


0 
X 







Other results to follow froa Olson, 
MMP 

Note: I have produced a ti^ht creen conpouod f co« 123 with 

the formila: T Ba Cu O . If Interested. s«t In touch 

12 3 X 
with ae. ^ - 



The above understood 



Oct« 



Date 




uate and sign everv entry. Ha«^ e K»ss(bly Important H Uncte^ied n inu o 

entry witnessed SiA)f5lHa I Sc jdosure of nSSSr o g Confi<*eatia*-Restricted 

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0,^Y O-^'-N 




The above understood 



Date 



and 



Dat« 



□ IBM Internal Use Ot* 

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legistered IBM ConGdentiar 
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24 



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BRIEF ATTACHMENT AM 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479,810 
Filed: June?, 1995 



Group Art Unit: 1751 
Exanfiiner: M. Kopec 



Date: April 14, 2005 
Docket: YO987-074BZ 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



In response to the Office Action dated July 28, 2004, please consider the 
following: 



SIXTH SUPPLEMENTAL AMENDMENT 



Sir: 



Serial No.: 08/479,810 



Page 1 of 5 



Docket: YO987-074BZ 



RECEIPT 

IN THE UNITED STATES PATEtlTAND TRADEMARK OFRCE 

/^^^^\ 

In re Patent Application of / Date: April 14, 2005 

Applicants: Bednorz et al. I ftpR 1 5 ?BD5 Docket: YO987-074BZ 

Serial No.: 08/479.810 ^ ^ Group Art Unit: 1751 

Filed: June 7, 1995 Xiira^^ Examiner: M. Kopec 

For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE. METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria. VA 22313-1450 



r era 
r c-n 



Sir: 



AFFIDAVIT UNDER 37 C,F,R, 1,132 ^f- 



L Thomas M. Shaw, being duly sworn, do hereby depose and state: ~^ 



* • 
ro 

U3 



1. I received a B. S. degree In Metallurgy from the University of Liverpool, Liverpool, 
England and a M. S. and a Ph.D. degree in Material Science (1981) from the University 
of California, Beri<eley. 

2. I refer to Attachments A to Z and AA herein which were submitted in a separate 
paper designated as "FIRST SUPPLEMENTAL AMENDMENT' In response to the 
Office Action dated July 28. 2004. I also refer to Attachments AB to AG which were 
submitted in a separate paper designated as 'THIRD SUPPLEMENTAL AMENDMENT" 
In response to the Office Action dated July 28. 2004. 

3. I have worked as a postdoctoral researcher in the Material Science Department 
of Cornell University forni 1981-1982. I have worked at Rockwell International Science 
Center in Thousand Oaks, California from 1982-1984 as a ceramic scientist. I have 
worked as a research staff member in Ceramics Science at the Thomas J. Watson 
Research Center of the International Business Machines Corporation in Yorktown 
Heights, New Yoric from 1 984 to the present. 



Serial No.: 08/479.810 



Page 1 of 21 



Docket: YO987-074BZ 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479,810 
Filed: June 7. 1995 



Group Art Unit: 1751 
Examiner: M. Kopec 



Date: April 14, 2005 
Docket: YO987-074BZ 



For. NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 

Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



I, Thomas M. Shaw, being duly sworn, do hereby depose and state: 

1. I received a B. S. degree in Metallurgy from the University of Liverpool, Liverpool, 
England and a M. S. and a Ph.D. degree in Material Science (1981) from the University 
of California, Berkeley. 

2. I refer to Attachments A to Z and AA herein which were submitted in a separate 
paper designated as "FIRST SUPPLEMENTAL AMENDMENT' in response to the 
Office Action dated July 28, 2004. I also refer to Attachments AB to AG which were 
submitted in a separate paper designated as "THIRD SUPPLEMENTAL AMENDMENT' 
in response to the Office Action dated July 28, 2004. 

3. I have worked as a postdoctoral researcher in the Material Science Department 
of Cornell University form 1981-1982. I have worked at Rockwell International Science 
Center in Thousand Oaks, California from 1982-1984 as a ceramic scientist. I have 
worked as a research staff member in Ceramics Science at the Thomas J. Watson 
Research Center of the International Business Machines Corporation in Yorktown 
Heights. New York from 1 984 to the present. 



Serial No.: 08/479,810 Page 1 of 21 Docket: YO987-074BZ 



AFFIDAVIT UNDER 37 C.F.R. 1.132 



Sir: 



4. I have worked in the fabrication of and characterization of ceramic materials of 
various types, including superconductors and related materials from 1984 to the 
present. 

5. My resume and list of publications is in Attachment 1 included with this affidavit. 

6. This affidavit is in addition to my affidavit dated December 15, 1998. I have 
reviewed the above-identified patent application (Bednorz-Mueller application) and 
acknowledge that it represents the work of Bednorz and Mueller, which is generally 
recognized as the first discovery of superconductivity in a material having a Tc ^ 26°K 
and that subsequent developments in this field have been based on this work. 

7. All the high temperature superconductors which have been developed based on 
the work of Bednorz and Mueller behave in a similar manner, conduct current in a 
similar manner, have similar magnetic properties, and have similar structural properties. 

8. Once a person of skill in the art knows of a specific type of composition 
described in the Bednorz-Mueller application which is superconducting at greater than 
or equal to 26°K, such a person of skill in the art, using the techniques described in the 
Bednorz-Mueller application, which includes all principles of ceramic fabrication known 
at the time the application was initially filed, can make the compositions encompassed 
by the claims of the Bednorz-Mueller application, without undue experimentation or 
without requiring ingenuity beyond that expected of a person of skill in the art of the 
fabrication of ceramic materials. This is why the wori< of Bednorz and Mueller was 
reproduced so quickly after their discovery and why so much additional work was done 
in this field within a short period after their discovery. Bednorz and Mueller's discovery 
was first reported in Z. Phys. B 64 page 189-193 (1996). 

9. The techniques for placing a superconductive composition into a 
superconducting state have been known since the discovery of superconductivity in 
1911 by Kameriingh-Onnes. 



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10. Prior to 1 986 a person having a bachelor's degree in an engineering discipline, 
applied science, chemistry, physics or a related discipline could have been trained 
within one year to reliably test a material for the presence of superconductivity and to 
flow a superconductive current in a superconductive composition. 

1 1 . Prior to 1 986 a person of ordinary skill in the art of fabricating a composition 
according to the teaching of the Bednorz-Mueller application would have: a) a Ph.D. 
degree in solid state chemistry, applied physics, material science, metallurgy, physics or 
a related discipline and have done thesis research including wori< in the fabrication of 
ceramic materials; or b) have a Ph.D. degree in these same fields having done 
experimental thesis research plus one to two years post Ph.D. wori< in the fabrication of 
ceramic materials; or c) have a master's degree in these same fields and have had five 
years of materials experience at least some of which is in the fabrication of ceramic 
materials. Such a person is referred to herein as a person of ordinary skill in the 
ceramic fabrication art. 

12. The general principles of ceramic science referred to by Bednorz and Mueller in 
their patent application and known to a person of ordinary skill in the ceramic fabrication 
art can be found in many books and articles published before their discovery, priority 
date (date of filing of their European Patent Office patent application EPO 0275343A1 , 
January 23, 1987) and initial US Application filing date (May 22, 1987). An exemplary 
list of books describing the general principles of ceramic fabrication are: 

a) Introduction to Ceramics, Kingery et al.. Second Edition, John 
Wiley & Sons, 1976, in particular pages 5-20, 269-319, 381-447 and 
448-51 3, a copy of which is in Attachment B. 

b) Polar Dielectrics and Their Applications^ Burfoot et al., University of 
California Press, 1979, in particular pages 13-33, a copy of which is in 
Attachment C. 



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c) Ceramic Processing Before Firing, Onoda et al., John Wiley & 
Sons, 1978, the entire book, a copy of which is in Attachment D. 

d) Structure, Properties and Preparation of Perovskite-Type 
Compounds, F. S. Galasso , Pergamon Press, 1969, in particular pages 
1 59-1 86, a copy of which Is In Attachment E. 

These references were previously submitted with the Affidavit of Thomas Shaw 
submitted December 15, 1998. 

1 3. An exemplary list of articles applying the general principles of ceramic fabrication 
to the types of materials described In Applicants' specification are: 

a) Oxygen Defect K2NiF4 - Type Oxides: The Compounds 
Lag-xSrxCuOt-xcv, Nguyen et al., Journal of Solid State Chemistry 39, 
1 20-1 27 (1 981 ). See Attachment F. 

b) The Oxygen Defect Perovskite BaLa4Cus-Oi3.4, A Metallic (This Is 
referred to In the Bednorz-Mueller application at page 21 , lines 1-2) 
Conductor, C. Michel et al.. Mat. Res. Bull., Vol. 20, pp. 667-671, 1985. 
See Attachment G. 

c) Oxygen Intercalation in Mixed Valence Copper Oxides Related to 
the Perovskite, C. Michel et al.. Revue de Chemie MInerale, 21 , p. 407, 
1984. (This is referred to In the Bednorz-Mueller application at page 27, 
lines 1-2). See Attachment H. 

d) Thermal Behaviour of Compositions In the Systems x BaTiOa + 
(1-x) Ba(Lno.5 Bos) O3, V.S. Chincholkar et al., Therm. Anal. 6th, Vol. 2., p. 
251-6,1980. See Attachment I. 



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14. The Bednorz-Mueller application in the paragraph bridging pages 6 and 7 states 
In regard to the high Tc materials: 

These compositions can carry supercurrents (i.e., electrical currents in a 
substantially zero resistance state of the composition) at temperatures 
greater than 26°K. In general, the compositions are characterized as 
mixed transition metal oxide systems where the transition metal oxide can 
exhibit multivalent behavior. These compositions have a layer-type 
crystalline structure, often perovskite-like, and can contain a rare earth or 
rare earth-like element. A rare earth-like element (sometimes termed a 
near rare earth element is one whose properties make it essentially a rare 
earth element. An example is a group NIB element of the periodic table, 
such as La. Substitutions can be found In the rare earth (or rare 
earth-like) site or In the transition metal sites of the compositions. For 
example, the rare earth site can also include alkaline earth elements 
selected from group HA of the periodic table, or a combination of rare 
earth or rare earth-like elements and alkaline earth elements. Examples 
of suitable alkaline earths include Ca, Sr, and Ba. The transition metal 
site can include a transition metal exhibiting mixed valent behavior, and 
can include more than one transition metal. A particularly good example 
of a suitable transition metal is copper. As will be apparent later, Cu- 
oxide based systems provide unique and excellent properties as high Tc 
superconductors. An example of a superconductive composition having 
high Tc is the composition represented by the formula RE-TM-0, where 
RE Is a rare earth or rare earthHike element, TM is a nonmagnetic 
transition metal, and 0 Is oxygen. Examples of transition metal elements 
Include Cu, Ni, Crete. In particular, transition metals that can exhibit 
multi-valent states are veiy suitable. The rare earth elements are typically 
elements 58-71 of the periodic table, including Ce, Nd, etc. 



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15. In the passage quoted in paragraph 14 the general formula is RE-TM-0 "where 
RE is a rare earth or rare earth-like element, TM is a nonmagnetic transition metal, and 
0 is oxygen." This paragraph states "Substitutions can be found in the rare earth (or 
rare earth-lil<e) site or in the transition metal sites of the compositions. For example, the 
rare earth site can also include alkaline earth elements selected from group HA of the 
periodic table, or a combination of rare earth or rare earth-like elements and alkaline 
earth elements." Thus applicants teach that RE can be something other than an rare 
earth. For example, it can be an alkaline earth, but is not limited to a alkaline earth 
element. It can be an element that has the same effect as an alkaline earth or 
rare-earth element, that is a rare earth like element. Also, this passage teaches that 
TM can be substituted with another element, for example, but not limited to, a rare 
earth, alkaline earth or some other element that acts in place of the transition metal. 

16. The following table is compiled from the Table 1 of the Article by Rao (See 
Attachment AB) and the Table of high Tc materials from the "CRC Handbook of 
Chemistry and Physics" 2000-2001 Edition (See Attachment AC). An asterisk in 
column 5 indicated that the composition of column 2 does not come within the scope of 
the claims allowed In the Office Action of July 28, 2004. 

17. I have reviewed the Office Action dated July 28, 2004, which states at page 6 
"The present specification is deemed to be enabled only for comp>ositions comprising a 
transition metal oxide containing at least a) an alkaline earth element and b) a 
rare-earth element of Group inB element." I disagree for the reasons given herein. 



18. Composite Table 



1 


2 


3 


4 


5 


6 


7 


# 


MATERIAL 


RAO 

ARTICLE 


HANDBOOK 
OFCHEM& 
PHYSICS 




ALKALINE 

EARTH 

ELEMENT 


RARE 
EARTH 
ELEME 
NT 


1 


La2Cu044^ 




v 


* 


N 


Y 


2 


La2-xSrx(Bax)Cu04 


V 


V 




Y 


Y 


3 


La2Cai-xSrxCu206 




V 




Y 


Y 



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4 


YBa2Cu307 


V 


V 




Y 


Y 


5 


YBaiCmOs 


V 


V 




Y 


Y 


6 


Y2Ba4Cu70i5 


V 


V 




Y 


Y 


7 


Bi2Sr2Cu06 


V 


V 


* 


Y 


N 


8 


Bi2CaSr2Cu208 


V 


V 


* 


Y 


N 


9 


Bi2Ca2Sr2eu30io 


V 


V 


* 


Y 


N 


10 


BhSrifLiii xCex^iCu^Oio 


V 


V 




Y 


Y 


11 


Tl2Ba2Cu06 


V 


V 


* 


Y 


N 


12 


Tl2CaBa2Cu208 


V 


V 


* 


Y 


N 


13 


Tl2Ca2Ba2Cu30io 




V 


* 


Y 


N 


14 


Tl(BaLa)Cu05 


V 


V 




Y 


Y 


15 


Tl(SrLa)Cu05 


V 


^ 




Y 


Y 


16 


(Tlo.5Pbo.5)Sr2Cu05 


V 




* 


Y 


N 


17 


TlCaBa2Cu207 


V 




* 


Y 


N 


18 


(Tlo.5Pbo.5)CaSr2Cu207 


V 




* 


Y 


N 


19 


TlSr2Yo.5Cao.5Cu207 








Y 


Y 


20 


TlCa2Ba2Cu308 




V 


* 


Y 


N 


21 


(Tlo.5Pbo.5)Sr2Ca2Cu309 


V 


V 


* 


Y 


N 


22 


TlBa2(Lni-xCex)2Cu209 


V 


V 




Y 


Y 


23 


Pb2Sr2Lno.5Cao5Cu308 




V 




Y 


Y 


24 


PbjfSrXa^jCuiOfi 


V 


V 




Y 


Y 


25 


(Pb,Cu)Sr2(Ln,Ca)Cu207 


V 


V 




Y 


Y 


26 


(Pb,Cu)(Sr,Eu)(Eu,Ce)Cu20x 




V 




Y 


Y 


27 


Nd2.xCexCu04 




V 


* 


N 


Y 


28 


Ca,.xNdxCu02 








Y 


Y 


29 


Sr,.xNdxCu02 


V 


V 




Y 


Y 


30 


Cai-xSrxCu02 






* 


Y 


N 


31 


Bao.6Ko.4Bi03 




V. 


* 


Y 


N 


32 


Jv D*? V-/ S AH 






* 


N 


Y 


33 


NdBa^Cu^O? 








Y 


Y 


34 


SmBaSrCuO? 




V 




Y 


Y 


35 


EuBaSrCutlOv 




V 




Y 


Y 


36 


BaSrCu307 






* 


Y 


N 


37 


DyBaSrCu307 








Y 

I- 


Y 


38 


HuBaSrCu307 




V 




Y 


Y 


39 


ErBaSrCu307 (Multiphase) 




V 




Y 


Y 


40 


TmBaSrCu307 (Multiphase) 








Y 


Y 



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41 


YBaSrCusO? 




V 


* 


Y 


Y 


42 


HgBa2Cu02 






* 


Y 


N 


43 


HgBazCaCusOfi 
(annealed in O2) 




V 


* 


Y 


N 


44 


HgBazCaiCujOg 




yl 


* 


Y 


N 


45 


HgBa2Ca3Cu40,o 






* 


Y 


N 



19. The first composition, Laz Cu 04+^ , has the form RE2CUO4 which is explicitly 
taught by Bednorz and Mueller. The d indicates that there is a nonstoichiometric 
amount of oxygen. 



20. The Bednorz-Mueller application teaches at page 1 1 , line 1 9 to page 1 2, line 7: 

An example of a superconductive compound having a layer-type stmcture 
in accordance with the present invention Is an oxide of the general 
composition RE2TMO4 where RE stands for the rare earths (lanthanides) 
or rare earth-like elements and TM stands for a transition metal. In these 
compounds the RE portion can be partially substituted by one or more 
members of the alkaline earth group of elements. In these particular 
compounds, the oxygen content is at a deficit. For example, one such 
compound that meets this general description is lanthanum copper oxide 
LaaCuOA... 

21 . The Bednorz-Mueller application at page 1 5, last paragraph states "Despite their 
metallic character, the Ba-La-Cu-0 type materials are essentially ceramics, as are other 
compounds of the RE2 TMO4 type, and their manufacture generally follows known 
principles of ceramic fabrication." 



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22. Compound number 27 of the composite table contains Nd and Ce, both rare 
earth elements. All of the other compounds of the composite table, except for number 
32, have O and one of the alkaline earth elements which as stated above is explicitly 
taught by applicants. Compound 31 is a BiOa compound In which TM is substituted by 
another element, here Bi, as explicitly taught by Applicants in the paragraph quoted 
above. 

23. The rare earth elements are Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, 
Er, Tm, Yb, and Lu. See the Handbook of Chemistry and Physics 59th edition 
1978-1 979 page 8262 in Appendix A. The transition elements are identified in the 
periodic table from the inside front cover of the Handbook of Chemistry and Physics In 
Appendix A. 

24. The basic theory of superconductivity has been known many years before 
Applicante' discovery. For example, see the book "Theory of Superconductivity", M. 
von Laue, Academic Press, Inc., 1952 (See Attachment AD). 

25. In the composite table, compound numbers 7 to 10 and 31 are Bismuth (Bi) 
compounds. Compound number 12 to 22 are Thallium (Tl) compounds. Compound 
numbers 23 to 26 are lead (Pb) compounds. Compounds 42 to 45 are Mercury (Hg) 
compounds. Those compounds that do not come within the scope of an allowed claims 
(the compounds which are not marked with an asterisk in column 3 of the composite 
table) are primarily the Bi, Tl, Pb and Hg compounds. These compounds are made 
according to the principles of ceramic science known prior to applicant's filing date. For 
example, Attachments J, K, L, and M contain the following articles: 

Attachment J - Phys. Rev. B. Vol. 38, No. 16, p. 6531 (1988) is directed to 
Thallium compounds. 

Attachment K - Jap. Joun. of Appl. Phys., Vol. 27, No. 2, p. I_209-L210 
(1988) Is directed to Bismuth (Bi) compounds. 



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Attachment L - Letter to Nature, Vol. 38, No. 2, p. 226 (18 March 1993) is 
directed to Mercury (Hg) compounds. 

Attachment M - Nature, Vol. 336. p. 211 (17 November 1988) is directed 
to Lead (Pb) based compounds. 

26. The article of Attachment J (directed to Tl compounds) states at page 6531 , left 
column: 

The samples were prepared by thoroughly mixing suitable amounts of 
TI2O3, CaO, BaOz, and CuO, and fonning a pellet of this mixture under 
pressure. The pellet was then wrapped in gold foil, sealed in quartz tube 
containing slightly less than 1 atm of oxygen, and fctaked for approximately 
3hat=:880°C. 

This is according to the general principles of ceramic science known prior to 
applicant's priority date. 

27. The article of Attachment K (directed to Bi compounds) states at page L209: 

The Bi-Sr-Ca-Cu-0 oxide samples were prepared from powder reagents 
of Bi203, SrCOa, CaCOa and CuO. The appropriate amounts of powders 
were mixed, calcined at 800-870*C for 5 h, thoroughly reground and then 
cold-pressed into disk-shape pellets (20 mm in diameter and 2 mm in 
thickness) at a pressure of 2 ton.cm^. Most of the pellets were sintered at 
about 870'C in air or in an oxygen atmosphere and then furnace-cooled to 
room temperature. 

This is according to the general principles of ceramic science known prior to 
applicant's priority date. 



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28. The article of Attachment L (directed to Hg compounds) states at page 226: 

The samples were prepared by solid state reaction between stoichiometric 
mixtures of BaaCuOa*^ and yellow HgO (98% purity, Aldrich). The 
precursor BaaCuOa*^ was obtained by the same type of reaction between 
BaOa (95% purity, Aldrich) and CuO (NormalPur, Prolabo) at 930°C in 
oxygen, according to the procedure described by De Leeuw et al.^. The 
powders were ground in an agate mortar and placed in silica tubes. All 
these operations were carried out in a dry box. After evacuation, the 
tut>es were sealed, placed in steel containers, as described in ref. 3, and 
heated for 5 h to reach -SOCC. The samples were then cooled in the 
furnace, reaching room temperature after ~1 0 h. 

This is according to the general principles of ceramic science known prior to 
applicants priority date. 

29. The article of Attachment M (directed to Pb compounds) states at page 21 1 , left 
column: 

The preparative conditions for the new materials are considerably more 
stringent than for the previously known copper-based superconductors. 
Direct synthesis of members of this family by reaction of the component 
metal oxides or cartjonates in air or oxygen at temperatures below 900°C 
is not possible because of the stability of the oxidized SrPbOs-based 
perovskite. Successful synthesis is accomplished by the reaction of PbO 
with pre-reacted (Sr, Ca, Ln) oxide precursors. The precursors are 
prepared from oxides and carisonates in the appropriate metal ratios, 
calcined for 16 hours (in dense AI2O3 crucibles) at 920-980°C in air with 
one intermediate grinding. 



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This is according to the principles of ceramic science l<nown prior to applicant's 
priority date. 

30. A person of ordinary skill in the art of the fabrication of ceramic materials would 
be motivated by the teaching of the Bednorz-Mueller application to investigate 
compositions for high superconductivity other than the compositions specifically 
fabricated by Bednorz and Mueller. 

31 . In Attachment U, there is a list of perovskite materials from pages 1 91 to 207 in 
the book "Structure, Properties and Preparation of Perovskite-Type Compounds" by F. 
S. Galasso, published in 1969, which Is Attachment E hereto. This list contains about 
300 compounds. Thus, what the tenri "Perovskite-type" means and how to make these 
compounds was well known to a person of ordinary skill in the art in 1969, more than 17 
years before the Applicants' priority date (January 23, 1987). 

This is clear evidence that a person of skill in the art of fabrication of ceramic 
materials knows (prior to Applicants' priority date) how to make the types of materials in 
Table 1 of the Rao Article and the Table from the Handbook of Chemistry and Physics 
as listed in the composite table above in paragraph 17. 

32. The standard reference "Landholt-Bomstein", Volumn 4, "Magnetic and Other 
Properties of Oxides and Related Compounds Part A" (1970) lists at page 148 to 206 
Perovskite and Perovskite-related stmctures. (See Attachment N). Section 3.2 starting 
at page 190 is entitled "Descriptions of perovskite-related structures". The German title 
is "Perowskit-anliche Strukturen". The German word "aniiche" can be translated in 
English as "like". The Langenscheidt's German-English, English-German Dictionary 
1970, at page 446 translates the English "like" as the Gemian "aniiche". (See 
Attachment O). Pages 126 to 147 of Attachment N describes "crystallographic and 
magnetic properties of perovskite and perovskite-related compounds", see title of 
Section 3 at page 126. Section 3.2.3.1 starting at page 192 of "Landholt-Bomstein" 
Vol. 4 (See Attachment N) is entitled "Bismuth Compounds". Thus Bismuth 



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perovskite-like compounds and how to make them were well known more than 16 years 
prior to Applicants' priority date. Thus the "Landholt Bomstein" tx)ok published in 1970, 
more than 16 years before Applicants' priority date (January 23, 1987), shows that the 
term "perovskite-like" or "perovskite related" is understood by persons of skill In the art 
prior to Applicants' priority date. Moreover, the "Landholt-Bornstein" book cites 
references for each compound listed. Thus a person of ordinary skill in the art of 
ceramic fabrication knows how to make each of these compounds. Pages 376-380 of 
Attachment N has figures showing the crystal structure of compounds containing 81 and 
Pb. 

33. The standard reference "Landholt-Bornstein, Volume 3, Ferro- and 
Antiferroelectric Substances" (1969) provides at pages 571-584 an index to 
substances. (See Attachment P). This list contains numerous Bi and Pb containing 
compounds. See, for example pages 578 and 582-584. Thus a person of ordinary skill 
in the art of ceramic fabrication would be motivated by Applicants' application to 
fabricate Bi and/or Pb containing compounds that come within the scope of the 
Applicants' claims. 

34. The standard reference "Landholt-Bornstein Volume 3 Ferro- and 
Antiferroelectric Substances" (1969) (See Attachment P) at page 37, section 1 is 
entitled "Perovskite-type oxides." This standard reference was published more than 17 
years before Applicants' priority date (January 23, 1987). The properties of 
perovskite-type oxides are listed from pages 37 to 88. Thus the term perovskite-type 
was well known and understood by persons of skill in the art of ceramic fabrication prior 
to Applicants' priority date and more than 17 years before Applicants' priority date 
persons of ordinary skill in the art knew how to make Bi, Pb and many other perovskite, 
perovskite-like, perovskite-related and perovskite-type compounds. 



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35. At page 1 4, line 1 0-1 5 of the Bednorz-Mueller application, Applicants' state 
"samples in the Ba-La-Cu-0 system, when subjected to x-ray analysis, revealed three 
individual crystallographic phases V.12. a first layer-type perovskite-lil<e phase, related 
to the K2N1F4 structure ..." Applicants' priority document EP0275343A1 filed July 27, 
1988, is entitled "New Superconductive Compounds of the K2NIF4 Structural Type 
Having a High Transition Temperature, and l\1ethod for Fabricating Same." See (See 
Attachment AE). The book "Stmcture and Properties of Inorganic Solids" by Francis S. 
Galasso, Pergamon Press (1969) at page 190 lists examples of Tallium (Tl) compounds 
in the K2NiF4 structure. (See Attachment Q). Thus based on Applicants' teachings prior 
to Applicants' priority date, a person of ordinary skill in the art of ceramic fabrication 
would be motivated to fabricate Thallium based compounds to test for high Tc 
superconductivity. 

36. The book "Crystal Stmctures" Volume 4, by Ralph W. G. Wyckoff, Interscience 
Publishers, 1960 states at page 96 "This structure, like these of Bi4Ti20i2 (IX, F12) and 
Ba BU Ti4 O4 (XI, 13) is built up of alternating BizOz and perovskite-like layers." Thus 
layer of perovskite-like Bismuth compounds was well known in the art in 1960 more 
than 26 years before Applicants' priority date. (See Attachment R). 

37. The book "Modern Oxide Materials Preparation, Properties and Device 
Applications" edited by Cockayne and Jones, Academic Press (1972) states (See 
Attachment S) at page 155 under the heading "Layer Structure Oxides and Complex 
Compounds": 

"A large number of layer structure compounds of general fomiula (BiaOa)^* 
(Ax-iBxOax+i)^" have been reported (Smolenskii et al. 1961; Subbarao, 
1962), where A = Ca, Sr, Ba, Pb, etc., B = Ti, Nb, Ta and x = 2, 3, 4, or 5. 
The structure had been previously investigated by Aurivillius (1949) who 
described them in terms of Alternate (BibOz)^* layers and perovskite layers 
of oxygen octahedra. Few have been found to be ferroelectric and 
include SrBizTazOg (Tc = 583'*K), PbBizTaaOg (To = 703"K), BiBigTisTiOia or 



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Bi4Ti30,2 (Tc = 948*'K), BaaBUTisOie (Tc = 598**K) and PbaBiATIgOis (Tc = 
SSS^'K). Only bismuth titanate Bi4Ti30i2 has been investigated in detail in 
the single crystal form and is finding applications in optical stores 
(Cummins, 1967) because of its unique ferroelectric-optical switching 
properties. The ceramics of other members have some interest because 
of their dielectric properties. More complex compounds and solid 
solutions are realizable in these layer stmcture oxides but none have 
significant practical application." 

Thus the term layered oxides was well known and understood prior to Applicants' 
priority date. Moreover, layered Bi and Pb compounds were well known in 1972 more 
than 15 years before Applicants' priority date. 

38. The standard reference "Landholt-Bornstein, Volume 3, Ferro and 
Antiferroelectric Substances" (1969) at pages 107 to 1 14 (See Attachment T) list 
"layer-structure oxides" and their properties. Thus the temn "layered compounds" was 
well known in the art of ceramic fabrication in 1 969 more than 1 6 years prior to 
Applicants' priority date and how to make layered compounds was well known prior to 
applicants priority date. 

39. Layer perovskite type Bi and Pb compounds closely related to the Bi and Pb high 
Tc compounds in the composite table above In paragraph 17 have been known for 
some time. For example, the following is a list of four articles which were published 
about 35 years prior to Applicants' first publication date: 

(1 ) Attachment V - "Mixed bismuth oxides with layer lattices", B. 
Aurivillius, Ari<iv Kemi 1 , 463, (1950). 

(2) Attachment W - "Mixed bismuth oxides with layered lattices ", B. 
Aurivillius, Ari<iv Kemi 1 , 499, (1950). 



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(3) Attachment X - "Mixed bismuth oxides with layered lattices ", B. 
Aurivillius, Arkiv Kemi 2, 519. (1951). 

(4) Attachment Y - "The structure of BizNbOsF and isomorphous 
compounds", B. Aurivillius, Ari<iv Kemi 5, 39, (1952). 

These articles will be referred to as Aurivillius 1, 2, 3 and 4, respectively. 

40. Attachment V (Aurivillius 1 ), at page 463, the first page, has the subtitle "I. The 
structure type of CaNb2Bi209. Attachment V states at page 463: 

X-ray analysis ... seemed to show that the structure was built up of 8120^"^ 
layers parallel to the basal plane and sheets of composition BiaTiaCFio". 
The atomic an-angement within the Bi2Ti302io- sheets seemed to be the 
same as in structure of the perovskite type and the stmcture could then 
be described as consisting of Bi2022* layers between which double 
perovskite layers are inserted. 

41 . Attachment V (Aurivillius 1 ) at page 464 has a section entitled "PbBi2Nb209 
Phase". And at page 471 has a section entitled "BiaNbTiOg". And at page 475 has a 
table of compounds having the "CaBi2Nb209 structure" listing the following compounds 
BbNbTiOg, BiaTaTiOg, CaBizNbzOa, SrBi2Nb209, SrBizTazOg, BaBizNbzOg, PbBizNbzOg, 
NaBlsNbAOia, KBi5Nb40i8. Thus Bi and Pb layered perovskite compounds were well 
known in the art about 35 years prior to Applicants' priority date. 

42. Attachment W (Aurivillius 2) at page 499, the first page, has the subtitle "H 
Structure of Bi4Ti30i2". And at page 510, Fig. 4 shows a crystal structure in which "A 
denotes a perovskite layer BiaTiaO^io", C Bi2022* layers and B unit cells of the 
hypothetical perovskite stmcture BiTiOa. 



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Docket: YO987-074BZ 



43. Attachment X (Auiivillius 3) has at page 519, the first page, the subtitle "m 
Structure of BaBi4Ti40is". And in the first paragraph on page 519 states referring to the 
articles of Attachments V (Aurivillius 1), and W (Aurivillius 2) "X ray studies on the 
compounds CaBizNbaOg [the article of Attachment V] and Bi4Ti30i2 [the article of 
Attachment W] have shown that the comparatively complicated chemical formulae of 
these compounds can be explained by simple layer structures being built up from 
BiaO^z* layers and perovskite layers. The unit cells are pictured schematically in Figs. 
1a and 1c." And Fig. 4 at page 526 shows "One half of a unit cell of BaBi4Ti40i5. A 
denotes the perovskite region and B the MozOa layer" where Me represents a metal 
atom. 

44. Attachment Y (Aurivillius 4) is direct to structures having the BisNioOsF structure. 

45. Attachment AA is a list of Hg containing solid state compounds from the 1 989 
Powder Diffraction File Index. Applicants do not have available to them an index from 
prior to Applicants' priority date. The Powder Diffraction File list is a compilation of all 
known solid state compounds with reference to articles directed to the properties of 
these compositions and the methods of fabrication. From Attachment AA it can be 
seen, for example, that there are numerous examples of Hg based compounds. 
Similarly, there are examples of other compounds in the Powder Diffraction File. A 
person of ordinary skill in the art is aware of the Powder Diffraction File and can from 
this file find a reference providing details on how to fabricate these compounds. Thus 
persons of ordinary skill in the art would be motivated by Applicants' teaching to look to 
the Powder Diffraction File for examples of previously fabricated composition expected 
to have properties similar to those described in Applicants' teaching. 

46. It is generally recognized that it is not difficult to fabricate transition metal oxides 
and in particular copper metal oxides that are superconductive after the discovery by 
Applicants of composition, such as transition metal oxides, that are high Tc 
superconductors. This is noted in the book "Copper Oxide Superconductors" by 
Charles P. Poole, Jr., Timir Datta and Horacio A. Farach, John Wiley & Sons (1998), 



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Docket: YO987-074BZ 



referred to herein as Poole 1988: Chapter 5 of Poole 1988 (See Attachment AF) in the 
book entitled "Preparation and Characterization of Samples" states at page 59 "[c]opper 
oxide superconductors with a purity sufficient to exhibit zero resistivity or to 
demonstrate levitation (Early) are not difficult to synthesize. We believe that this is at 
least partially responsible for the explosive worldwide growth in these materials". Poole 
1988 further states at page 61 "[i]n this section three methods of preparation will be 
described, namely, the solid state, the coprecipitation, and the sol-gel techniques 
(Hatfi). The widely used solid-state technique permits off-the-shelf chemicals to be 
directly calcined into superconductors, and it requires little familiarity with the subtle 
physicochemical process involved in the transformation of a mixture of compounds into 
a superconductor." Poole 1988 further states at pages 61-62 "[l]n the solid state 
reaction technique one starts with oxygen-rich compounds of the desired components 
such as oxides, nitrates or cartxjnates of Ba, Bi, La, Sr, Ti, Y or other elements. ... 
These compounds are mixed in the desired atomic ratios and ground to a fine powder 
to facilitate the calcination process. Then these room-temperature-stabile salts are 
reacted by calcination for an extended period (~20hr) at elevated temperatures 
(~900°C). This process may be repeated several times, with pulverizing and mixing of 
the partially calcined material at each step." This is generally the same as the specific 
examples provided by Applicants and as generally described at pages 8, line 19, to 
page 9, line 5, of the Bednorz-Mueller application which states "[t]he methods by which 
these superconductive compositions can be made can use known principals of ceramic 
fabrication, including the mixing of powders containing the rare earth or rare earth-like, 
alkaline earth, and transition metal elements, coprecipitation of these materials, and 
heating steps in oxygen or air. A particularly suitable superconducting material in 
accordance with this invention is one containing copper as the transition metal." 
Consequently, it is my opinion that Applicants have fully enabled high Tc materials 
oxides and their claims. 



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Docket: YO987-074BZ 



47. Charles Poole et al. published another book In 1995 entitled "Superconductivity" 
Academic Press which has a Chapter 7 on "Perovskite and Cuprate Crystallographic 
Structures". (See Attachment Z). This book will be referred to as Poole 1995. 

At page 179 of Poole 1995 states: 

V. PEROVSKITE-TYPE SUPERCONDUCTING STRUCTURES 

In their first report on high-termperature superconductors Bednorz and 

MOeller (1986) referred to their samples as "metallic, oxygen-deficient ... 

perovskite-like mixed-valence copper compounds." Subsequent work has 

confimied that the new superconductors do indeed possess these 

characteristics. 

I agree with this statement. 

48. The book "The New Superconductors", by Frank J. Owens and Charles P. 
Poole, Plenum Press, 1996, referred to herein as Poole 1996 in Chapter 8 entitled 
"New High Temperature Superconductors" starting a page 97 (See Attachment AG) 
shows in Section 8.3 starting at page 98 entitled "Layered Structure of the Cuprates" 
schematic diagrams of the layered stmcture of the cuprate superconductors. Poole 
1996 states in the first sentence of Section 8.3 at page 98 "All cuprate superconductors 
have the layered stmcture shown in Fig. 8.1 ." This is consistent with the teaching of 
Bednorz and Mueller that "These compositions have a layer-type Crystalline Structure 
often Perovskite-like" as noted in paragraph 14 above. Poole 1996 further states in the 
first sentence of Section 8.3 at page 98 "The flow of supercurrent takes place in 
conduction layers and bonding layers support and hold together the conduction layers". 
The caption of Fig. 8.1 states "Layering scheme of the cuprate superconductors". Fig. 
8.3 shows details of the conduction layers for difference sequence of copper oxide 
planes and Fig. 8.4 presents details of the tending layers for several of the cuprates ■ 
which include binding layers for lanthanum superconductor La2Cu04, neodymium 
superconductor Nd2Cu04, yttrium superconductor YBa2Cu302n+4, bismuth 



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Docket: YO987-074BZ 



superconductor Bi2Sr2Can.i CunOam^, thallium superconductor Tl2Ba2Ca„.iCunOa>f4, and 
mercury superconductor HgBa2Can.iCun02m.2. Fig. 8.5 at pages 102 and 103 show a 
schematic atomic structure showing the layering scheme for thallium superconductors. 
Fig. 8.10 at page 109 shows a schematic crystal structure showing the layering scheme 
for La2Cu04. Fig. 8.1 1 at page 110 shows a schematic crystal structure showing the 
layering scheme for HgBa2Ca2Cu30»+x. The layering shown in Poole 1996 for high Tc 
superconductors is consistent with the layering as taught by Bednorz and Mueller in 
their patent application. 

49. Thus Poole 1988 states that the high Tc superconducting materials "are not 
difficult to synthesize" and Poole 1995 states that "the new superconductors do indeed 
possess [the] characteristics" that Applicants' specification describes these new 
superconductors to have. Poole 1996 provide details showing that high Tc 
superconductors are layered or layer-like as taught by Bednorz and Mueller. Therefore, 
as of Applicants' priority date persons of ordinary skill in the art of ceramic fabrication 
were enabled to practice Applicants' invention to the full scope that it is presently 
claimed, including in the claims that are not allowed from the teaching in the 
Bednorz-Mueller application without undue experimentation that is by following the 
teaching of Bednorz and Mueller in combination with what was known to persons of 
ordinary skill in the art of ceramic fabrication. The experiments to make high To 
superconductors not specifically Identified In the Bednorz-Mueller application were 
made by principles of ceramic fabrication prior to the date of their first publication. It is 
within the skill of a person of ordinary skill in the art of ceramic fabrication to make 
compositions according to the teaching of the Bednorz-Mueller application to determine 
whether or not they are high To superconductors without undue experimentation. 



Serial No.: 08/479,810 



Page 20 of 21 



Docket: YO987-074BZ 



50. I have personally made many samples of high Tc superconductors following the 
teaching of Bednorz and Mueller as found in their patent applications. In making these 
materials It was not necessary to use starting materials in stoichiometric proportions to 
produce a high Tc superconductor with Insignificant secondary phases or multi-phase 
compositions, having a superconducting portion and a non-superconducting portion, 
where the composite was a high Tc superconductor. Consequently, following the 
teaching of Bednorz and Mueller and principles of ceramic science known prior to their 
discovery, I made, and persons of skill in the ceramic arts were able to make, high Tc 
superconductors without exerting extreme care in preparing the composition. Thus I 
made and persons of skill in the ceramic arts were able to make high Tc 
superconductors following the teaching of Bednorz and Mueller, without 
experimentation beyond what was well known to a person of ordinary skill in the 
ceramic arts prior to the discovery by Bednorz and Mueller. 

51 . I hereby swear that all statements made herein of my knowledge are true and 
that all statements made on information and belief are believed to be true; and further, 
that these statements were made with the knowledge that willful false statements and 
the like so made are punishable by fine or imprisonment, or both, under Section 1001 
of Title 18 of the United States Code and that such willful false statements made 
jeopardize the validity of the application or patent issued thereon. 





Thomas M. Shaw 




, 2005. 



DANIEL P. MORRIS 
NOTARY PUBLIC, State of New York 
No. 4888676 
Qualified in Westchester County 
Commission Expires March 1 6. Ifc, ' 



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Docket: YO987-074BZ 




ATTACHMENT 1 



1 



Thomas M. Shaw 



IBM Thomas J. Watson Research Center 
P.O. Box 218 
Yorktown Heights, NY 10598 
Phone: (914) 945-3196 

Education: 

1981 Ph.D. Materials Science - University of California at Berkeley 

1978 Masters of Science Materials Science - University of California at Berkeley 
1975 Bachelors of Science Engineering in Metallurgy and Materials Science - University of 

Liverpool 

Work Experience: 

1994-Present Research Staff Member at IBM Thomas J. Watson Research Center working in 
Materials Science 

1984-1994 Research Staff Member at IBM Thomas J. Watson Research Center working in 
Ceramics Science 

1982-1984 Member of the technical staff at Rockwell International Science Center working in 
Ceramics Science 

1981-1982 Postdoctoral Associate at Cornell University working in Ceramics Science 

Professional Positions: 

A fellow of the American Ceramics Society 

Honors: 

1981 John E. Dom Award for thesis. 
Publications: 

Has authored or co-authored more that 150 publications and 21 patents. 

His research interests include, ferroelectric thin films, processing and microstructure control of 
ceramic materials, microscopy of materials, interfacial energy driven processes, liquid phase 
sintering, porous materials, diffusion in thin fihns, electrical and mechanical properties materials 
and the reliability of interconnect structures. 



** TX STPTUS REPORT ** 



PS OF fiPR 14 ' 05 15:06 PflGE.01 



IBM 



DATE TI^E TO/FROM MODE MIN/^C PGS CMDtt STftTUS 

09 04/14 14:59 917032991475 IF— S 07' 24" 029 OK 



BRIEF ATTACHMENT AN 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479.810 
Filed: June 7, 1995 



Group Art Unit: 1751 
Examiner: M. Kopec 



Date: April 5, 2005 
Docket: YO987-074BZ 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



In response to the Office Action dated July 28, 2004, please consider the 
following: 



FIFTH SUPPLEMENTAL AMENDMENT 



Sir: 



Serial No.: 08/479.810 



Page 1 of 5 



Docket: YO987-074BZ 




IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 

In re Patent Application of Date: April 4. 2005 

Applicants: Bednorzetal. Docket: YO987-074BZ 

Serial No.: 08/479.810 Group Art Unit: 1751 

Filed: June 7, 1995 Examiner M. Kopec 

For NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 

Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 

AFFIDAVIT UNDER 37 C.F.R. 1.132 

Sir: 

I, Chang C. Tsuei. being duly sworn, do hereby depose and state: 

1. I received a B. S. degree in Mechanical Engineering from National Taiwan 
University (1960), and M. S. and Ph.D. degrees in Material Science (1963, 1966) 
respectively from California Institute of Technology. 

2. I refer to Attachments A to Z and AA herein which were submitted in a separate 
paper designated as "FIRST SUPPLEMENTAL AMENDMENr in response to the 
Office Action dated July 28, 2004. I also refer to Attachments AB to AG which were 
submitted in a separate paper designated as "THIRD SUPPLEMENTAL AMENDMENT" 
in response to the Office Action dated July 28, 2004. 

3. I have worked as a research staff member and manger in the physics 0 ^ 
superconducting, amorphous and structured materials at the Thomas J. Wate^n ^ 
Research Center of the International Business Machines Corporation In Yo^own'f* )_ 
Heights, New York from 1 973 to the present. f^^. ^ o 2 

c- 2: 

4. I have worked in the fabrication pf and characterization of high temper^r^ 
superconductor and related materials from 1 973 to the present. 



Serial No.: 08/479.810 



Page 1 of 21 



Docket: YO987-074BZ 



SS^L^^i^^. l^^IBM-PLEXANDRIA 7832991476 10 917008623281 P. 05/06 




IN THE UNITED STATES PATENT AND TRADEMARK OFRCE 

in re Patent Application of Date: April 4. 2005 

Applicants: Bednorz et al. Docket: YO987-074BZ 

Serial No.: 08/479.810 Group Art Unit 1751 

Ried: June 7. 1995 Examiner M. Kopec 

For NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
' TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 

Commissioner for Patents 
P.O. Box 1450 
Alexandria. VA 22313-1450 

AFFIDAVIT UNDER 37 C.F.R. 1.132 

Sir. 

I. Chang C. Tsuei. being duly sworn, do hereby depose and state: 

1 . I received a B. S. degree in Mechanical Engineering from National Tai\wan 
University (1960), and M. S. and Ph.D. degrees in Material Science (1963, 1966) 
respectively from Califbmia Institute of Technology. 

2. 1 refer to Attachments A to Z and AA herein which were submitted in a s^rate 
paper designated as "FIRST SUPPLEMENTAL AMENDMENT* in response to the 
Office Action dated July 28, 2004. I also refer to Attachments AB to AG which were 
submitted in a separate paper designated as THIRD SUPPLEMENTAL AMENDMENT" 
in response to the Office Action dated July 28. 2004. 

3. I have worked as a research staff member and manger in the physics of 
superconducting, amorphous and structured materials at the Thomas J. Watson 
Research Center of the International Business Machines Corporation in Yorktown 
Heights, New York from 1973 to the present. . 

4. I have worthed in the fabrication of and characterization of high temperature 
superconductor and related materials from 1973 to the present. 



Serial No.: 08/479.810 



Page 1 of 21 



Docket: YO987-074B2 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz at al. 
Serial No.: 08/479,810 
Filed: June?, 1995 



Group Art Unit: 1751 
Examiner: IVI. Kopec 



Date: April 4, 2005 
Docket: YO987-074BZ 



For NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE. METHODS FOR THEIR USE AND PREPARATION 

Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



I, Chang C. Tsuei, being duly sworn, do hereby depose and state: 

1. I received a B. S. degree in Mechanical Engineering from National Taiwan 
University (1960), and M. S. and Ph.D. degrees in Material Science (1963, 1966) 
respectively from California Institute of Technology. 

2. I refer to Attachments A to Z and AA herein which were submitted in a separate 
paper designated as "FIRST SUPPLEMENTAL AMENDMENT" in response to the 
Office Action dated July 28, 2004. I also refer to Attachments AB to AG which were 
submitted in a separate paper designated as "THIRD SUPPLEMENTAL AMENDMENT" 
in response to the Office Action dated July 28, 2004. 

3. I have worked as a research staff member and manger in the physics of 
superconducting, amorphous and structured materials at the Thomas J. Watson 
Research Center of the International Business Machines Corporation in Yorktown 
Heights, New York from 1973 to the present. 

4. I have worked in the fabrication of and characterization of high temperature 
superconductor and related materials from 1973 to the present. 



AFFIDAVIT UNDER 37 C.F.R. 1.132 



Sir: 



Serial No.: 08/479,810 



Page 1 of 21 



Docket: YO987-074BZ 



5. My resume and list of publications is in Attachment 1 included with this affidavit. 



6. This affidavit is in addition to my affidavit dated December 1 5, 1 998. I have 
reviewed the above-identified patent application (Bednorz-Mueller application) and 
acknowledge that it represents the work of Bednorz and Mueller, which is generally 
recognized as the first discovery of superconductivity in a material having a Tc > 26°K 
and that subsequent developments in this field have been based on this work. 

7. All the high temperature superconductors which have been developed based on 
the work of Bednorz and Mueller behave in a similar manner, conduct current in a 
similar manner, have similar magnetic properties, and have similar structural properties. 

8. Once a person of skill in the art knows of a specific type of composition 
described in the Bednorz-Mueller application which is superconducting at greater than 
or equal to 26°K, such a person of skill in the art, using the techniques described in the 
Bednorz-Mueller application, which includes all principles of ceramic fabrication known 
at the time the application was initially filed, can make the compositions encompassed 
by the claims of the Bednorz-Mueller application, without undue experimentation or 
without requiring ingenuity beyond that expected of a person of skill in the art of the 
fabrication of ceramic materials. This is why the work of Bednorz and Mueller was 
reproduced so quickly after their discovery and why so much additional work was done 
in this field within a short period after their discovery. Bednorz and Mueller's discovery 
was first reported in Z. Phys. B 64 page 189-193 (1996). 

9. The techniques for placing a superconductive composition into a 
superconducting state have been known since the discovery of superconductivity in 
1911 by Kamertingh-Onnes. 



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Docket: YO987-074BZ 



10. Prior to 1986 a person having a bachelor's degree in an engineering discipline, 
applied science, chemistry, physics or a related discipline could have been trained 
within one year to reliably test a material for the presence of superconductivity and to 
flow a superconductive current in a superconductive composition. 

1 1 . Prior to 1 986 a person of ordinary skill in the art of fabricating a composition 
according to the teaching of the Bednorz-Mueller application would have: a) a Ph.D. 
degree in solid state chemistry, applied physics, material science, metallurgy, physics or 
a related discipline and have done thesis research including work in the fabrication of 
ceramic materials; or b) have a Ph.D. degree in these same fields having done 
experimental thesis research plus one to two years post Ph.D. work in the fabrication of 
ceramic materials; or c) have a master's degree in these same fields and have had five 
years of materials experience at least some of which is in the fabrication of ceramic 
materials. Such a person is referred to herein as a person of ordinary skill in the 
ceramic fabrication art. 

12. The general principles of ceramic science referred to by Bednorz and Mueller in 
their patent application and known to a person of ordinary skill in the ceramic fabrication 
art can be found in many books and articles published before their discovery, priority 
date (date of filing of their European Patent Office patent application EPO 0275343A1, 
January 23, 1987) and initial US Application filing date (May 22, 1987). An exemplary 
list of books describing the general principles of ceramic fabricafion are: 

a) Introduction to Ceramics, Kingery et al.. Second Edition, John 
Wiley & Sons, 1976, in particular pages 5-20, 269-319. 381-447 and 
448-51 3. a copy of which is in Attachment B. 

b) Polar Dielectrics and Their Applications, Burfoot et al., University of 
California Press, 1979, in particular pages 13-33, a cppy of which is in 
Attachment C. 



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Docket: YO987-074BZ 



c) Ceramic Processing Before Firing, Onoda et a!., John Wiley & 
Sons, 1978, the entire book, a copy of which is in Attachment D. 

d) Structure, Properties and Preparation of Perovskite-Type 
Compounds, F. S. Galasso , Pergamon Press, 1969, in particular pages 
159-186, a copy of which is in Attachment E. 

These references were previously submitted with the Affidavit of Thomas Shaw 
submitted December 15, 1998. 

1 3. An exemplary list of articles applying the general principles of ceramic fabrication 
to the types of materials described in Applicants' specification are: 

a) Oxygen Defect K2NiF4 - Type Oxides: The Compounds 
La2.xSrxCu04-xo+-, Nguyen et al., Journal of Solid State Chemistry 39, 
120-127(1981). See Attachment F. 

b) The Oxygen Defect Perovskite BaLa4Cu5-0i3.4, A Metallic (This is 
refen'ed to in the Bednorz-Mueller application at page 21, lines 1-2) 
Conductor, C. Michel et al.. Mat. Res. Bull., Vol. 20, pp. 667-671, 1985. 
See Attachment G. 

c) Oxygen Intercalation in Mixed Valence Copper Oxides Related to 
the Perovskite, C. Michel et al.. Revue de Chemie Minerale, 21, p. 407, 
1984. (This is refen-ed to in the Bednorz-Mueller application at page 27, 
lines 1-2). See Attachment H. 

d) Thermal Behaviour of Compositions in the Systems x BaTiOa + 
(1-x) Ba(Lno.5 Bos) O3, V.S. Chincholkar et al.. Therm. Anal. 6th, Vol. 2., p. 
251-6,1980. See Attachment I. 



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14. The Bednorz-Mueller application in the paragraph bridging pages 6 and 7 states 
in regard to the high Tc materials: 

These compositions can carry supercurrents (i.e., electrical currents in a 
substantially zero resistance state of the composition) at temperatures 
greater than 26'*K. In general, the compositions are characterized as 
mixed transition metal oxide systems where the transition metal oxide can 
exhibit multivalent behavior. These compositions have a layer-type 
crystalline structure, often perovskite-like, and can contain a rare earth or 
rare earth-like element. A rare earth-like element (sometimes termed a 
near rare earth element is one whose properties make it essentially a rare 
earth element. An example is a group IIIB element of the periodic table, 
such as La. Substitutions can be found in the rare earth (or rare 
earth-like) site or in the transition metal sites of the compositions. For 
example, the rare earth site can also include alkaline earth elements 
selected from group IIA of the periodic table, or a combination of rare 
earth or rare earth-like elements and alkaline earth elements. Examples 
of suitable alkaline earths include Ca, Sr, and Ba. The transition metal 
site can include a transition metal exhibiting mixed valent behavior, and 
can include more than one transition metal. A particularly good example 
of a suitable transition metal is copper. As will be apparent later, Cu- 
oxide based systems provide unique and excellent properties as high Tc 
superconductors. An example of a superconductive composition having 
high Tc is the composition represented by the formula RE-TM-0, where 
RE is a rare earth or rare earth-like element, TM is a nonmagnetic 
transition metal, and 0 is oxygen. Examples of transition metal elements 
include Cu. Ni, Cr etc. In particular, transition metals that can exhibit 
multi-valent states are very suitable. The rare earth elements are typically 
elements 58-71 of the periodic table, including Ce, Nd, etc. 



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Docket: YO987-074BZ 



15. In the passage quoted in paragraph 14 the general fonnula is RE-TM-O "where 
RE is a rare earth or rare earth-like element, TM is a nonmagnetic transition metal, and 
0 is oxygen." This paragraph states "Substitutions can be found in the rare earth (or 
rare earth-like) site or in the transition metal sites of the compositions. For example, the 
rare earth site can also include alkaline earth elements selected from group IIA of the 
periodic table, or a combination of rare earth or rare earth-like elements and alkaline 
earth elements." Thus applicants teach that RE can be something other than an rare 
earth. For example, it can be an alkaline earth, but is not limited to a alkaline earth 
element. It can be an element that has the same effect as an alkaline earth or 
rare-earth element, that is a rare earth like element. Also, this passage teaches that 
TM can be substituted with another element, for example, but not limited to, a rare 
earth, alkaline earth or some other element that acts in place of the transition metal. 

16. The following table is compiled from the Table 1 of the Article by Rao (See 
Attachment AB) and the Table of high Tc materials from the "CRC Handbook of 
Chemistry and Physics" 2000-2001 Edition (See Attachment AC). An asterisk in 
column 5 indicated that the composition of column 2 does not come within the scope of 
the claims allowed in the Office Action of July 28, 2004. 

17. I have reviewed the Office Action dated July 28, 2004, which states at page 6 
"The present specification is deemed to be enabled only for compositions comprising a 
transition metal oxide containing at least a) an alkaline earth element and b) a 
rare-earth element of Group mB element." I disagree for the reasons given herein. 



18. Composite Table 



1 


2 


3 


4 


5 


6 


7 


u 


MATERIAL 


RAO 

ARTICLE 


HANDBOOK 
OFCHEM& 
PHYSICS 




ALKALINE 

EARTH 

ELEMENT 


RARE 
EARTH 
ELEME 
NT 


1 


La2Cu04+5 






* 


N 


Y 


2 


La2.xSrx(Bax)Cu04 




V 




Y 


Y 


3 


La2Cai.xSrxCu206 


V 


V 




Y 


Y 



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Docket: YO987-074BZ 



4 


YBazCuaOy 


a/ 


V 




Y 


Y 


5 


YBazCmOg 




V 




Y 


Y 


6 


Y2Ba4Cu70i5 


V 


V 




Y 


Y 


7 


Bi2Sr2Cu06 




V 


* 


Y 


N 


8 


BizCaSraCuzOs 




V 


* 


Y 


N 


9 


BiaCaaSraGuaOlo 




V 


* 


Y 


N 


10 


Bi2Sr2(Lni.xCex)2Cu20,o 




>/ 




Y 


Y 


11 


TUBazCuOe 


V 


V 


* 


Y 


N 


12 


Tl2CaBa2Cu208 


V 


V 


* 


Y 


N 


13 


Tl2Ca2Ba2Cu30io 




V 


* 


Y 


N 


14 


Tl(BaLa)Cu05 








Y 


Y 


15 


Tl(SrLa)Cu05 




V 




Y 


Y 


16 


(Tlo5Pbo-5)Sr2Cu05 




V 


* 


Y 


N 


17 


TlCaBazCuzO? 




V 


* 


Y 


N 


18 


(Tlo.5Pbo.5)CaSr2Cu207 




V 


* 


Y 


N 


19 


TlSrzYasCaosCuzOT 




V 




Y 


Y 


20 


TlCa2Ba2Cu308 




V 


* 


Y 


N 


21 


(Tlo.5Pbo.5)Sr2Ca2Cu309 




V 


* 


Y 


N 


22 


TlBa2(Lni-xCex)2Cu209 


V 


V 




Y 


Y 


23 


Pb2Sr2Liio sCao sCusOg 




V 




Y 


Y 


24 


Pb2(Sr,La)2Cu206 








Y 


Y 


25 


(Pb,Cu)Sr2(Ln,Ca)Cu207 


V 


V 




Y 


Y 


26 


(Pb,Cu)(Sr,Eu)(Eu,Ce)Cu20x 




V 




Y 


Y 


27 


Nd2.xCexCu04 






* 


N 


Y 


28 


Cai.xNdxCuOi 








Y 


Y 


29 


Sri.xNdxCuOz 








Y 


Y 


30 


Ca,.xSrxCu02 




V 




Y 


N 


31 


Bao-fiKo^BiOa 




V 


* 


Y 


N 


32 


Rb2C5C60 






* 


N 


Y 


33 


NdBa2Cu307 








Y 


Y 


34 


SmBaSrCu07 








Y 


Y 


35 


EuBaSrCu307 




V 




Y 


Y 


36 


BaSrCu307 






* 


Y 


N 


37 


DyBaSrCu307 




V 




Y 


Y 


38 


HuBaSrCujO? 








Y 


Y 


39 


ErBaSrCu307 (Multiphase) 








Y 


Y 


40 


TmBaSrCu307 (Multiphase) 








Y 


Y 



Serial No.: 08/479,810 Page 7 of 21 Docket: YO987-074BZ 



41 


YBaSrCuaO? 




V 


* 


Y 


Y 


42 


HgBa2Cu02 




V 


* 


Y 


N 


43 


HgBaaCaCuzOe 
(annealed in O2) 




V 


* 


Y 


N 


44 


HgBa2Ca2Cu308 




V 


* 


Y 


N 


45 


HgBa2Ca3Cu40io 






* 


Y 


N 



19. The first composition, La2 Cu Oa*s , has the form RE2CUO4 which is explicitly 
taught by Bednorz and Mueller. The S indicates that there is a nonstoichiometric 
amount of oxygen. 



20. The Bednorz-Mueller application teaches at page 1 1 , line 1 9 to page 12, line 7: 

An example of a superconductive compound having a layer-type structure 
in accordance v\^ith the present invention is an oxide of the general 
composition RE2TMO4 where RE stands for the rare earths (lanthanides) 
or rare earth-like elements and TM stands for a transition metal. In these 
compounds the RE portion can be partially substituted by one or more 
members of the alkaline earth group of elements. In these particular 
compounds, the oxygen content is at a deficit. For example, one such 
compound that meets this general description is lanthanum copper oxide 
La2Cu04... 

21 . The Bednorz-Mueller application at page 1 5, last paragraph states "Despite their 
metallic character, the Ba-La-Cu-0 type materials are essentially ceramics, as are other 
compounds of the RE2 TMO4 type, and their manufacture generally follows known 
principles of ceramic fabrication." 



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22. Compound number 27 of the composite table contains Nd and Ce. both rare 
earth elements. All of the other compounds of the composite table, except for number 
32. have O and one of the alkaline earth elements which as stated above is explicitly 
taught by applicants. Compound 31 is a BiOa compound in which TM is substituted by 
another element, here Bi, as explicitly taught by Applicants in the paragraph quoted 
above. 

23. The rare earth elements are Sc, Y, La, Ce, Pr, Nd, Pm, Sm. Eu. Gd, Tb, Dy, Ho, 
Er, Tm, Yb. and Lu. See the Handbook of Chemistry and Physics 59th edition 
1978-1979 page B262 in Appendix A. The transition elements are identified in the 
periodic table from the inside front cover of the Handbook of Chemistry and Physics in 
Appendix A. 

24. The basic theory of superconductivity has been known many years before 
Applicants* discovery. For example, see the book "Theory of Superconductivity", M. 
von Laue. Academic Press, Inc.. 1952 (See Attachment AD). 

25. In the composite table, compound numbers 7 to 10 and 31 are Bismuth (Bi) 
compounds. Compound number 12 to 22 are Thallium (Tl) compounds. Compound 
numbers 23 to 26 are lead (Pb) compounds. Compounds 42 to 45 are Mercury (Hg) 
compounds. Those compounds that do not come within the scope of an allowed claims 
(the compounds which are not marked with an asterisk in column 3 of the composite 
table) are primarily the Bi. Tl, Pb and Hg compounds. These compounds are made 
according to the principles of ceramic science known prior to applicant's filing date. For 
example, Attachments J, K, L. and M contain the following articles: 

Attachment J - Phys. Rev. B. Vol. 38, No. 16, p. 6531 (1988) is directed to 
Thallium compounds. 



Attachment K - Jap. Joun. of Appl. Phys., Vol. 27, No. 2, p. L209-L210 
(1988) is directed to Bismuth (Bi) compounds. 



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Attachment L - Letter to Nature, Vol. 38, No. 2, p. 226 (18 March 1993) is 
directed to IVIercury (Hg) compounds. 

Attachment M - Nature, Vol. 336, p. 211 (17 November 1988) is directed 
to Lead (Pb) based compounds. 

26. The article of Attachment J (directed to Tl compounds) states at page 6531 , left 
column: 

The samples were prepared by thoroughly mixing suitable amounts of 
TI2O3, CaO, BaOz, and CuO, and fomiing a pellet of this mixture under 
pressure. The pellet was then wrapped in gold foil, sealed in quartz tube 
containing slightly less than 1 atm of oxygen, and baked for approximately 
3 h at = 880-C. 

This is according to the general principles of ceramic science known prior to 
applicant's priority date. 

27. The article of Attachment K (directed to Bi compounds) states at page L209: 

The Bi-Sr-Ca-Cu-0 oxide samples were prepared from powder reagents 
of Bi203, SrCOs, CaCOa and CuO. The appropriate amounts of powders 
were mixed, calcined at 800-870°C for 5 h, thoroughly reground and then 
cold-pressed into disk-shape pellets (20 mm in diameter and 2 mm in 
thickness) at a pressure of 2 ton.cm^ Most of the pellets were sintered at 
about 870°C in air or in an oxygen atmosphere and then furnace-cooled to 
room temperature. 

This is according to the general principles of ceramic science known prior to 
applicant's priority date. 



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28. The article of Attachment L (directed to Hg compounds) states at page 226: 

The samples were prepared by solid state reaction between stoichiometric 
mixtures of BazCuOa*^ and yellow HgO (98% purity. Aldrich). The 
precursor BaaCuOa+rf was obtained by the same type of reaction between 
BaOa (95% purity, Aldrich) and CuO (NonnalPur, Prolabo) at 930°C in 
oxygen, according to the procedure described by De Leeuw et al.^. The 
powders were ground in an agate mortar and placed in silica tubes. All 
these operations were carried out in a dry box. After evacuation, the 
tubes were sealed, placed in steel containers, as described in ref. 3, and 
heated for 5 h to reach ~800°C. The samples were then cooled in the 
fumace, reaching room temperature after ~10 h. 

This is according to the general principles of ceramic science known prior to 
applicant's priority date. 

29. The article of Attachment M (directed to Pb compounds) states at page 21 1 , left 
column: 

The preparative conditions for the new materials are considerably more 
stringent than for the previously known copper-based superconductors. 
Direct synthesis of members of this family by reaction of the component 
metal oxides or cartjonates in air or oxygen at temperatures below 900°C 
is not possible because of the stability of the oxidized SrPbOa-based 
perovskite. Successful synthesis is accomplished by the reaction of PbO 
with pre-reacted (Sr, Ca, Ln) oxide precursors. The precursors are 
prepared from oxides and carbonates in the appropriate metal ratios, 
calcined for 16 hours (in dense AI2O3 crucibles) at 920-980°C in air with 
one intermediate grinding. 



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This is according to the principles of ceramic science known prior to applicant's 
priority date. 

30. A person of ordinary skill in the art of the fabrication of ceramic materials would 
be motivated by the teaching of the Bednorz-Mueller application to investigate 
compositions for high superconductivity other than the compositions specifically 
fabricated by Bednorz and Mueller. 

31 . In Attachment U, there is a list of perovskite materials from pages 1 91 to 207 in 
the book "Structure, Properties and Preparation of Perovskite-Type Compounds" by F. 
S. Galasso, published in 1969, which is Attachment E hereto. This list contains about 
300 compounds. Thus, what the temn "Perovskite-type" means and how to make these 
compounds was well known to a person of ordinary skill in the art in 1969, more than 17 
years before the Applicants' priority date (January 23, 1987). 

This is clear evidence that a person of skill in the art of fabrication of ceramic 
materials knows (prior to Applicants' priority date) how to make the types of materials in 
Table 1 of the Rao Article and the Table from the Handbook of Chemistry and Physics 
as listed in the composite table above in paragraph 17. 

32. The standard reference "Landholt-Bornstein", Volumn 4, "Magnetic and Other 
Properties of Oxides and Related Compounds Part A" (1970) lists at page 148 to 206 
Perovskite and Perovskite-related structures. (See Attachment N). Section 3.2 starting 
at page 1 90 is entitled "Descriptions of perovskite-related structures". The German title 
is "Perowskit-anliche Strukturen". The German word "aniiche" can be translated in 
English as "like". The Langenscheidt's Gemian-English, English-German Dictionary 
1970, at page 446 translates the English "like" as the Gemian "aniiche". (See 
Attachment O). Pages 126 to 147 of Attachment N describes "crystallographic and 
magnetic properties of perovskite and perovskite-related compounds", see title of 
Section 3 at page 126. Section 3.2.3.1 starting at page 192 of "Landholt-Bornstein" 
Vol. 4 (See Attachment N) is entitled "Bismuth Compounds". Thus Bismuth 



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Docket: YO987-074BZ 



perovskite-like compounds and how to make them were well known more than 16 years 
prior to Applicants' priority date. Thus the "Landholt Bornstein" book published in 1970, 
more than 16 years before Applicants' priority date (January 23, 1987). shows that the 
term "perovskite-like" or "perovskite related" is understood by persons of skill in the art 
prior to Applicants' priority date. Moreover, the "Landholt-Bornstein" book cites 
references for each compound listed. Thus a person of ordinary skill in the art of 
ceramic fabrication knows how to make each of these compounds. Pages 376-380 of 
Attachment N has figures showing the crystal structure of compounds containing Bi and 
Pb. 

33. The standard reference "Landholt-Bornstein, Volume 3, Ferro- and 
Antiferroelectric Substances" (1969) provides at pages 571-584 an index to 
substances. (See Attachment P). This list contains numerous Bi and Pb containing 
compounds. See, for example pages 578 and 582-584. Thus a person of ordinary skill 
in the art of ceramic fabrication would be motivated by Applicants' application to 
fabricate Bi and/or Pb containing compounds that come within the scope of the 
Applicants' claims. 

34. The standard reference "Landholt-Bornstein Volume 3 Ferro- and 
Antiferroelectric Substances" (1969) (See Attachment P) at page 37. section 1 is 
entitled "Perovskite-type oxides." This standard reference was published more than 17 
years before Applicants' priority date (January 23, 1987). The properties of 
perovskite-type oxides are listed from pages 37 to 88. Thus the term perovskite-type 
was well known and understood by persons of skill in the art of ceramic fabrication prior 
to Applicants' priority date and more than 17 years before Applicants' priority date 
persons of ordinary skill in the art knew how to make Bi, Pb and many other perovskite, 
perovskite-like, perovskite-related and perovskite-type compounds. 



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Docket: YO987-074BZ 



35. At page 14, line 1 0-1 5 of the Bednorz-Mueller application, Applicants' state 
"samples in the Ba-La-Cu-0 system, when subjected to x-ray analysis, revealed three 
individual crystallographic phases V.12. a first layer-type perovskite-like phase, related 
to the KaNipA structure ..." Applicants' priority document EP0275343A1 filed July 27, 
1988, is entitled "New Superconductive Compounds of the K2NiF4 Structural Type 
Having a High Transition Temperature, and Method for Fabricating Same." See (See 
Attachment AE). The book "Structure and Properties of Inorganic Solids" by Francis S. 
Galasso, Pergamon Press (1969) at page 190 lists examples of Tallium (Tl) compounds 
in the K2NiF4 structure. (See Attachment Q). Thus based on Applicants' teachings prior 
to Applicants' priority date, a person of ordinary skill in the art of ceramic fabrication 
would be motivated to fabricate Thallium based compounds to test for high Tc 
superconductivity. 

36. The book "Crystal Structures" Volume 4, by Ralph W. G. Wyckoff, Interscience 
Publishers, 1960 states at page 96 "This structure, like these of Bi4Ti20i2 (IX, F12) and 
Ba BU Ti4 O4 (XI, 13) is built up of altemating Bi202 and perovskite-like layers." Thus 
layer of perovskite-like Bismuth compounds was well known in the art in 1960 more 
than 26 years before Applicants' priority date. (See Attachment R). 

37. The book "Modern Oxide Materials Preparation. Properties and Device 
Applications" edited by Cockayne and Jones, Academic Press (1972) states (See 
Attachment S) at page 155 under the heading "Layer Structure Oxides and Complex 
Compounds": 

"A large number of layer structure compounds of general formula (Bi202)^* 
(Ax-iBx03x*i)^' have been reported (Smolenskii et al. 1 961 ; Subbarao, 
1962). where A = Ca, Sr, Ba, Pb, etc., B = Ti, Nb, Ta and x = 2. 3. 4. or 6. 
The structure had been previously investigated by Aurivillius (1949) who 
described them in temns of Alternate (Bi202)^* laiyers and perovskite layers 
of oxygen octahedra. Few have been found to be ferroelectric and 
include SrBizTazOs (Tc = 583°K). PbBizTazOs (Tc = 703°K), BiBi3Ti2TiOi2 or 



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Docket: YO987-074BZ 



Bi4Ti30i2 (Tc = 948*'K), BazBUTigOie (Tc = 598°K) and Pb2Bi4Ti50i8 (Tc = 
583°K). Only bismuth titanate Bi4Ti30i2 has been investigated in detail in 
the single crystal fomi and is finding applications in optical stores 
(Cummins, 1967) because of its unique ferroelectric-optical switching 
properties. The ceramics of other members have some interest because 
of their dielectric properties. More complex compounds and solid 
solutions are realizable in these layer structure oxides but none have 
significant practical application." 

Thus the term layered oxides was well known and understood prior to Applicants' 
priority date. Moreover, layered Bi and Pb compounds were well known in 1972 more 
than 1 5 years before Applicants' priority date. 

38. The standard reference "Landholt-Bornstein, Volume 3, Ferro and 
Antiferroelectric Substances" (1969) at pages 107 to 114 (See Attachment T) list 
"layer-structure oxides" and their properties. Thus the temi "layered compounds" was 
well known in the art of ceramic fabrication In 1969 more than 16 years prior to 
Applicants' priority date and how to make layered compounds was well known prior to 
applicants priority date. 

39. Layer perovskite type Bi and Pb compounds closely related to the Bi and Pb high 
Tc compounds in the composite table above in paragraph 17 have been known for 
some time. For example, the following is a list of four articles which were published 
about 35 years prior to Applicants' first publicafion date: 

(1) Attachment V - "Mixed bismuth oxides with layer lattices", B. 
Aurivillius, Arkiv Kemi 1 , 463, (1950). 

(2) Attachment W - "Mixed bismuth oxides with layered lattices ", B. 
Aurivillius, Ari<iv Kemi 1 , 499, (1950). 



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(3) Attachment X - "Mixed bismuth oxides with layered lattices B. 
Aurivillius, Arkiv Kemi 2. 519, (1951). 

(4) Attachment Y - "The structure of Bi2Nb05F and isomorphous 
compounds", B. Aurivillius, Arkiv Kemi 5, 39, (1952). 

These articles will be referred to as Aurivillius 1, 2, 3 and 4, respectively. 

40. Attachment V (Aurivillius 1), at page 463, the first page, has the subtitle "I. The 
structure type of CaNb2Bi209. Attachment V states at page 463: 

X-ray analysis ... seemed to show that the structure was built up of Bi20V 
layers parallel to the basal plane and sheets of composition Bi2Ti30^io'. 
The atomic arrangement within the Bi2Ti30^io' sheets seemed to be the 
same as in structure of the perovskite type and the structure could then 
be described as consisting of Bi20V layers between which double 
perovskite layers are inserted. 

41 Attachment V (Aurivillius 1) at page 464 has a section entitled "PbBi2Nb209 
Phase". And at page 471 has a section entitled "BiaNbTiOg". And at page 475 has a 
table of compounds having the "CaBi2Nb209 structure" listing the following compounds 
BisNbTiOg, BisTaTiOa, CaBi2Nb209, SrBi2Nb209, SrBi2Ta209. BaBi2Nb209, PbBi2Nb209, 
NaBi5Nb40i8, KBi5Nb40i8. Thus Bi and Pb layered perovskite compounds were well 
known in the art about 35 years prior to Applicants' priority date. 

42. Attachment W (Aurivillius 2) at page 499, the first page, has the subtitle "II 
Structure of Bi4Ti30i2". And at page 510, Fig. 4 shows a crystal structure in which "A 
denotes a perovskite layer Bi2Ti30^o', C Bi20V layers and B unit cells of the 
hypothetical perovskite structure BITiOa. 



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Docket: YO987-074BZ 



43. Attachment X (Aurivillius 3) has at page 519. the first page, the subtitle "HI 
Structure of BaBi4Ti40i5". And in the first paragraph on page 519 states referring to the 
articles of Attachments V (Aurivillius 1). and W (Aurivillius 2) "X ray studies on the 
compounds CaBi2Nb209 [the article of Attachment V] and Bi4Ti30i2 [the article of 
Attachment W] have shown that the comparatively complicated chemical formulae of 
these compounds can be explained by simple layer structures being built up from 
BiaOV layers and perovskite layers. The unit cells are pictured schematically in Figs, 
la and 1c." And Fig. 4 at page 526 shows "One half of a unit cell of BaBUTi40i5. A 
denotes the perovskite region and B the Me204 layer" where Me represents a metal 
atom. 

44. Attachment Y (Aurivillius 4) is direct to structures having the BisNioOsF structure. 

45. Attachment AA is a list of Hg containing solid state compounds from the 1 989 
Powder Diffraction File Index. Applicants do not have available to them an index from 
prior to Applicants' priority date. The Powder Diffraction File list is a compilation of all 
known solid state compounds with reference to articles directed to the properties of 
these compositions and the methods of fabrication. From Attachment AA it can be 
seen, for example, that there are numerous examples of Hg based compounds. 
Similarly, there are examples of other compounds in the Powder Diffraction File. A 
person of ordinary skill in the art is aware of the Powder Diffraction File and can from 
this file find a reference providing details on how to fabricate these compounds. Thus 
persons of ordinary skill in the art would be motivated by Applicants' teaching to look to 
the Powder Diffraction File for examples of previously fabricated composition expected 
to have properties similar to those described in Applicants' teaching. 



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Docket: YO987-074BZ 



46. It is generally recognized that it is not difficult to fabricate transition metal oxides 
and in particular copper metal oxides that are superconductive after the discovery by 
Applicants of composition, such as transition metal oxides, that are high Tc 
superconductors. This is noted in the book "Copper Oxide Superconductors" by 
Charles P. Poole, Jr., Timir Datta and Horacio A. Farach, John Wiley & Sons (1998), 
referred to herein as Poole 1988: Chapter 5 of Poole 1988 (See Attachment AF) in the 
book entitled "Preparation and Characterization of Samples" states at page 59 "[cjopper 
oxide superconductors with a purity sufficient to exhibit zero resistivity or to 
demonstrate levitation (Early) are not difficult to synthesize. We believe that this is at 
least partially responsible for the explosive worldwide growth in these materials". Poole 
1988 further states at page 61 "[i]n this section three methods of preparation will be 
described, namely, the solid state, the coprecipitation, and the sol-gel techniques 
(Hatfi). The widely used solid-state technique permits off-the-shelf chemicals to be 
directly calcined into superconductors, and it requires little familiarity with the subtle 
physicochemical process involved in the transformation of a mixture of compounds into 
a superconductor." Poole 1988 further states at pages 61-62 "[i]n the solid state 
reaction technique one starts with oxygen-rich compounds of the desired components 
such as oxides, nitrates or carbonates of Ba, Bi, La, Sr. Ti, Y or other elements. ... 
These compounds are mixed in the desired atomic ratios and ground to a fine powder 
to facilitate the calcination process. Then these room-temperature-stabile salts are 
reacted by calcination for an extended period (-ZOhr) at elevated temperatures 
(~900°C), This process may be repeated several times, with pulverizing and mixing of 
the partially calcined material at each step." This is generally the same as the specific 
examples provided by Applicants and as generally described at pages 8. line 19, to 
page 9, line 5, of the Bednorz-Mueller application which states "[t]he methods by which 
these superconductive compositions can be made can use known principals of ceramic 
fabrication, including the mixing of powders containing the rare earth or rare earth-like, 
alkaline earth, and transition metal elements, coprecipitation of these materials, and 
heating steps in oxygen or air. A particularly suitable superconducting material in 
accordance with this invention is one containing copper as the transition metal." 



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Consequently, it is my opinion that Applicants have fully enabled high Tc materials 
oxides and their claims. 

47. Charles Poole et al. published another book In 1995 entitled "Superconductivity" 
Academic Press which has a Chapter 7 on "Perovskite and Cuprate Crystallographic 
Stnjctures". (See Attachment Z). This book will be referred to as Poole 1995. 

At page 179 of Poole 1995 states: 

V. PEROVSKITE-TYPE SUPERCONDUCTING STRUCTURES 

In their first report on high-temnperature superconductors Bednorz and 

Mueller (1986) referred to their samples as "metallic, oxygen-deficient ... 

perovskite-like mixed-valence copper compounds." Subsequent work has 

confirmed that the new superconductors do indeed possess these 

characteristics. 

I agree with this statement. 

48. The book 'The New Superconductors", by Frank J. Owens and Charles P. 
Poole, Plenum Press, 1996, referred to herein as Poole 1996 in Chapter 8 entitled 
"New High Temperature Superconductors" starting a page 97 (See Attachment AG) 
shows in Section 8.3 starting at page 98 entitled "Layered Structure of the Cuprates" 
schematic diagrams of the layered structure of the cuprate superconductors. Poole 
1996 states In the first sentence of Section 8.3 at page 98 "All cuprate superconductors 
have the layered structure shown In Fig. 8.1 ." This Is consistent with the teaching of 
Bednorz and Mueller that 'These compositions have a layer^type Crystalline Structure 
often Perovskite-like" as noted in paragraph 14 above. Poole 1996 further states in the 
first sentence of Section 8.3 at page 98 "The flow of supercurrent takes place In 
conduction layers and bonding layers support and hold together the conduction layers". 
The caption of Fig. 8.1 states "Layering scheme of the cuprate superconductors". Fig. 
8.3 shows details of the conduction layers for difference sequence of copper oxide 



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Docket: YO987-074BZ 



planes and Fig. 8.4 presents details of the bonding layers for several of the cuprates 
which include binding layers for lanthanunn superconductor La2Cu04, neodymium 
superconductor Nd2Cu04, yttrium superconductor YBa2Cu302n+4, bismuth 
superconductor Bi2Sr2Can.i Cun02n+4, thallium superconductor Ti2Ba2Can.iCun02n+4, and 
mercury superconductor HgBa2Ca„.iCun02n+2. Fig. 8.5 at pages 102 and 103 show a 
schematic atomic structure showing the layering scheme for thallium superconductors. 
Fig. 8.10 at page 109 shows a schematic crystal structure showing the layering scheme 
for La2Cu04. Fig. 8.11 at page 110 shows a schematic crystal structure showing the 
layering scheme for HgBa2Ca2Cu308«. The layering shown in Poole 1996 for high Tc 
superconductors is consistent with the layering as taught by Bednorz and Mueller in 
their patent application. 

49. Thus Poole 1 988 states that the high Tc superconducting materials "are not 
difficult to synthesize" and Poole 1995 states that "the new superconductors do indeed 
possess [the] characteristics" that Applicants' specification describes these new 
superconductors to have. Poole 1996 provide details showing that high Tc 
superconductors are layered or layer-like as taught by Bednorz and Mueller. Therefore, 
as of Applicants' priority date persons of ordinary skill in the art of ceramic fabrication 
were enabled to practice Applicants' invention to the full scope that it is presently 
claimed, including in the claims that are not allowed from the teaching in the 
Bednorz-Mueller application without undue experimentation that is by following the 
teaching of Bednorz and Mueller in combination with what was known to persons of 
ordinary skill in the art of ceramic fabrication. The experiments to make high Tc 
superconductors not specifically identified in the Bednorz-Mueller application were 
made by principles of ceramic fabrication prior to the date of their first publication. It is 
within the skill of a person of ordinary skill in the art of ceramic fabrication to make 
compositions according to the teaching of the Bednorz-Mueller application to detennine 
whether or not they are high Tc superconductors without undue experimentation. 



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50. I have personally made many samples of high To superconductors following the 
teaching of Bednorz and Mueller as found in their patent applications. In making these 
materials it was not necessary to use starting materials in stoichiometric proportions to 
produce a high Tc superconductor with insignificant secondary phases or multi-phase 
compositions, having a superconducting portion and a non-superconducting portion, 
where the composite was a high Tc superconductor. Consequently, following the 
teaching of Bednorz and Mueller and principles of ceramic science known prior to their 
discovery, I made, and persons of skill in the ceramic arts were able to make, high Tc 
superconductors without exerting extreme care in preparing the composition. Thus I 
made and persons of skill in the ceramic arts were able to make high Tc 
superconductors following the teaching of Bednorz and Mueller, without 
experimentation beyond what was well known to a person of ordinary skill in the 
ceramic arts prior to the discovery by Bednorz and Mueller. 

51 . I hereby swear that all statements made herein of my knowledge are true and 
that all statements made on information and belief are believed to be tme; and further, 
that these statements were made with the knowledge that willful false statements and 
the like so made are punishable by fine or imprisonment, or both, under Section 1001 
of Title 18 of the United States Code and that such willful false statements made 
jeopardize the validity of the application or patent issued thereon. 




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Attachment 1 



Chang C. Tsuei 



IBM Thomas J. Watson Research Center 
P.O. Box 218 
Yorktown Heights, NY 10598 
Phone: (914) 945-2799 
Fax: (914) 945-2141 



Education: 

Ph.D. 1966 Materials Science - California Institute of Technology 

M.S. 1 963 Materials Science - California Institute of Technology 

B.S. 1960 Mechanical Engineering - National Taiwan University 



Professional Positions: 

IBM Thomas J. Wotson Research Center 



Research Staff Member, Superconductivity 
Manager, Physics of Structured Materials 
Manager, Physics of Amorphous Materials 
Acting Manager, Superconductivity 
Research Staff Member 

Invited Professor in Solid State Physics 

Visiting Scholar in Applied Physics 



1993 -Present 

1983- 1993 

1979-1983 

1974-1975 

1973- 1979 
Universite Paris-Sud 

1996-1997 
Harvard University 

1980 (summer) 
Stanford University 

09/1982 -04/1983 Visiting Scholar in Applied Physics 
California Institute of Technology 

1 972 - 1 973 Senior Research Associate in AppUed Physics 

1969 - 1972 Senior Research Fellov^ in Materials Science 

1 966 - 1 969 Research Fellow in Materials Science 



Honors: 

2000 Dynamic Achiever Award from the Organization of Chinese Americans 
2000 IBM Corporate Award 

1998 Bodo von Borries Lectureship sponsored by the Bodo von Borries Stiftung of Germany. 
1998 Co-recipient of the Oliver E. Buckley Condensed Matter Physics Prize of the American 
Physical Society 

1996-1997 Appointment as Invited Professor at the Universite Paris-Sud 
1996 Elected to Academia Sinica 

1996 Academic Achievement Award from the Chinese American Academic and Professional 
Society 

1995 IBM Outstanding Innovation Award for contributions to the work on half integer flux 

quantization observed with a scanning SQUID microscope 
1 992 Mzpc Planck Research Prize from the Max Planck Society and the Alexander von 

Humbolt Foundation of Germany 
1 990 IBM Outstanding Technical Achievement Award for contributions to the understanding 

of electrical properties of grain boundaries in high-Tc superconductors 
1 984 IBM Invention Achievement Award 



Chang C. Tsuei - page 2 



1 980 Invention Achievement Award 
Professional Societies Honors: 

200 1 Fellow of the American Association for the Advancement of Science 
1996 Academician of Academia Sinica 
1974 Fellow of American Physical Society 



Publications: available upon request 



BRIEF ATTACHMENT AO 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz at al. 
Serial No.: 08/479.810 
Filed: June 7, 1995 



Group Art Unit: 1751 
Examiner: M. Kopec 



Date: April 5, 2005 
Docket: YO987-074BZ 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 2231 3-1450 



In response to the Office Action dated July 28, 2004, please consider the 
following: 



FIFTH SUPPLEMENTAL AMENDMENT 



Serial No.: 08/479,810 



Page 1 of 5 



Docket: YO987-074BZ 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 

Applicants: Bednorzetal. 

Serial No.: 08/479,810 

Filed: June 7, 1995 

Fon NEW SUPERCONDUCTIVE 
TEMPERATURE, METHOD 

Commissioner for Patents 
P.O. Box 1450 
Alexandria. VA 22313-1450 




Date: April 4, 2005 

Docket: YO987-074BZ 

Group Art Unit: 1751 

Examiner. M. Kopec 

, HAVING HIGH TRANSITION 
JLISE AND PREPARiATION 



Sir: 



AFFIDAVIT UNDER 37 C.F.R. 1.132 

I, Timottiy Dinger, being duly sworn, do hereby depose and ste te: 



I received a B. S. degree in Ceramic Engineering (1981) from ^lew Yortc'State 



College of Ceramics. Alfred University, an M. S. degree (1983) and a 



_,-r. 



CD 

m 
3J 



on 
I* 

-o 
I 



CD 



O — 

2 



o 



Ph.D. degree 



(1986), both in Material Science from the University of California at B(jriceley. 

2. I refer to Attachments A to Z and AA herein which were submitted in a separate 
paper designated as "FIRST SUPPLEMENTAL AMENDMENT" in response to the 
Office Action dated July 28. 2004. I also refer to Attachments AB to ^G which were 
submitted in a separate paper designated as THIRD SUPPLEMENTAL AMENDMENT' 
in response to the Office Action dated July 28, 2004. 



I have woriced as a research staff member in Material Science 



at the Thomas J. 



Watson Research Center of the International Business Machines Corooration in 



Yori<town Heights. New Yorl< from 1986 to 2001 . From 2001 to the p 
worked as an l/T Manager in the IBM Chief Infonmation Officer organ 

4. I have worked in the fabrication of and characterization of high 
superconductor materials from 1987 to 1991. 



esent, I have 
zation. 

temperature 



Serial No.: 08/479,810 



Pagel of 21 



Docket: YO987-074BZ 



APR 05 2005 15:38 FR IBM-flLEXANDRIA 



7032991476 TO 917008623281 



P. 06/06 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 

Applicants: Bednorzetal. 

Serial No.: 08/479.810 

Filed: June?, 1995 

Fon NEW SUPERCONDUCTIVE O 
TEMPERATURE, METHO---^ 

Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 




Date: April 4. 2005 

Docket YO987-074B2 

Group Art Unit 1751 

Examinen M. Kopec 

iDS HAVING HIGH TRANSITION 
^ JJSE AND PREPArtATlON 



Sir. 



APpiDJt VIT UNDER 37 C.F.R. 1.132 

I, Timothy Dinger, being duly sworn, do hereby depose and sts 



1 . I received a B. S. degree in Ceramic Engineering (1 981) from 
College of Ceramics. Alfred University, an M. S. degree (1983) and a 
(1986). both in M^ferlti- Science from the Ufliversity of California at 



te: 



^ew York State 
Ph.D. degree 
afecKeley. 



2. I refer to Altadiments A to Z and AA herein which were submit ted In a separate 
paper designated as "FIRST SUPPLEMENTAL AMENDMENT' in response to the 
Office Action dated July 28. 2004. I also refer to Attachments AB to AG which were 
submitted in a separate paper designated as THIRD SUPPLEMENT «VL AMENDMENT' 
in response to the OfTice Action dated July 28, 2004. 



I have woriced as a research staff member in Material Science 



at the Thomas J. 



Watson Research Center of the Intemational Business Machines Conoration in 
Yorktown Heights, New York from 1986 to 2001 . From 2001 to the p 



esent. I have 



worked as an l/T Manager in the IBM Chief Information Officer organ zation 



,4. I have vroriced in the fabrication of and characterization of higli 
superconductor materials from 1987 to 1991. 



temperature 



Serial No.: 08/479,810 



Page 1 of 21 



Doc<et YO987-074BZ 



>»rtk THTdii Dane od: M^st 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorzetal. 
Serial No.: 08/479.810 
Filed: June?. 1995 



Group Art Unit: 1751 
Examiner: M. Kopec 



Date: April 4, 2005 
Docket: YO987-074BZ 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE. METHODS FOR THEIR USE AND PREPARATION 

Commissioner for Patents 
P.O. Box 1450 
Alexandria. VA 22313-1450 



I, Timothy Dinger, being duly sworn, do hereby depose and state: 

1 . I received a B. S. degree in Ceramic Engineering (1 981 ) from New York State 
College of Ceramics. Alfred University, an M. S. degree (1983) and a Ph.D. degree 
(1986), both in Material Science from the University of California at Berkeley. 

2. I refer to Attachments A to Z and AA herein which were submitted in a separate 
paper designated as "FIRST SUPPLEMENTAL AMENDMENT' in response to the 
Office Action dated July 28. 2004. I also refer to Attachments AB to AG which were 
submitted in a separate paper designated as "THIRD SUPPLEMENTAL AMENDMENT' 
in response to the Office Action dated July 28, 2004. 

3. I have worked as a research staff member in Material Science at the Thomas J. 
Watson Research Center of the International Business Machines Corporation in 
Yorictown Heights. New York from 1 986 to 2001 . From 2001 to the present. I have 
worthed as an l/T Manager in the IBM Chief Information Officer organization. 

4. I have worthed in the fabrication of and characterization of high temperature 
superconductor materials from 1987 to 1991. 

Serial No.: 08/479.810 Page 1 of 21 Docket: YO987-074BZ 



AFFIDAVIT UNDER 37 C.F.R. 1.132 



Sir: 



5. My resume and list of publications is in Attachment 1 included with this affidavit. 



6. This affidavit is in addition to my affidavit dated December 15. 1998. I have 
reviewed the above-identified patent application (Bednorz-Mueller application) and 
acknowledge that it represents the work of Bednorz and Mueller, which is generally 
recognized as the first discovery of superconductivity in a material having a Tc > 26°K 
and that subsequent developments in this field have been based on this work. 

7. All the high temperature superconductors which have been developed based on 
the work of Bednorz and Mueller behave in a similar manner, conduct current in a 
similar manner, have similar magnetic properties, and have similar structural properties. 

8. Once a person of skill in the art knows of a specific type of composition 
described in the Bednorz-Mueller application which is superconducting at greater than 
or equal to 26°K, such a person of skill in the art, using the techniques described in the 
Bednorz-Mueller application, which includes all principles of ceramic fabrication known 
at the time the application was initially filed, can make the compositions encompassed 
by the claims of the Bednorz-Mueller application, without undue experimentation or 
without requiring ingenuity beyond that expected of a person of skill in the art of the 
fabrication of ceramic materials. This is why the wori< of Bednorz and Mueller was 
reproduced so quickly after their discovery and why so much additional work was done 
in this field within a short period after their discovery. Bednorz and Mueller's discovery 
was first reported in Z. Phys. B 64 page 189-193 (1996). 

9. The techniques for placing a superconductive composition into a 
superconducting state have been known since the discovery of superconductivity in 
1911 by Kameriingh-Onnes. 



Serial No.: 08/479,810 



Page 2 of 21 



Docket: YO987-074BZ 



10. Prior to 1986 a person having a bachelor's degree in an engineering discipline, 
applied science, chemistry, physics or a related discipline could have been trained 
within one year to reliably test a material for the presence of superconductivity and to 
flow a superconductive current in a superconductive composition. 

1 1 . Prior to 1 986 a person of ordinary skill in the art of fabricating a composition 
according to the teaching of the Bednorz-Mueller application would have: a) a Ph.D. 
degree In solid state chemistry, applied physics, material science, metallurgy, physics or 
a related discipline and have done thesis research including work in the fabrication of 
ceramic materials; or b) have a Ph.D. degree in these same fields having done 
experimental thesis research plus one to two years post Ph.D. work in the fabrication of 
ceramic materials; or c) have a master's degree in these same fields and have had five 
years of materials experience at least some of which is in the fabrication of ceramic 
materials. Such a person is referred to herein as a person of ordinary skill in the 
ceramic fabrication art. 

12. The general principles of ceramic science refen-ed to by Bednorz and Mueller in 
their patent application and known to a person of ordinary skill in the ceramic fabrication 
art can be found in many books and articles published before their discovery, priority 
date (date of filing of their European Patent Office patent application EPO 0275343A1, 
January 23, 1987) and initial US Application filing date (May 22. 1987). An exemplary 
list of books describing the general principles of ceramic fabrication are: 

a) Introduction to Ceramics, Kingery et al.. Second Edition, John 
Wiley & Sons, 1976, in particular pages 5-20, 269-319, 381-447 and 
448-513, a copy of which is in Attachment B. 

b) Polar Dielectrics and Their Applications, Burfoot et al. , University of 
, California Press, 1979, in particular pages 13-33, a copy of which is in 

Attachment C. 



Serial No.: 08/479,810 



Page 3 of 21 



Docket: YO987-074BZ 



c) Ceramic Processing Before Firing, Onoda et al., John Wiley & 
Sons, 1978, the entire book, a copy of which is in Attachment D. 

d) Structure, Properties and Preparation of Perovskite-Type 
Compounds, F. S. Galasso , Pergamon Press, 1969, in particular pages 
159-186, a copy of which is in Attachment E. 

These references were previously submitted with the Affidavit of Thomas Shaw 
submitted December 15, 1998. 

1 3. An exemplary list of articles applying the general principles of ceramic fabrication 
to the types of materials described in Applicants' specification are: 

a) Oxygen Defect K2NIF4 - Type Oxides: The Compounds 
La2-xSrxCu04-x/2+-, Nguyen et al.. Journal of Solid State Chemistry 39, 
1 20-1 27 (1 981 ). See Attachment F. 

b) The Oxygen Defect Perovskite BaLa4Cu5.0i3.4, A Metallic (This is 
referred to in the Bednorz-Mueller application at page 21 , lines 1-2) 
Conductor, C. Michel et al.. Mat. Res. Bull., Vol. 20, pp. 667-671, 1985. 
See Attachment G. 

c) Oxygen Intercalation in Mixed Valence Copper Oxides Related to 
the Perovskite, C. Michel et al.. Revue de Chemie Minerale, 21. p. 407, 
1984. (This is referred to in the Bednorz-Mueller application at page 27. 
lines 1-2). See Attachment H. 

d) Themial Behaviour of Compositions in the Systems x BaTiOs + 
(1-x) Ba(Lno.5 Bo.§) O3, V.S. Chincholkar et a!.. Therm. Anal. 6th, Vol., 2., p. 
251-6,1980. See Attachment I. 



Serial No.: 08/479,810 Page 4 of 21 Docket: YO987-074BZ 



14. The Bednorz-Mueller application in the paragraph bridging pages 6 and 7 states 
in regard to the high Tc materials: 

These compositions can carry supercun-ents (i.e., electrical currents in a 
substantially zero resistance state of the composition) at temperatures 
greater than 26°K. In general, the compositions are characterized as 
mixed transition metal oxide systems where the transition metal oxide can 
exhibit multivalent behavior. These compositions have a layer-type 
crystalline structure, often perovskite-like, and can contain a rare earth or 
rare earth-like element. A rare earth-like element (sometimes termed a 
near rare earth element is one whose properties make it essentially a rare 
earth element. An example is a group IIIB element of the periodic table, 
such as La. Substitutions can be found in the rare earth (or rare 
earth-like) site or in the transition metal sites of the compositions. For 
example, the rare earth site can also include alkaline earth elements 
selected from group HA of the periodic table, or a combination of rare 
earth or rare earth-like elements and alkaline earth elements. Examples 
of suitable alkaline earths include Ca, Sr, and Ba. The transition metal 
site can include a transition metal exhibiting mixed valent behavior, and 
can include more than one transition metal. A particularly good example 
of a suitable transition metal is copper. As will be apparent later, Cu- 
oxide based systems provide unique and excellent properties as high Tc 
superconductors. An example of a superconductive composition having 
high Tc is the composition represented by the formula RE-TM-0, where 
RE is a rare earth or rare earth-like element, TM is a nonmagnetic 
transition metal, and 0 is oxygen. Examples of transition metal elements 
include Cu, Ni, Cr etc. In particular, transition metals that can exhibit 
multi-valent states are very suitable. The rare earth elements are typically 
elements 58-71 of the periodic table, including Ce, Nd, etc. 



Serial No.: 08/479,810 



Page 5 of 21 



Docket: YO987-074BZ 



15. In the passage quoted in paragraph 14 the general formula is RE-TM-0 "where 
RE is a rare earth or rare earth-like element, TM is a nonmagnetic transition metal, and 
0 is oxygen." This paragraph states "Substitutions can be found in the rare earth (or 
rare earth-like) site or in the transition metal sites of the compositions. For example, the 
rare earth site can also include alkaline earth elements selected from group IIA of the 
periodic table, or a combination of rare earth or rare earth-like elements and alkaline 
earth elements." Thus applicants teach that RE can be something other than an rare 
earth. For example, it can be an alkaline earth, but is not limited to a alkaline earth 
element. It can be an element that has the same effect as an alkaline earth or 
rare-earth element, that is a rare earth like element. Also, this passage teaches that 
TM can be substituted with another element, for example, but not limited to. a rare 
earth, alkaline earth or some other element that acts in place of the transition metal. 

16. The following table (in paragraph 18) is compiled from the Table 1 of the Article 
by Rao (See Attachment AB) and the Table of high Tc materials from the "CRC 
Handbook of Chemistry and Physics" 2000-2001 Edition (See Attachment AC). An 
asterisk in column 5 indicated that the composition of column 2 does not come within 
the scope of the claims allowed in the Office Action of July 28, 2004. 

17. I have reviewed the Office Action dated July 28, 2004, which states at page 6 
"The present specification is deemed to be enabled only for compositions comprising a 
transition metal oxide containing at least a) an alkaline earth element and b) a 
rare-earth element of Group niB element." I disagree for the reasons given herein. 



1 8. Composite Table 



1 


2 


3 


4 


5 


6 


7 


u 


MATERIAL 


RAO 

ARTICLE 


HANDBOOK 
OF CHEM & 
PHYSICS 




ALKALINE 

EARTH 

ELEMENT 


RARE 
EARTH 
ELEME 
NT 


1 


La2Cu044^ 


V 




* 


N 


Y 


2 


La2.xSrx(Bax)Cu04 


V 


V 




Y 


Y 


3 


La2Cai.xSrxCu206 




V 




Y 


Y 



Serial No.: 08/479.810 



Page 6 of 21 



Docket: YO987-074BZ 



4 


YBazCusOT 




V 




Y 


Y 


5 


YBazCmOg 


V 






Y 


Y 


6 


Y2Ba4Cu70i5 


V 


V 




Y 


Y 


7 


BizSraCuOe 


V 


V 


* 


Y 


N 


8 


BizCaSraCuzOg 


V 


V 


* 


Y 


N 


9 


BizCazSrjCusOio 


V 


V 


* 


Y 


N 


10 


Bi2Sr2(Lni.xCex)2Cu20io 








Y 


Y 


11 


Tl2Ba2Cu06 


V 




* 


Y 


N 


12 


Tl2CaBa2Cu208 






* 


Y 


N 


13 


Tl2Ca2Ba2Cu30,o 


V 




* 


Y 


N 


14 


Tl(BaLa)Cu05 


V 






Y 


Y 


15 


Tl(SrLa)Cu05 


f 

V 






Y 


Y 


16 


(Tlo.5Pbo.5)Sr2Cu05 


V 




* 


Y 


N 


17 


TlCaBa2Cu207 


V 




* 


Y 


N 


18 


(Tlo.5Pbo.5)CaSr2Cu207 


/ 

V 




* 


Y 


N 


19 


TlSr2Yo.5Cao.5Cu207 


V 


f 




Y 


Y 


20 


TlCa2Ba2Cu308 


f 

V 


1 

V 


* 


Y 


N 


21 


(Tlo.5Pbo.5)Sr2Ca2Cu309 


V 


V 


* 


Y 


N 


22 


TlBa2(Ln,.xCex)2Cu209 


V 






Y 


Y 


23 


Pb2Sr2Lno.5Cao sCusOg 


V 


V 




Y 


Y 


24 


Pb2(Sr,La)2Cu206 


V 


V 




Y 


Y 


25 


(Pb,Cu)Sr2(Ln,Ca)Cu207 


V 


V 




Y 


Y 


26 


(Pb,Cu)(Sr,Eu)(Eu,Ce)Cu20x 








Y 


Y 


27 


Nd2-xCexCu04 


V 


V 


* 


N 


Y 


28 


Cai.xNdxCuOj 


V 






Y 


Y 


29 


Sri.xNdxCu02 


V 






Y 


Y 


30 


Cai.xSrxCu02 




V 


* 


Y 


N 


31 


Bao-ftKo^BiOa 




V 


* 


Y 


N 


32 


Rb2C5C60 




V 


* 


N 


Y 


33 


NdBajCujO? 








Y 


Y 


34 


SmBaSrCuO? 








Y 


Y 


35 


EuBaSrCu307 








Y 


Y 


36 


BaSrCu307 






* 


Y 


N 


37 


DyBaSrCu307 








Y 


Y 


38 


HuBaSrCu307 








Y 


— 1 

Y 


39 


ErBaSrCu307 (Multiphase) 




V 




Y 


Y 


40 


TmBaSrCu307 (Multiphase) 








Y 


Y 



Serial No.: 08/479,810 



Page 7 of 21 



Docket: YO987-074BZ 



41 


YBaSrCujOv 




V 


* 


Y 


Y 


42 


HgBa2Cu02 




V 


* 


Y 


N 


43 


HgBaaCaCuzOfi 
(annealed in O2) 




V 


* 


Y 


N 


44 


HgBaaCaaCuaOg 




V 


* 


Y 


N 


45 


HgBa2Ca3Cu40io 




V 


* 


Y 


N 



19. The first composition, La2 Cu Oa*s , has the form RE2CUO4 which is explicitly 
taught by Bednorz and Mueller. The <5 indicates that there is a nonstoichiometric 
amount of oxygen. 



20. The Bednorz-Mueller application teaches at page 1 1 , line 1 9 to page 12, line 7: 

An example of a superconductive compound having a layer-type structure 
in accordance with the present invention is an oxide of the general 
composition RE2TMO4 where RE stands for the rare earths (lanthanides) 
or rare earth-like elements and TM stands for a transition metal. In these 
compounds the RE portion can be partially substituted by one or more 
members of the alkaline earth group of elements. In these particular 
compounds, the oxygen content is at a deficit. For example, one such 
compound that meets this general description is lanthanum copper oxide 
La2Cu04... 

21 . The Bednorz-Mueller application at page 1 5, last paragraph states "Despite their 
metallic character, the Ba-La-Cu-0 type materials are essentially ceramics, as are other 
compounds of the RE2 TMO4 type, and their manufacture generally follows known 
principles of ceramic fabrication." 



Serial No.: 08/479,810 



Page 8 of 21 



Docket: YO987-074BZ 



22. Compound number 27 of the composite table contains Nd and Ce, both rare 
earth elements. All of the other compounds of the composite table, except for number 
32, have O and one of the alkaline earth elements which as stated above is explicitly 
taught by applicants. Compound 31 is a BiOs compound in which TM is substituted by 
another element, here Bi, as explicitly taught by Applicants in the paragraph quoted 
above. 

23. The rare earth elements are Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, 
Er. Tm, Yb, and Lu. See the Handbook of Chemistry and Physics 59th edition 
1978-1979 page B262 in Appendix A. The transition elements are identified in the 
periodic table from the inside front cover of the Handbook of Chemistry and Physics in 
Appendix A. 

24. The basic theory of superconductivity has been known many years before 
Applicants' discovery. For example, see the book 'Theory of Superconductivity", M. 
von Laue, Academic Press, Inc., 1952 (See Attachment AD). 

25. In the composite table, compound numbers 7 to 10 and 31 are Bismuth (Bi) 
compounds. Compound number 12 to 22 are Thallium (Tl) compounds. Compound 
numbers 23 to 26 are lead (Pb) compounds. Compounds 42 to 45 are Mercury (Hg) 
compounds. Those compounds that do not come within the scope of an allowed claims 
(the compounds which are not marked with an asterisk in column 3 of the composite 
table) are primarily the Bi, Tl, Pb and Hg compounds. These compounds are made 
according to the principles of ceramic science known prior to applicant's filing date. For 
example. Attachments J, K, L, and M contain the following articles: 

Attachment J - Phys. Rev. B. Vol. 38, No. 16, p. 6531 (1988) is directed to 
Thallium compounds. 

Attachment K - Jap. Joun. of Appl. Phys., Vol. 27, No. 2, p. L209-L210 
(1988) is directed to Bismuth (Bi) compounds. 



Serial No.: 08/479.810 



Page 9 of 21 



Docket: YO987-074BZ 



Attachment L - Letter to Nature, Vol. 38, No. 2, p. 226 (18 March 1993) is 
directed to Mercury (Hg) compounds. 

Attachment M - Nature, Vol. 336, p. 211 (17 November 1988) is directed 
to Lead (Pb) based compounds. 

26. The article of Attachment J (directed to Tl compounds) states at page 6531 , left 
column: 

The samples were prepared by thoroughly mixing suitable amounts of 
TI2O3, CaO, Ba02, and CuO, and forming a pellet of this mixture under 
pressure. The pellet was then wrapped in gold foil, sealed in quartz tube 
containing slightly less than 1 atm of oxygen, and baked for approximately 
3hat^880-C. 

This is according to the general principles of ceramic science known prior to 
applicant's priority date. 

27. The article of Attachment K (directed to Bi compounds) states at page L209: 

The Bi-Sr-Ca-Cu-O oxide samples were prepared from powder reagents 
of Bi203, SrCOa, CaCOa and CuO. The appropriate amounts of powders 
were mixed, calcined at 800-870°C for 5 h, thoroughly reground and then 
cold-pressed into disk-shape pellets (20 mm in diameter and 2 mm in 
thickness) at a pressure of 2 ton.cm^ Most of the pellets were sintered at 
about 870°C in air or in an oxygen atmosphere and then furnace-cooled to 
room temperature. 

This is according to the general principles of ceramic science known prior to 
applicant's priority date. 



Serial No.: 08/479,810 



Page 10 of 21 



Docket: YO987-074BZ 



28. The article of Attachment L (directed to Hg compounds) states at page 226: 

The samples were prepared by solid state reaction between stoichiometric 
mixtures of BaaCuOa+i and yellow HgO (98% purity, Aldrich). The 
precursor Ba2Cu03+rf was obtained by the same type of reaction between 
BaOz (95% purity, Aldrich) and CuO (NormalPur, Proiabo) at 930°C in 
oxygen, according to the procedure described by De Leeuw et al.^ The 
powders were ground In an agate mortar and placed in silica tubes. All 
these operations were earned out in a dry box. After evacuation, the 
tubes were sealed, placed in steel containers, as described in ref. 3, and 
heated for 5 h to reach ~800°C. The samples were then cooled in the 
furnace, reaching room temperature after -10 h. 

This is according to the general principles of ceramic science known prior to 
applicant's priority date. 

29. The article of Attachment M (directed to Pb compounds) states at page 21 1 , left 
column: 

The preparative conditions for the new materials are considerably more 
stringent than for the previously known copper-based superconductors. 
Direct synthesis of members of this family by reaction of the component 
metal oxides or cartionates in air or oxygen at temperatures below 900°C 
is not possible because of the stability of the oxidized SrPbOa-based 
perovskite. Successful synthesis is accomplished by the reaction of PbO 
with pre-reacted (Sr, Ca, Ln) oxide precursors. The precursors are 
prepared from oxides and carbonates in the appropriate metal ratios, 
calcined for 16 hours (in dense AI2O3 crucibles) at 920-980"C in air with 
one intermediate grinding. 



Serial No.: 08/479,810 



Page 11 of 21 



Docket: YO987-074BZ 



This is according to the principles of ceramic science l<nown prior to applicant's 
priority date. 

30. A person of ordinary skill in the art of the fabrication of ceramic materials would 
be motivated by the teaching of the Bednorz-Mueller application to investigate 
compositions for high superconductivity other than the compositions specifically 
fabricated by Bednorz and Mueller. 

31 . In Attachment U, there is a list of perovskite materials from pages 191 to 207 in 
the book "Structure, Properties and Preparation of Perovskite-Type Compounds" by F. 
S. Galasso, published in 1969, which is Attachment E hereto. This list contains about 
300 compounds. Thus, what the term "Perovskite-type" means and how to make these 
compounds was well known to a person of ordinary skill in the art in 1969, more than 17 
years before the Applicants' priority date (January 23, 1987). 

This is clear evidence that a person of skill in the art of fabrication of ceramic 
materials knows (prior to Applicants' priority date) how to make the types of materials in 
Table 1 of the Rao Article and the Table from the Handbook of Chemistry and Physics 
as listed in the composite table above in paragraph 17. 

32. The standard reference "Landholt-Bornstein", Volumn 4, "Magnetic and Other 
Properties of Oxides and Related Compounds Part A" (1970) lists at page 148 to 206 
Perovskite and Perovskite-related structures. (See Attachment N). Section 3.2 starting 
at page 190 is entitled "Descriptions of perovskite-related structures". The German title 
is "Perowskit-anliche Strukturen." The German word "aniiche" can be translated in 
English as "like". The Langenscheidt's German-English, English-German Dictionary 
1970, at page 446 translates the English "like" as the Gemrian "aniiche". (See 
Attachment O). Pages 126 to 147 of Attachment N describes "crystallographic and 
magnetic properties of perovskite and perovskite-related compoundis", see title of 
Section 3 at page 126. Section 3.2.3.1 starting at page 192 of "Landholt-Bornstein" 
Vol. 4 (See Attachment N) is entitled "Bismuth Compounds". Thus Bismuth 



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perovskite-like compounds and how to make them were well known more than 16 years 
prior to Applicants' priority date. Thus the "Landholt Bornstein" book published in 1970, 
more than 16 years before Applicants' priority date (January 23, 1987), shows that the 
temi "perovskite-like" or "perovskite related" is understood by persons of skill in the art 
prior to Applicants' priority date. Moreover, the "Landholt-Bornstein" book cites 
references for each compound listed. Thus a person of ordinary skill in the art of 
ceramic fabrication knows how to make each of these compounds. Pages 376-380 of 
Attachment N has figures showing the crystal structure of compounds containing Bi and 
Pb. 

33. The standard reference "Landholt-BQrnstein, Volume 3, Ferro- and 
Antiferroelectric Substances" (1969) provides at pages 571-584 an index to 
substances. (See Attachment P). This list contains numerous Bi and Pb containing 
compounds. See, for example pages 578 and 582-584. Thus a person of ordinary skill 
in the art of ceramic fabrication would be motivated by Applicants' application to 
fabricate Bi and/or Pb containing compounds that come within the scope of the 
Applicants' claims. 

34. The standard reference "Landholt-Bornstein Volume 3 Ferro- and 
Antiferroelectric Substances" (1969) (See Attachment P) at page 37, section 1 is 
entitled "Perovskite-type oxides." This standard reference was published more than 17 
years before Applicants' priority date (January 23, 1987). The properties of 
perovskite-type oxides are listed from pages 37 to 88. Thus the term perovskite-type 
was well known and understood by persons of skill in the art of ceramic fabrication prior 
to Applicants' priority date and more than 17 years before Applicants' priority date 
persons of ordinary skill in the art knew how to make Bi, Pb and many other perovskite, 
perovskite-like, perovskite-related and perovskite-type compounds. 



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Docket: YO987-074BZ 



35. At page 14, line 10-15 of the Bednorz-Mueller application, Applicants' state 
"samples in the Ba-La-Cu-0 system, when subjected to x-ray analysis, revealed three 
individual crystallographic phases V.I 2. a first layer-type perovskite-like phase, related 
to the K2NiF4 structure ..." Applicants' priority document EP0275343A1 filed July 27, 
1988, is entitled "New Superconductive Compounds of the K2NiF4 Structural Type 
Having a High Transition Temperature, and Method for Fabricating Same." See (See 
Attachment AE). The book "Structure and Properties of Inorganic Solids" by Francis S. 
Galasso. Pergamon Press (1969) at page 190 lists examples of Tallium (Tl) compounds 
in the K2NiF4 structure. (See Attachment Q). Thus based on Applicants' teachings prior 
to Applicants' priority date, a person of ordinary skill in the art of ceramic fabrication 
would be motivated to fabricate Thallium based compounds to test for high Tc 
superconductivity. 

36. The book "Crystal Structures" Volume 4, by Ralph W. G. Wyckoff, Interscience 
Publishers, 1960 states at page 96 'This structure, like these of Bi4Tl20i2 (IX, F12) and 
Ba Bu Ti4 O4 (XI, 13) is built up of alternating Bi202 and perovskite-like layers." Thus 
layer of perovskite-like Bismuth compounds was well known in the art in 1960 more 
than 26 years before Applicants' priority date. (See Attachment R). 

37. The book "Modern Oxide Materials Preparation, Properties and Device 
Applications" edited by Cockayne and Jones, Academic Press (1972) states (See 
Attachment S) at page 155 under the heading "Layer Structure Oxides and Complex 
Compounds": 

"A large number of layer structure compounds of general fomiula (Bi202)^* 
(Ax-iBxOsx+i)^' have been reported (Smolenskii et al. 1 961 ; Subbarao, 
1962), where A = Ca, Sr, Ba, Pb, etc.. B = Tl, Nb, Ta and x = 2, 3, 4, or 5. 
The structure had been previously investigated by Aurivillius (1949) who 
described them in terms of Alternate (Bi202)^* layers and perovskite layers 
of oxygen octahedra. Few have been found to be ferroelectric and 
include SrBi2Ta209 (Tc = 583''K). PbBizTazOg (Tc = 703'*K). BiBi3Ti2TiOi2 or 



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Bi4Ti30i2 (Tc = 948°K), Ba2Bi4Ti50i8 (Tc = 598"K) and Pb2Bi4Ti50i8 (Tc = 
583"* K). Only bismuth titanate Bi4Ti30i2 has been investigated in detail in 
the single crystal form and is finding applications in optical stores 
(Cummins, 1967) because of its unique ferroelectric-optical switching 
properties. The ceramics of other members have some interest because 
of their dielectric properties. More complex compounds and solid 
solutions are realizable in these layer structure oxides but none have 
significant practical application." 

Thus the term layered oxides was well known and understood prior to Applicants* 
priority date. Moreover, layered Bi and Pb compounds were well known in 1972 more 
than 15 years before Applicants' priority date. 

38. The standard reference "Landhoit-Bornstein. Volume 3, Ferro and 
Antiferroelectric Substances" (1969) at pages 107 to 1 14 (See Attachment T) list 
"layer-structure oxides" and their properties. Thus the temi "layered compounds" was 
well known in the art of ceramic fabrication in 1969 more than 16 years prior to 
Applicants' priority date and how to make layered compounds was well known prior to 
applicants priority date. 

39. Layer perovskite type Bi and Pb compounds closely related to the Bi and Pb high 
Tc compounds in the composite table above in paragraph 17 have been known for 
some time. For example, the following is a list of four articles which were published 
about 35 years prior to Applicants' first publication date: 

(1) Attachment V - "Mixed bismuth oxides with layer lattices", B. 
Aurivillius, Arkiv Kemi 1, 463, (1950). 

(2) Attachment W - "Mixed bismuth oxides with layered lattices ", B. 
Aurivillius. Arkiv Kemi 1. 499. (1950). 



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(3) Attachment X - "Mixed bismuth oxides with layered lattices ", B. 
Aurivillius, Arkiv Kemi 2, 519, (1951). 

(4) Attachment Y - 'The structure of Bi2Nb05F and isomorphous 
compounds", 8. Aurivillius, Arl^iv Kemi 5, 39, (1952). 

These articles will be referred to as Aurivillius 1, 2, 3 and 4, respectively. 

40. Attachment V (Aurivillius 1), at page 463, the first page, has the subtitle "I. The 
structure type of CaNbaBizOg. Attachment V states at page 463: 

X-ray analysis ... seemed to show that the structure was built up of BizOV 
layers parallel to the basal plane and sheets of composition Bi2Ti30^o'. 
The atomic arrangement within the BizTlaO^o' sheets seemed to be the 
same as in structure of the perovskite type and the structure could then 
be described as consisting of BizOV layers between which double 
perovskite layers are inserted. 

41 . Attachment V (Aurivillius 1) at page 464 has a section entitled "PbBizNbzOg 
Phase". And at page 471 has a section entitled "BiaNbTlOg". And at page 475 has a 
table of compounds having the "CaBizNbzOa structure" listing the following compounds 
BiaNbTiOg, BisTaTiOa, CaBizNbzOg, SrBizNbaOg. SrBizTazOg, BaBiaNbzOg, PbBizNbzOg, 
NaBi5Nb40i8, KBi5Nb40i8. Thus Bi and Pb layered perovskite compounds were well 
known in the art about 35 years prior to Applicants' priority date. 

42. Attachment W (Aurivillius 2) at page 499. the first page, has the subtitle "D 
Structure of Bi4Ti30i2". And at page 510, Fig. 4 shows a crystal structure in which "A 
denotes a perovskite layer BizTiaO^o", C BizOV layers and B unit cells of the 

i 

hypothetical perovskite structure BiTiOa. 



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Docket: YO987-074BZ 



43. Attachment X (Aurivillius 3) has at page 519, the first page, the subtitle "III 
Structure of BaBi4Ti40i5". And in the first paragraph on page 519 states referring to the 
articles of Attachments V (Aurivillius 1), and W (Aurivillius 2) *'X ray studies on the 
compounds CaBi2Nb209 [the article of Attachment V] and Bi4Ti30i2 [the article of 
Attachment W] have shown that the comparatively complicated chemical formulae of 
these compounds can be explained by simple layer structures being built up from 
Bi20V layers and perovskite layers. The unit cells are pictured schematically in Figs, 
la and 1c." And Fig. 4 at page 526 shows "One half of a unit cell of BaBi4Ti40i5. A 
denotes the perovskite region and B the Me204 layer" where Me represents a metal 
atom. 

44. Attachment Y (Aurivillius 4) is direct to structures having the BisNioOsF structure. 

45. Attachment AA is a list of Hg containing solid state compounds from the 1989 
Powder Diffraction File Index. Applicants do not have available to them an index from 
prior to Applicants' priority date. The Powder Diffraction File list is a compilation of all 
known solid state compounds with reference to articles directed to the properties of 
these compositions and the methods of fabrication. From Attachment AA it can be 
seen, for example, that there are numerous examples of Hg based compounds. 
Similarly, there are examples of other compounds in the Powder Diffraction File. A 
person of ordinary skill in the art is aware of the Powder Diffraction File and can from 
this file find a reference providing details on how to fabricate these compounds. Thus 
persons of ordinary skill in the art would be motivated by Applicants' teaching to look to 
the Powder Diffraction File for examples of previously fabricated composition expected 
to have properties similar to those described in Applicants' teaching. 



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46. It is generally recognized that it is not difficult to fabricate transition metal oxides 
and in particular copper metal oxides that are superconductive after the discovery by 
Applicants of composition, such as transition metal oxides, that are high Tc 
superconductors. This is noted in the book "Copper Oxide Superconductors" by 
Charles P. Poole, Jr., Timir Datta and Horacio A. Farach, John Wiley & Sons (1998), 
refen-ed to herein as Poole 1988: Chapter 5 of Poole 1988 (See Attachment AF) in the 
book entitled "Preparation and Characterization of Samples" states at page 59 "[c]opper 
oxide superconductors with a purity sufficient to exhibit zero resistivity or to 
demonstrate levitation (Early) are not difficult to synthesize. We believe that this is at 
least partially responsible for the explosive worldwide growth in these materials". Poole 
1988 further states at page 61 "[i]n this section three methods of preparation will be 
described, namely, the solid state, the coprecipitation, and the sol-gel techniques 
(Hatfi). The widely used solid-state technique permits off-the-shelf chemicals to be 
directly calcined into superconductors, and it requires little familiarity with the subtle 
physicochemical process involved in the transformation of a mixture of compounds into 
a superconductor." Poole 1988 further states at pages 61-62 "[i]n the solid state 
reaction technique one starts with oxygen-rich compounds of the desired components 
such as oxides, nitrates or carbonates of Ba, Bi, La, Sr, Ti, Y or other elements. ... 
These compounds are mixed in the desired atomic ratios and ground to a fine powder 
to facilitate the calcination process. Then these room-temperature-stabile salts are 
reacted by calcination for an extended period (-'20hr) at elevated temperatures 
(-900°C). This process may be repeated several times, with pulverizing and mixing of 
the partially calcined material at each step." This is generally the same as the specific 
examples provided by Applicants and as generally described at pages 8, line 19, to 
page 9, line 5, of the Bednorz-Mueller application which states "[t]he methods by which 
these superconductive compositions can be made can use known principals of ceramic 
fabrication, including the mixing of powders containing the rare earth or rare earth-like, 
alkaline earth, and transition metal elements, coprecipitation of these materials, and 
heating steps in oxygen or air. A particularly suitable superconducting material in 
accordance with this invention is one containing copper as the transition metal." 



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Docket: YO987-074BZ 



Consequently, it is my opinion that Applicants have fully enabled high Tc materials 
oxides and their claims. 

47. Charles Poole et al. published another book in 1995 entitled "Superconductivity" 
Academic Press which has a Chapter 7 on "Perovskite and Cuprate Crystallographic 
Structures". (See Attachment Z). This book will be referred to as Poole 1995. 

At page 179 of Poole 1 995 states: 

V. PEROVSKITE-TYPE SUPERCONDUCTING STRUCTURES 

In their first report on high-termperature superconductors Bednorz and 

Mueller (1986) referred to their samples as "metallic, oxygen-deficient ... 

perovskite-like mixed-valence copper compounds." Subsequent work has 

confirmed that the new superconductors do indeed possess these 

characteristics. 

I agree with this statement. 

48. The book "The New Superconductors", by Frank J. Owens and Charles P. 
Poole, Plenum Press, 1996, referred to herein as Poole 1996 in Chapter 8 entitled 
"New High Temperature Superconductors" starting a page 97 (See Attachment AG) 
shows in Section 8.3 starting at page 98 entitled "Layered Structure of the Cuprates" 
schematic diagrams of the layered structure of the cuprate superconductors. Poole 
1996 states in the first sentence of Section 8.3 at page 98 "All cuprate superconductors 
have the layered structure shown in Fig. 8.1 ." This is consistent with the teaching of 
Bednorz and Mueller that "These compositions have a layer-type Crystalline Structure 
often Perovskite-like" as noted in paragraph 14 above. Poole 1996 further states in the 
first sentence of Section 8.3 at page 98 "The flow of supercurrent takes place in 
conduction layers and bonding layers support and hold together the conduction layers". 
The caption of Fig. 8.1 states "Layering scheme of the cuprate superconductors". Fig. 
8.3 shows details of the conduction layers for difference sequence of copper oxide 



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Docket: YO987-074BZ 



planes and Fig. 8.4 presents details of the bonding layers for several of the cuprates 
which include binding layers for lanthanum superconductor La2Cu04, neodymium 
superconductor Nd2Cu04, yttrium superconductor YBa2Cu302n+4, bismuth 
superconductor Bi2Sr2Can-i Cun02n+4. thallium superconductor Tl2Ba2Can.iCun02n+4, and 
mercury superconductor HgBazCan-iCunOzn.a- Fig. 8.5 at pages 102 and 103 show a 
schematic atomic structure showing the layering scheme for thallium superconductors. 
Fig. 8.10 at page 109 shows a schematic crystal structure showing the layering scheme 
for La2Cu04. Fig. 8.1 1 at page 110 shows a schematic crystal structure showing the 
layering scheme for HgBa2Ca2Cu308+x. The layering shown in Poole 1996 for high Tc 
superconductors is consistent with the layering as taught by Bednorz and Mueller in 
their patent application. 

49. Thus Poole 1 988 states that the high Tc superconducting materials "are not 
difficult to synthesize" and Poole 1995 states that "the new superconductors do indeed 
possess [the] characteristics" that Applicants' specification describes these new 
superconductors to have. Poole 1996 provide details showing that high Tc 
superconductors are layered or layer-like as taught by Bednorz and Mueller. Therefore, 
as of Applicants' priority date persons of ordinary skill in the art of ceramic fabrication 
were enabled to practice Applicants' invention to the full scope that it is presently 
claimed, Including in the claims that are not allowed from the teaching in the 
Bednorz-Mueller application without undue experimentation that is by following the 
teaching of Bednorz and Mueller in combination with what was known to persons of 
ordinary skill in the art of ceramic fabrication. The experiments to make high Tc 
superconductors not specifically identified in the Bednorz-Mueller application were 
made by principles of ceramic fabrication prior to the date of their first publication. It is 
within the skill of a person of ordinary skill in the art of ceramic fabrication to make 
compositions according to the teaching of the Bednorz-Mueller application to determine 
whether or not they are high Tc superconductors without undue experimentation. 

! i 



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50. I have personally made many samples of high Tc superconductors following the 
teaching of Bednorz and Mueller as found in their patent applications. In making these 
materials it was not necessary to use starting materials in stoichiometric proportions to 
produce a high Tc superconductor with insignificant secondary phases or multi-phase 
compositions, having a superconducting portion and a non-superconducting portion, 
where the composite was a high Tc superconductor. Consequently, following the 
teaching of Bednorz and Mueller and principles of ceramic science known prior to their 
discovery, I made, and persons of skill In the ceramic arts were able to make, high Tc 
superconductors without exerting extreme care in preparing the composition. Thus I 
made and persons of skill in the ceramic arts were able to make high Tc 
superconductors following the teaching of Bednorz and Mueller, without 
experimentation beyond what was well known to a person of ordinary skill in the 
ceramic arts prior to the discovery by Bednorz and Mueller. 

51 . I hereby swear that all statements made herein of my knowledge are true and 
that all statements made on information and belief are believed to be true; and further, 
that these statements were made with the knowledge that willful false statements and 
the like so made are punishable by fine or imprisonment, or both, under Section 1001 
of Title 18 of the United States Code and that such willful false statements made 
jeopardize the validity of the application or patent issued thereon. 



Date: 





Sworn to before me this 




day of April. 2005. 



Notary Public 




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Page 21 of 21 



Docket: YO987-074BZ 



APR 04 ' 05 10:02 FRJBM B-3 2H-04 914 76S 3794 TO 8^23281 P. 02 



50. I have personally made many samples of high Tc superconductors following the 
teaching of Bednorz and Mueller as found in the:, patent applications. In making these 
materials it was not necessary to use starting materials in stoichiometric proportions to 
produce a high Tc superconductor with insignificant secondary phases or multi-phase 
compositions, having a superconducting portion and a non-superconducting portion, 
where ttie composite was a high Tc superconductor. Consequently, following the 
teaching of Bednorz and Mueller and principles of ceramic science known prior to their 
discovery, I made, and persons of skill in the ceramic arts were able to make, high T, 
superconductors without exerting extreme care in preparing the composition. Thus I 
made and persons of skill in the ceramic arts were able to make high T* 
superconductors following the teaching of Bednorz and Mueller, without 
experimentation beyond what was well known to a person of ordinary skill in the 
ceramic arts prior to the discovery by Bednorz and Mueller. 

51 . I hereby swear that all statements made herein of my knowledge are tore and 
that all statements made on infomnation and belief are believed to be tnje; and further, 
that these statements were made wrth the knowledge that willful false statements and 
the like so made are punishable by fine or imprisonment, or both, under Section 1001 
of Title 1 8 of the United States Code and that such willful false statements made 
jeopardize the validity of the application or patent issued thereon. 

Date: ^; ^^'>^ 




Sworn to before me this day of April. 2005 




Notary Public / ^.^^uST?^-^^ 



Serial No.: 08/479,810 

ftPR 04 '05 15:i2 



Page 21 of 21 



Docket: YO987^074BZ 



TOTAL PPGE.02 
914 766 3794 PAGE. 02 



Attachment 1 





Timothy R. Dinger 
Resume 



April 5, 2005 



Timothy R. Dinger 
IBM Corporate Headquarters 
Enterprise On Demand Transformation and CIO Organization 

294 Route 100 
SomerSyNY 10589 



Telephone: (914) 766-3507 
FAX: (914)766-7145 
e-mail address: dinger@us.ibm.com 



Title 



IBM Corporate Headquarters, Enterprise On Demand Transformation and CIO Organization - 
Manager, B2B Technology Strategy and Architecture, (2001 - present). Responsibility to define 
B2B technology strategy and architecture for IBM*s On Demand Infrastructure and reduce that 
strategy to practice by developing and maintaining IBM's edge-of-enterprise B2B Gateway in 
support of the IBM Business Unit B2B strategies. 



Ph.D. (1986) - Materials Science and Engineering, University of California at Berkeley 
M.S. (1983) - Materials Science and Engineering, University of California at Berkeley 
B.S, (1981) - Ceramic Engineering, Alfred University 

Professional Experience 

Information Systems Department, IBM Research Division, Yorktown Heights, NY, Senior 
Manager/Research Staff Member - Watson Information Systems, (1998-2001). Responsibilities 
included financial planning and decision-making for IBM's worldwide Research Division (8 
laboratories worldwide) and formation of and coordination of the Research Division's program 
to influence and support the goals of the IBM CIO. 

Information Systems Department, IBM Research Division, Yorktown Heights, NY, 
Manager/Research Staff Member - Server Systems Engineering, (1997 - 1 998). 

Physical Sciences Department, IBM Research Division, Yorktown Heights, NY, 
Manager/Research Staff Member - Center for Scalable Computing Solutions, (1994-1996). 



Semiconductor Research and Development Center, IBM Microelectronics Division, East 
Fishkill, NY, Manager/Research Staff Member - Advanced Logic Interconnection Technology, 
(1993-1994). 



Education 



Page 1 



. ^ T, T^- — April 5, 2005 

Timothy R. Dinger ^ 

Resume 



Semiconductor Research and Development Center, fflM Microelectronics Division, East 
Fishkill, NY, Technical Assistant to John E. Kelly ID, the Director of the SRDC (1993). 

IBM Thomas J Watson Research Center, Yorktown Heights, NY, Manager/Research Staff 
Member, Interconnection Performance and Reliability Group, Semiconductor Research and 
Development Center (1991 - 1993). 

IBM T.J. Watson Research Center, Research Staff Member, Ceramic Materials Group, System 
Technology and Science Department (1987 - 1991). 

BM T J Watson Research Center, Postdoctoral Fellow, Exploratory Packaging Materials and 
Processes Group, Semiconductor Science and Technology Department (1986-1987). 

University of California, Berkeley, CA, Graduate Student Research Assistant (1981-1985). 

Uwrence Livermore National Laboratory, Livermore, CA, Research Assistant, Ceramic Science 
Group (1981). 

Selected Publications (currently author/coauthor of 47 publications, 5 U.S. Patents) 

T P Smith in T R. Dinger, D.C. Edelstein, J.R. Paraszczak, and T.H. Ning, "The Wiring 
Challenge: Complexity and Crowding," Future Trends in Microelectronics: Reflections on 
.i,.P..HtnN«notechnologv. S. Luryi, J. Xu, and A. Zaslavsky, eds.NATO ASI Series, Vol. 323, 
Kluwer Academic Publishers, Boston, pp. 45-56, 1996. 

T R Dinger T.K. Worthington, W.J. Gallagher and R.L. Sandstrom, "Direct Observation of 
Electronic Anisotropy in Single-Crystal Y.BajCujOx," Phys. Rev. Lett., 58, [25], 
2687-2690(1987). 

T K Worthington W.J. Gallagher, and T.R. Dinger, "Anisotropic Nature of High-Temperature 
Superconductivity^n Single-Crystal Y.Ba^CuaO,..," P/i>'^. /?^v. Le^^. 59, [10], ^ 

T.R. Dinger and S.W. Tozer, "Old Behaviour in New Materials," Nature, 332, 204, 17 March 
1988. 

T R Dinger R.S. Rai and G. Thomas, "Crystallization Behavior of aGlass in the YjOj-SiOz-AlN 
System," J. Am. Cer. Soc, TL [4] , 236-44(1988). 

G J Dolan G.V. Chandrashekhar, T.R. Dinger, C. Feild and F. Holtzberg, "Vortex Structure in 
YBa2Cuj07 and Evidence for hitrinsic Pinning," Phys. Rev. Lett.. 62,'[7], 827-830(1989). 

GJ Dolan F Holtzberg, C. Feild, and T.R. Dinger, "Anisotropic Vortex Structure in 
Y\B^2Cny6,r Phys. Rev. Le«., 62, [18], 2184-2187(1989). 



Page 2 



Timothy R. Dinger 
Resume 



April 5, 2005 



T.R. Dinger, GJ. Dolan, D. Keane, T.R. McGuire, T.K. Worthington, R.M. Yandrofski and Y. 
Yeshurun, "Flux Pinning in Single-Crystal YBa2Cu307.x High Temperature Superconducting 
Compounds: Processing and Related Properties , Proceedings of the 1989 Symposium on Hi^ 
Temperature Superconducting Oxides: Processing and Related Properties, 1 18th Annual 
Meeting of TMS-AIME, Las Vegas, Nevada, February 27 - March 3, 1989, Edited by S.H. 
Whang and A. DasGupta, The Minerals, Metals & Materials Society, Warrendale, PA, 1989, pp. 
23-40. 

Awards 

IBM Major Outstanding Technical Achievement Award - 2005 

IBM Outstanding Technical Achievement Award - 2004 

IBM Second Plateau Invention Achievement Award - 1 994 

IBM First Plateau Invention Achievement Award - 1991 

IBM Outstanding Technical Achievement Award - 1989 

IBM First Patent Application Award - 1989 

Atlantic Richfield Foundation Fellowship (U.C. Berkeley) - 1985 

Regent's Fellowship (U.C. Berkeley) - 1984 

A.L. Ehrman Memorial Scholarship and S.M, Tasheira Scholarship (U.C. Berkeley) - 1982 

Summa Cum Laude (Alfred University, College of Engineering, 1st in class) - 1981 

Alcoa Scholarship (Alfred University) - 1981 

Refractories Foundation Scholarship (Alfred University) - 1980 

Kodak Scholarship (Alfred University) - 1 979 

Tredennick Scholarship - 1988 through 1981 

Pennsylvania State University Scholar (declined) - 1 997 ^ 
National Merit Scholarship Competition finalist -1977 



Page 3 



Timothy R. Dinger 
Resume 



April 5, 2005 



Professional Organizations and Affiliations 

Chaimian, Technical Advisory Board, E2open Corporation 
Association of Computing Machinery (ACM) 
hstitute of Electonics and Electrical Engineers (IEEE) 



Page 4 



BRIEF ATTACHMENT AP 



RECEIPT 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 

In re Patent Application of Date: April 1 2. 2006 

Applicants: Bednorzetal. Docket: YO987-074BZ 

Serial No.: 08/479.810 Group Art Unit: 1751 

Filed: June 7. 1995 Examiner: M. Kopec 

For NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE. METHODS FOR THEIR USE AND PREPARATION 

Mail Stop: AF 

Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



Sin 



SECOND AMENDMENT 
AFTER FINAL REJECTION 




In response to the Final Office Action dated October 20. 2005 and the Advisory 
Action dated Decemlwr 28, 2005. please consider the following: 



i 



Serial No.: 08/479,810 



Page 1 of 138 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 



Date: ApriM 0,2006 



Applicants: Bednorz et al. 



Docket: YO987-074BZ 



Serial No.: 08/479,810 



Group Art Unit: 1751 



Filed: June 7, 1995 



Examiner: M. Kopec 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 

Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



I, Dennis Newns, declare that: 

1 . I received a B. A. degree in Chemistry form Oxford University United Kingdom in 
1964 and a Ph.D. degree in Theoretical Physical Chemistry form the University of 
London in 1967. 



AFFIDAVIT OF DENNIS NEWNS 



UNDER 37 C.F.R. 1.132 



Sir: 



Page 1 of 16 



2. I am a theoretical solid state scientist. My resume and curriculum vitae are 
attached. 

3. The USPTO response dated October 20, 2005 at page 4 regarding the subject 
application cites Schuller et al "A Snapshot View of High Temperature 
Superconductivity 2002" (report from workshop on High Temperature 
Superconductivity held April 5-8, 2002 in San Diego) which the examiner states 
"discusses both the practical applications and theoretical mechanisms relating to 
superconductivity." 

4. The Examiner at page 4 of the Office Action cites page 4 of Schuller et al which 
states: 

"Basic research in high temperature superconductivity, because the 
complexity of the materials, brings together expertise from materials 
scientists, physicists and chemists, experimentalists and theorists... It 
is important to realize that this field is based on complex materials and 
because of this materials science issues are crucial. Microstructures, 
crystallinity, phase variations, nonequilibrium phases, and overall 
structural issues play a crucial role and can strongly affect the physical 
properties of the materials. Moreover, it seems that to date there are 
no clear-cut directions for searches for new superconducting phases, 
as shown by the serendipitous discovery of superconductivity in MgB2. 
Thus studies in which the nature of chemical bonding and how this 
arises in existing superconductors may prove to be fruitful. Of course, 
"enlightened" empirical searches either guided by chemical and 



Page 2 of 16 



materials intuition or systematic searches using well-defined strategies 
may prove to be fruitful. It is interesting to note that while empirical 
searches in the oxides gave rise to many superconducting systems, 
similar (probable?) searches after the discovery of superconductivity in 
MgBa have not uncovered any new superconductors. " 

5. The Examiner at pages 4 -5 of the Office Action cites pages 5- 6 of Schuller et al 
which state: 

"The theory of high temperature superconductivity has proven to be 
elusive to date. This is probably as much caused by the fact that in 
these complex materials it is very hard to establish uniquely even the 
experimental phenomenology, as well as by the evolution of many 
competing models, which seem to address only particular aspects of 
the problem. The Indian story of the blind men trying to characterize 
the main properties of an elephant by touching various parts of its 
body seems to be particularly relevant. It is not even clear whether 
there Is a single theory of superconductivity or whether various 
mechanisms are possible. Thus it is impossible to summarize, or even 
give a complete general overview of all theories of superconductivity 
and because of this, this report will be very limited in its theoretical 
scope." 

6. The Examiner at page 5 of the Office Action cites page 7 of Schuller et al which 
states: 



Page 3 of 16 



"Thus far, the existence of, a totally new superconductor has proven 
impossible to predict from first principles. Therefore their discovery has 
been based largely on empirical approaches, intuition, and. even 
serendipity. This unpredictability is at the root of the excitement that 
the condensed matter community displays at the discovery of a new 
material that is superconducting at high temperature." 
7. I am submitting this declaration to clarify what Is meant by predictability in theoretical 
solid state science. All solid state materials, even elemental solids, present 
theoretical problems. That difficulty begins with the basic mathematical formulation 
of quantum mechanics and how to take into account all interactions that are 
involved in atoms having more than one electron and where the Interactions 
between the atoms may be covalent, ionic or Van der Waals interactions. A theory 
of a solid is based on approximate mathematical fomialisms to represent these 
interactions. A theoretical solid state scientist makes an assessment using physical 
intuition, mathematical estimation and experimental results as a guide to focus on 
features of the complex set of interactions that this assessment suggests are 
dominate in their effect on the physical phenomena for which the theorist is 
attempting to develop a theory. This process results in what is often referred to as 
mathematical formalism. This formalism is then applied to specific examples to 
determine whether the formalism produces computed results that agree with 
measured experimental results. This process can be considered a "theoretical 
exjDeriment." For example, applying the theoretical formalism to a particular crystal 



Page 4 of 16 



structure comprised of a particular set of atoms to compute a value of a desired 
property is in this context a 'Iheoretical experiment." 

8. Even when a successful theoretical formalism is developed, that formalism does 
not produce a list of materials that have a particular property that is desired. Rather 
for each material of interest the same "theoretical experiment' must be conducted. 
Moreover, even if such a "theoretical experimenf indicates that the particular 
material investigated has the property, there is no assurance that it does without 
experimentally fabricating the material and experimentally testing whether it has that 
property, 

9. For example, semiconductors have been studied both experimentally and 
theoretically for more than 50 years. The theory of semiconductors is well 
understood. A material is a semiconductor when there is a filled valence band that 
is separated from the next empty or almost empty valence band by an energy that is 
of the order of the thermal energy of an electron at ambient temperature. The 
electrical conductivity of the semiconductor is controlled by adding dopants to the 
semiconductor crystal that either add electrons to the empty valence band or 
remove electrons from the filled valence band. Notwithstanding this theoretical 
understanding of the physical phenomena of semiconductivity, that understanding 
does not permit either a theoretical or experimental solid state scientist to know a 
priori \Nha\ materials will in fact be a semiconductor. Even with the well developed 
semiconductor theoretical formalisms, that theory cannot be asked the question 
"can you list for me all materials that will be a semiconductor?" Just as an 
experimentalist must do, the theoretical scientist must select a particular material for 



Page 5 of 16 



examination. If the particular material already exists an experimentalist can test that 
material for the semiconducting property. If the particular material does not exist, 
the theoretical solid state scientist must first determine what the crystal structure will 
be of that material. This in of itself may be a formidable theoretical problem to 
determine accurately. Once a crystal stmcture is decided on, the theoretical 
formalism is applied in a "theoretical experimenf to determine if the material has the 
arraignment of a fully filled valence and an empty valence band with the correct 
energy spacing. Such a theoretical experiment generally requires the use of a 
computer to compute the energy band stmcture to determine if for the selected 
composition the correct band configuration is present for the material to be a 
semiconductor. This must be verified by experiment. Even with the extensive 
knowledge of semiconducting properties such computations are not 100% accurate 
and thus theory cannot predict with 1 00% accuracy what material will be a 
semiconductor. Experimental confirmation is needed. Moreover, that a theoretical 
computation is a "theoretical experimenf in the conceptual sense not different than 
a physical experiment. The theorist starting out on a computation, just as an 
experimentalist staring out on an experiment, has an intuitive feeling that, but does 
not know whether, the material studied will in fact be a semiconductor. As stated 
above solid state scientists, both theoretical and experimental, are initially guided 
by physical intuition based on prior experimental and theoretical work. Experiment 
and theory complement each other, at times one is ahead of the other in an 
understanding of a problem, but which one is ahead changes over time as an 
understanding of the physical phenomena develops. 



Page 6 of 1 6 



10. This description of the semiconductor situation is for illustration of the capability of 
theory in solid state science where there is a long history of both experimental and 
theoretical developments. 

11. Superconductivity was first discovered by H. Kammerlingh Onnes in 191 1 and the 
basic theory of superconductivity has been known many years before Applicants' 
discovery. For example, see the book "Theory of Superconductivity", M. von Laue, 
Academic Press, Inc., 1952 (See Attachment AD of the Third Supplementary 
Amendment dated March 1 , 2005). Prior to applicants' discovery superconductors 
were grouped into two types: Type I and Type II. 

12. The properties of Type I superconductors were modeled successfully by the efforts 
of John Bardeen, Leon Cooper, and Robert Schrleffer in what is commonly called 
the BCS theory. A key conceptual element in this theory is the pairing of electrons 
close to the Fermi level into Cooper pairs through interaction with the crystal lattice. 
This pairing results from a slight attraction between the electrons related to lattice 
vibrations; the coupling to the lattice is called a phonon interaction. Pairs of 
electrons can behave very differently from single electrons which are fermions and 
must obey the Pauli exclusion principle. The pairs of electrons act more like bosons 
which can condense into the same energy level. The electron pairs have a slightly 
lower energy and leave an energy gap above them on the order of .001 eV which 
inhibits the kind of collision interactions which lead to ordinary resistivity. For 
temperatures such that the thermal energy is less than the band gap, the material 
exhibits zero resistivity. 



Page 7 of 16 



13. There are about thirty pure metals which exhibit zero resistivity at low temperatures 
and have the property of excluding magnetic fields from the interior of the 
superconductor (Melssner effect). They are called Type I superconductors. The 
superconductivity exists only below their critical temperatures and below a critical 
magnetic field strength. Type I and Type II superconductors (defined below) are well 
described by the BCS theory. 

14. Starting in 1930 with lead-bismuth alloys, a number of alloys were found which 
exhibited superconductivity; they are called Type ll_superconductors. They were 
found to have much higher critical fields and therefore could carry much higher 
current densities while remaining in the superconducting state. 

15. Ceramic materials are expected to be insulators - certainly not superconductors, 
but that is just what Georg Bednorz and Alex Muller, the inventors of the patent 
application under examination, found when they studied the conductivity of a 
lanthanum-barium-copper oxide ceramic in 1986. Its critical temperature of 30 K 
was the highest which had been measured to date, but their discovery started a 
surge of activity which discovered materials exhibiting superconducting behavior in 
excess of 1 25 K. The variations on the ceramic materials first reported by Bednorz 
and Muller which have achieved the superconducting state at much higher 
temperatures are often just referred to as high temperature superconductors and 
form a class of their own. 

16. It is generally believed by theorists that Cooper pairs result in High Tc 
superconductivity. What is not understood is why the Cooper pairs remain together 
at the higher temperatures. A phonon is a vibration of the atoms about their 



Page 8 of 16 



equilibrium positiins in a crystal. As temperature increases these vibrations are 
more complex and the amplitude of these vibrations is larger. How the Cooper pairs 
interact with the phonons at the lower temperature, when these oscillations are less 
complex and of lower amplitude, is understood, this is the BCS theory. Present 
theory Is not able to take into account the more complex and larger amplitude 
vibrations that occur at the higher temperatures, 

17. The article of Schuller referred to by the Examiner in paragraphs 4, 5 and 6 present 
essentially the same picture. 

18. In paragraph 4 above Schuller states "Of course, 'enlightened' empirical searches 
either guided by chemical and materials intuition or systematic searches using 
well-defined strategies may prove to be fruitful. It is interesting to note that while 
empirical searches in the oxides gave rise to many superconducting systems, similar 
(probable?) searches after the discovery of superconductivity in MgBa have not 
uncovered any new superconductors," Schuller is acknowledging that experimental 
researchers using intuition and systematic searches found the other known high Tc 
superconductors. Systematic searching is applying what is known to the 
experimental solid state scientist, that is, knowledge of how to fabricate compounds 
of the same class as the compounds in which Bednorz and Muller first discovered 
High Tc superconductivity. That a similar use of intuition and systematic searching 
"after the discovery of superconductivity in MgB2 have not uncovered any new 
superconductors" is similar to a "theoretical experiment" that after the computation 
is done does not show that the material studied has the property being investigated, 
such as semiconductivity. The Schuller article was published in April 2002 



Page 9 of 16 



approximately one year after the expermental discovery of superconductivity in 
MgBa was reported on in March 2001 (Reference 8 of the Schuller article. See 
paragraph 19 of this affidavit.) This limited time of only one year is not sufficient to 
conclude that systematic searching "after the discovery of superconductivity in MgBa 
" cannot uncover any new superconductors. Experimental investigations of this 
type are not more unpredictable than theoretical investigations since the 
experimental investigation has a known blue print or course of actions, just as does 
a "theoretical experiment." Just as an physical experimental investigation may lead 
to a null result a "theoretical experiment" may lead to a null result. In the field of 
High Tc superconductivity physical experiment is as predictable as a well developed 
theory since the experimental procedures are well known even though very 
complex. Experimental complexity does not mean the field of High Tc 
superconductivity is unpredictable since the methods of making these material are 
so well known. 

19. In paragraph 4 above Schuler refers the discovery of MgBa citing the paper of 
Nagamatsu et al. Nature Vol. 410, March 2001 in which the MgBa is reported to 
have a Tc of 39 K, a layered graphite crystal structure and made from powders 
using know ceramic processing methods. MgBa has a substantially simpler structure 
than the first samples reported on my Bednorz and Muller and therefore can be 
more readily investigated theoretically. There have been recent reports by Warren 
Pickett of the University of California at Davis and by Man/in L. Cohen and Steven 
Louie at the University of California at Berkeley describing progress in a theoretical 
understanding of the Tc of MgB2. It is not surprising that progress in the theory of 



Page 10 of 16 



superconductivity at 39 K has been made based on this relatively simple material. 

In fact a few months after the Schuller article was published in April 20002 Marvin 

.L Cohen and Steven Louie were authors on an article Choi, HJ; Roundy, D; Sun, 

H; Cohen, ML; Louie, SG "First-principles calculation of the superconducting 

transition in MgB2 within the anisotropic Eliashberg formalism " PHYSICAL REVIEW 

B; JUL 1 , 2002; Vol. 66; p 2051 3. The following is from the Abstract of this article: 

" We present a study of the superconducting transition in MgB2 using the 
ab initio pseudopotential density-functional method, a fully anisotropic 
Eliashberg equation, and a conventional estimate for //*. Our study shows 
that the anisotropic Eliashberg equation, constructed with ab initio 
calculated momentum-dependent electron-phonon interaction and 
anharmonic phonon frequencies, yields an average electron-phonon 
coupling constant 2=0.61 , a transition temperature Tc=39 K, and a boron 
isotope-effect exponent a(B)=0.32. The calculated values for Tc. L and 
a(B) are in excellent agreement with transport, specific-heat, and 
isotope-effect measurements, respectively . The individual values of the 
electron-phonon coupling A(k,k(')) on the various pieces of the Fermi 
surface, however, vary from 0.1 to 2.5. The observed Tc is a result of both 
the raising effect of anisotropy in the electron-phonon couplings and the 
lowering effect of anharmonicity in the relevant phonon modes." 
(Emphasis added) 



Thus the statement of the Schuller article in paragraph 5 above "The theory of high 
temperature superconductivity has proven to be elusive to date" is not totally accurate 
since shortly after the publication of the Schuller article a theory of the Tc of MgBa was 
published by Man/in .L. Cohen and Steven Louie. 



A month later they expanded on this in the article Choi, HJ; Roundy, D; Sun, H; 

Cohen, ML; Louie, SG "The origin of the anomalous superconducting properties of 

MgB2" NATURE, AUG 15, 2002;Vol 41 8; pp 758-760. The following is from the 

Abstract of this article: 

" Magnesium diboride ... differs from ordinary metallic superconductors in 
several important ways, including the failure of conventional models ... to 
predict accurately its unusually high transition temperature, the effects of 
isotope substitution on the critical transition temperature, and its 

Page 11 of 16 



anomalous specific heat .... A detailed examination of the energy 
associated with the formation of charge-carrying pairs, referred to as the 
'superconducting energy gap', should clarify why MgBa is different. Some 
early experimental studies have indicated that MgBa has multiple gaps.... 
Here we report an ab initio calculation of the superconducting gaps in 
MgBg and their effects on measurable quantities. An important feature is 
that the electronic states dominated by orbitals in the boron plane couple 
strongly to specific phonon modes, making pair formation favourable. This 
explains the high transition temperature, the anomalous structure in the 
specific heat, and the existence of multiple gaps in this material. Our 
analvsis suggests comparable or higher transition temperatures mav 
result in lavered materials based on B. C and N with partially filled planar 
orbitals. (Emphasis added) 



Thus the statement in the Schuller article in paragraph 5 above "Thus far, the existence 
of, a totally new superconductor has proven Impossible to predict from first principles" 
was shown by the work of Marvin .L. Cohen and Steven Louie published shortly after 
the article of Schuller also to be not totally accurate. 

20. In paragraph 5 above Schuller states "The theory of high temperature 
superconductivity has proven to be elusive to date." As stated above although solid 
state theorist believe that Cooper Pairs are the mechanism of the High Tc 
superconductors, we do not as of yet completely understand how to create a 
mathematical formalism that takes Into account the atomic vibrations at these higher 
temperatures to theoretically permit that electrons to remain paired. 

21. In paragraph 5 above Schuller further states "This is probably as much caused by 
the fact that in these complex materials it is very hard to establish uniquely even the 
experimental phenomenology." Even though these materials are complex that 
complexity does not have to be understood to make these material since 
experimental solid state scientists well understand the method of making these 
materials. The book "Copper Oxide Superconductors" by Charles P. Poole, Jr., 

Page 12 of 16 



Timir Datta and Horacio A, Farach, John Wiley & Sons (1998), [(See Attachment 23 
of The Fifth Supplemental Amendment dated March 1 , 2004)] referred to herein as 
Poole 1988 states in Chapter 5 entitled "Preparation and Characterization of 
Samples" states at page 59: 

"Copper oxide superconductors with a purity sufficient to exhibit zero resistivity 
or to demonstrate levitation (Early) are not difficult to synthesize. We believe 
that this is at least partially responsible for the explosive worldwide growth in 
these materials". 

Poole et al. further states at page 61 : 

"In this section three methods of preparation will be described, namely, the solid 
state, the coprecipitation, and the sol-gel techniques (Hatfi). The widely used 
solid-state technique permits off-the-shelf chemicals to be directly calcined into 
superconductors, and it requires little familiarity with the subtle physicochemical 
process involved in the transformation of a mixture of compounds into a 
superconductor." 

22.lt is thus clear that experimentalists knew, at the time of Benorz and Muller's 
duscovery, how to make the High Tc class of material and that to do so it was not 
necessary to precisely understand the experimental phenomenology, 

23. Charles Poole et al. published another book in 1995 entitled "Superconductivity" 
Academic Press which has a Chapter 7 on "Perovskite and Cuprate Crystallographic 
Structures". (See Attachment Z of the First Supplementary Amendment dated 



Page 13 of 16 



March 1 , 2005). This book will be referred to as Poole 1995. At page 179 of Poole 
1995 states: 

"V. PEROVSKITE-TYPE SUPERCONDUCTING STRUCTURES 

In their first report on high-termperature superconductors Bednorz and Muller 
(1986) referred to their samples as "metallic, oxygen-deficient ... perovskite-like 
mixed-valence copper compounds." Subsequent work has confirmed that the 
new superconductors do indeed possess these characteristics." 

24. Thus Poole 1988 states that the high Tc superconducting materials "are not difficult 
to synthesize" and Poole 1995 states that "the new superconductors do indeed 
possess [the] characteristics" that Applicants' specification (the patent application 
currently under examination) describes these new superconductors to have. 

25. In paragraph 5 above Schuller states: 

"The theory of high temperature superconductivity has proven to be 
elusive to date. This is ....caused by the fact ... the evolution of many 
competing models, which seem to address only particular aspects of 
the problem. The Indian story of the blind men trying to characterize 
the main properties of an elephant by touching various parts of its 
body seems to be particulariy relevant. It is not even clear whether 
there is a single theory of superconductivity or whether various 
mechanisms are possible. Thus it is impossible to summarize, or even 
give a complete general overview of all theories of superconductivity 
and because of this, this report will be very limited in its theoretical 
scope." 



Page 14 of 16 



The initial development of a theory always considers the problem from many 
different aspects until the best and most fruitful approach is realized. That at this 
time "It is not even clear whether there is a single theory of superconductivity or 
whether various mechanisms are possible" does not mean that experimental solid 
state scientists do not know how make this class of High Tc materials. As stated by 
Poole 1988 and Poole 1995 the experimental solid state scientist does know how to 
make this class of High Tc materials. 
26. The Examiner at page 5 of the Office Action cites page 7 of Schuller et al which 
states: 

"Thus far, the existence of, a totally new superconductor has proven 
impossible to predict from first principles. Therefore their discovery has 
been based largely on empirical approaches, intuition, and. even 
serendipity. This unpredictability is at the root of the excitement that 
the condensed matter community displays at the discovery of a new 
material that is superconducting at high temperature." 
A first principles theory that accurately predicts all physical properties of a material 
does not exist for as simple a material as water in its solid form as ice which may 
very well be the most extensively studied solid material. Most theories of solid state 
materials have phenomenological components that are approximations based on 
empirical evidence. As stated above solid state theoretical scientists have not as of 
yet formulated a theoretical formalism that accounts for electrons remaining paired 
as Cooper pairs at higher temperatures. But this does not prevent experimental 
scientists from fabricating materials that have structurally similar properties to the 



Page 15 of 16 



materials first discovered by Bednorz and Muller, This is particularly true since the 
basic theory of superconductivity were also well known at the time of their discovery 
and the methods of making these materials was well known at the time of their 
discovery. It was not necessary at the time of their discovery to have the specific 
theoretical mechanism worked out in detail in order to make samples to test for High 
Tc superconductivity. Even Schuller acknowledges "empirical searches in the 
oxides gave rise to many superconducting systems." 
27. 1 hereby declare that all statements made herein of my knowledge are true and that 
all statements made on information and belief are believed to be true; and further, 
that these statements were made with the knowledge that willful false statements 
and the like so made are punishable by fine or imprisonment, or both, under Section 
1001 of Title 18 of the United States Code and that such willful false statements 
made jeopardize the validity of the application or patent issued thereon. 




Page 16 of 16 



Dr. Dennis M> Newns 

Address: Physical Science Division, IBM T.J. Watson Laboratory, Yorktown Hgts, NY. 
Phone: (914) 945-3014 
E-mail: dennisn@us.ibra.coni 

Professional Prep^lration and Appointments 

1986-Present Physical Science Division, IBM T.J. Watson Laboratory. 
1981 Reader, Imperial College London. 
1971 Lecturer, Imperial College London. 

1969 Postdoctoral Fellow, Department of Physics, Cambridge University. 
1967 Postdoctoral Fellow, James Pranck Institute, University of Chicago. 
1967 Ph.D, Imperial College London. 

Relevant Publications 

1. "Polaronic Effects in Mixed and Intermediate Valence Compounds", 
D.M. Newns and A. C. Hewson, 

J. Phys, C, 12 1665 (1979). 

2. "Mott transition field effect transistor", 
D.M. Newns, J.A. Misewich, and C.C. Tsuei, 
Appl. Phys. Lett 73 780 (1998). 

3. "Room-temperature ferromagnetic nanotubes controlled by electron or hole doping", 
L. Krusin-Elbaum, D.M. Newns and H. Zeng, 

Nature 431 672 (2004). 

4. "Chaurge-exchange in atom-surface scattering - thermal versus quantum-mechanical non-adiabaticity" , 
R. Brako and D.M. Newns, 

Surf. Scl 108 253 (1981). 

5. "Desorption induced by multiple electronic-transitions", 
JA Misewich, TF Heinz and D.M. Newns, 

Phys. Rev. Lett 68 3737 (1992). 



1 



Significant Publications 



1. "On the solution of the Coqbhn-Schrieffer Hamiltonian by the large-N expansion technique", 
N. Read and D.M. Newns, 

J. Phys. C 16 3273 (1983). 

2. "AnomsJous isotope effect and vanhove singularity in superconducting Cu oxides" 
C-C. Tsuei, D.M. Newns and C.C. Chi, 

Phys. Rev. Lett 65 2724-2727 (1990). 

3. "Effect of parallel velocity on charge fraction in ion-surface scattering", 
J. Vanwunnik, R. Brako, K. Makoshi and D.M. Newns, 

Surf. Sci. 12 618-623 (1983). 

4. "Quasi-classical trsinsport at a van hove singularity in cuprate superconductors", 
D.M. Newns, C.C. Tsuei and R.P. Huebener, 

Phys. Rev. Lett 73 1695-1698 (1994). 

5. "Self-Consistent Model of Hydrogen Chemisorption" D. Newns, Phys. Rev. 178 1123-1135 
(1969). 

Synergistic Activities 

1. Work with undergraduate and high school interns as part of the IBM summer research pro- 
gram. 

2. Interact with students at APS March meeting lunches. 

Recent Collaborators 

W. Donath, M. Shabes, B. Lengfield, M. Eleftheriou, P. Pattnaik, C. Zhou, 1. Morgenstern, T. 
Husslein, P.B. Moore, Q.F. Zhong, L. Krusin-Elbaum, H. Zeng, H.J. Wen, R. Ludeke, T. Doderer, 
M.L. Klein, J.A. Misewich, C.C. Tsuei, and G.J. Martyna. 

Graduate and Postdoctoral Advisors 

Thesis Advisor : E.P. Wohlfarth, Imperial College, London. 
Postdoctoral Advisor : P.W. Anderson, University of Chicago. 
Postdoctoral Advisor : RW. Anderson, Princeton University. 



BRIEF ATTACHMENT AQ 



RECEIPT 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 

In re Patent Application of Date: April 12, 2006 

Applicants: Bednorzetal. Docket: YO987-074BZ 

Serial No.: 08/479,810 Group Art Unit: 1751 

Filed: June 7. 1995 Examiner: M. Kopec 

For NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE. METHODS FOR THEIR USE AND PREPARATION 

Mail Stop: AF 

Commissfoner for Patents 
P.O. Box 1450 
Alexandria. VA 22313-1450 



Sir 



SECOND AMENDMENT 
AFTER FINAL REJECTION 




In response to the Final Office Action dated October 20. 2005 and the Advisory 
Action dated Deceml>er 28, 2005, please consider the following: 



i 



Serial No.: 08/479.810 



Page 1 of] 38 





IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorzetal, 
Serial No.: 08/479.810 
Filed: June?, 1995 



Date: February 2, 2006 
Docket: YO987-074BZ 
Group Art Unit: 1751 
Examiner: M. Kopec 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 

Commissioner for Patents 
P.O. Box 1450 
Alexandria. VA 2231 3-1 450 



I. J.Georg Bednorz , declare that: 

1 . I am a coinventor of the referenced application. 

2. I received a M. S. Degree in Minerology/Crystallography {1 976) from the 
University of Muenster in Gemnany and a Ph.D. degree in Natural Science (1982) 
from the Swiss Federal Institute of Technology (ETH) in Zuerich - Switzerland. 



3. The USPTO response dated October 20, 2005 at page 7 cites the following web 
page http://www.nobelchanneLcom/leamingstudio/introduction.sps?id=295&eid=0 
Which states 

It is worth noUog that there is no accepted theory to explain the 
high-temperature behavior of this type of compound. The BCS theorv, 
which has proven to be a useful tool in understanding 
lower-temperature materials, does not adequately explain how the 
Cooper pairs in the new compounds hold together at such high 
temperatures. When Bednorz was asked how high-temperature 
superconductivltv works, he replied, "If I could tell you, many of the 
theorists wor1<ing on the problem would be very surprised." 

4. This declaration is to explain the meaning of the statement attributed to me "If 
I could tell you, many of the theorists working on the problem would be very 
surprised" in response to a question from the interviewer about the mechanism of 
High Tc superconductivity. 



DECLARATION OF GEORG BEDNORZ 
UNDER 37 C.F,R, 1.132 



Sir: 



Page I of 2 




9 



5. Following the discovery of the High Tc superconductivity in oxides by my 
coinventor Alex Mueller and me, the enomnous research effort conducted by 
experimentalist specialized in different disciplines of solid state science created a 
very complex scenario. After our discovery new layered perovskite-like 
CuO-compounds with comparable and higher Tc were discovered of the type that are 
reported on in our original publication and that are described in our patent 
application. These new materials were made according to known principles of 
ceramic science that we described in our patent application. The rapid experimental 
developments were guided by previous wori< on materials having related the 
composition and stmcture. This enormous amount of new infoonation collected over 
a short period of time made it hard to get a clear picture at that time of the 
experimental situation for both experimental specialists and theorists. In addition to 
showing superconductivity at temperatures higher than previously observed, this new 
infomnation included novel and unusual properties, so far unexplained in the 
superconducting and normal state, I am an experimental scientist and in the field of 
solid state science, because of the complexities of theory and experiment, workers in 
the field are either experimentalist or theorist and typically not both. In this field, 
including thotfield of high Tc superconductivity, theory utilizes complex mathematical 
procedures about which theorists are experts. Thus theorists wori<ing in the field 
would have been surprised if, I, as an experimentalist, had been the sole person in 
the field to gain a sufficient overview and experimental and theoretical insight, to 
propose a final theory of high temperature superconductivity at this eariy stage of 
research. 

6. I hereby declare that all statements made herein of my knowledge are toie 
and that all statements made on infomnation and belief are believed to be true; and 
further, that these statements were made with the knowledge that willful false 
statements and the like so made are punishable by fine or imprisonment, or both, 
under Section 1001 of Title 18 of the United States Code and that such willful false 
statements made jeopardize the validity of the application or patent issued thereon. 




Page 2 of 2 



BRIEF ATTACHMENT AR 




IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479,810 
Filed: June 7, 1995 



Group Art Unit: 1751 
Examiner: IVI, Kopec 



Date: March 1, 2004 
Docket: YO987-074BZ 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



FIFTH SUPPLEMENTAL AMENDMENT 



In response to the Office Action dated February 4, 2000: 



ATTACHMENT 57 




^^,0 STAT^ 
Patent mn^ Trmdt 

W««t*»nflton. O.C. 20231 ™w 



; SEP.tAt WUMSER ! nUNCOATE _ 

0 7 / 0 V j< c-* 0 7 0 . / ' 7 I -c : i ^ou ? 



J. DAVID ELLtr T 



FIRST KAMED IKVENTOR 



J ATTCRNO^OOCKET KO. 

.7- YiVi/:::7- 07'^ 



Af?T U?4IT 
J 3 



^ T>itt«pp«catiooha«beoaettmi^ EI R<«P<>««w to coa«mink^ HtH« action is made final. 

A shorteood stataitofy period for wspoosa to tfe selto expire ^ month(s). dayslromihe date o( thi* tetiof. 

FaSire to lespood wiiNn pe«xi for resp<yi« 

PaftI THEroUJ0WlflGATTACHUEm^tS)AREPAOTOFTTO "^^^^^^^^ 

1. □ Notoo»RefeiWK»sCrtedbyExamif>er.PTO«92. i- □ Notk» re Patent Drawirto. PTC«4fi. 

3. □ ItotfcaofArtCitod by Applicant. PTO-1449. □ Notk» of Inlonnal Patent Appfication. Fonn PTO-ISa 

5, □ Intomialioo CO H(w to Effect Drawing Cha^ □ \ 

Partd SOMMARYOFACnON 

are foidb>g in the appScation. 



2.n Cbitns _^ ^ have^beoo c^^. 

a.D Claims '7)_^'^H^-. 

.^^^. \'\\ n-l^ , "iO S^ LOi.1 + (n^ ^ V L_arei^. 

5.n Claims — are objectad to. , 

Q Claims : = ^ subject to restrktioo or election reqiiremeoL 

- T.^TOsappicafioohasboen-SedwithWofindctew^ 
. IL □ Fomw* Aawrw* are requined in 

9. □ Tbe axrected or wteStite <*awings have been reoei«d on : . Under 37 C.F.R 1.84 these drwrings 

« □•ooepe^: a iwt»owp«^t»oe e^pbftafioo or Notice re Patent 

10. DTI»pcopesod •ddHi(>nalor«ubrttote«»ieo<s)o(diw^ : ha* (hove) been D appreved by the 

. examiner; D dttapproved by the examifwf (see expfanation}. 

11. □ The proposed dramng conection. fited . has been O approved;. □ dsapproved (we exptanation). 

12. D Acfaww»ed9emenlismadeo*thec*aimlbrpriort^ Dboenreooived □ not been received 

O been fled in parent appTication. serial no. : • * 

13 O Sincelhisappfcafooapppeafstobeincondrtooforal(wancee)ooep^ 

acconlanoe vwlh the practk* under Ex parte Ouayte. 193S C D. 1 1; 453 O.G. 21^^ 

14.nOhef 



1- Applicant's election with traverse of Group I in Paper No. 22 
is acknowledged. The traversal is on the ground (s) that the claims 
of Groups I, II and TIT are not distinct. This is not found 
persuasive because the Examiner maintains that the superconductive 
product, process of making and method of use are directed to 
patentally distinct inventions. Although there are broad "process" 
and "method" claims that appear to encompass a great deal of 
subject matter, the limitations in the dependent claims distinguish 
the claims of the Groups I, TI and III. 

The requirement is stil] deemed proper and is therefore made 
FINAL. 

2. The objection to the specification and objection of claims l- 
11, 27-35, 40-54, 60-63 and 65-68 under 35 USC 112, first 
paragraph, is maintained. 

3. The following is a quotation of the first paragraph of 35 
U.S.C. § 112: 

The specification shall contain a written description of the 
invention, and of the manner and process of making and using 
it, in such full, clear, concise, and exact terms as to enable 
any person skilled in the art to which it pertains, or w>th 
which it is most nearly connected, to make and use the same 
and shall set forth the best mode contemplated by the inventor 
of carrying out his invention. 

The specification is objected to under 35 U.S.C. § 312, first 
paragraph, as failing to provide an enabling disclosure 
commensurate with the scope of the claims. 

4. The Applicants assert that "the scope of the claims as 
presently worded is reasonable and fully merited" (page 17 of 



Serial No. 07/53.307 
Art. Unit. 13 5 



-3- 



response) - The Examiner disagrees. The present claims are broad 
enough to include a substantia] number of inoperable compositions. 

5. The rejection of claims 1-11, 27-35, 40-54. 60-63 and 65-68 
under 35 USC 112, second paragraph is maintained. 

6. Claims 1-11, 27-35. 40-54, 60-63 and 65-68 are rejected 
under 36 U.S.C. § 112, second paragraph, as being indefinite for 
failing to particularly point out and distinctly claim the subject 
matter which applicant regards as the invention. 

7. The amended term "rare earth-like" is vague, with respect to 
the lack of stoichiometry . Applicants argue the superconductive 
properties can be measured as the composition is varied- This is 
unpersuasive because the present claims broad enough to require an 
undue amount of experimentation. 

8. The Examiner maintains that the term "doping" is vague. 
Neither the claim or the specification discuss the limits of the 
effective amounts of doping. 

q. The Applicants assert that a discussion of "electron-phonon 
interactions to produce superconductivity" is found in the 
specification. The Examiner maintains that the term is not 
adequately .explained. The specification fails to teach how one 
determines how to enhance the "electron-phonon" interactions? 
3 0. The term "at least four elements" is indefinite considering 
the number of elements^ in the periodic table. 



Serial No. 07/53,307 
Art Unit 115 



■4- 



11. The rejection of claims 1-11. 27-35, 40-54, 60-63 and 65-68 
under 35 USC ]0;^/103 is maintajned. 

12. Claims 1-11, 27-35, 40-54, 60-63 and 65-68 are rejected under 
35 U.S-C. § 102(b) as anticipated by or, in the alternative, under 
35 U.S-C. § 103 as obvious over each of Shaplygin et.al., Nguyen 
et.al-, Michel et.al. ( M^t. Res. Bull, and Revue de Chjmie ) . 

13. The Applicants argue that "no prima facie case has been made 
that the composition anticipates or renders obvious the subject 
matter" (page 28 of response). The Examiner maintains that these 
materials appear to be identical to those presently claimed except 
that the superconductive properties are not disclosed. Applicants 
have not provided any evidence that the compositions of the cited 
references are in any way excluded by the languange of the present 
claims, i.e. Applicants have failed to show that these materials 
are not superconductive. Applicant's composition claims do not 
appear to exclude these materials. 

14. Applicants further Avgne that under United States patent Taw 
they are entitled to claim compositions which might happen to 
overlap a portion of the concention ranges broadly recited in the 
cited references. "The broad statement of a concentration range in 
the prior art does not necessarily preclude later invention within 
the concentration range" (page 29 of response). The Examiner fails 
to understand how Applicant's IncrediWy broad claims,, some of 



Seria] No. 07/53,307 ^ 
Art Unit. 33 5 



which require only the presence of a "doped transition meta] oxide" 
(see claim 42), in anyway fal] "within" the scope of the 
co^^positions disclosed in the prior art. The cited references 
disclose very specific compostions that not only fall within the 
scope of the clain^s, but appear to be identical to those 
compositions disclosed in the specification as being 
superconducting- The Examiner maintains that these materials are 
inherently superconductive and therefore render the claim 
unpatentable. 

15. With respect to Applicants arguements under 35 USC 103 
regarding the "question of non-analogous art" and the assertion the 
cited prior art is irrevelant to the present clain,. the Examiner 
maintains that for the present "composition" claims the references 
directed to what appear to be identical materials (both in 
composition and inherent properities) are clearly relevant. The 
cited individual disclosures appear to be sufficient to maintain 
the rejection, the Examiner is not relying on any secondary 
references to modify the teachings in the references- 

,6. The rejection of claims 1-2, 5-11, 40-44, 46. 48, 53-54, 60, 
62 and 66 under 35 USC 102/103 Is maintained. 

17. Claims 1-2, 5-31. 40-44, 46, 48, 53-54, 60, 62 and 66 are 

rejected under 35 U.S.C. § 102(b) as anticipated by or, in the 
alternative, under 35 U.S.C. § 103 aa obvious over each of Perron- 




# i§ 



Serial No. 07/f>3,.307 
Art Unit 1J5 



Simon et..al., Mossner et.al . , Chincholkar en.al., Amad et-.al., 
Blasse et.al., Kurihara et.al. and Anderton et.al. 
18. This rejection is maintained for the reasons set forth in the 
previous paragraphs. The Examiner maintains that the cited 
references appear to disclose materials which inherently provide 
superconductive properties and therefore render the present claims 
unpatentable . 



19- THIS ACTION IS MADE FINAL- Applicant is reminded of the 
extension of time policy as set forth in 37 C.F.R. § 1.336(a). 



A SHORTENED STATUTORY PERIOD FOR RESPONSE TO THIS FTNAI.. ACTION 
IS SET TO EXPIRE THREE MONTHS FROM THE DATE OF THIS ACTION. IN THE 
EVENT A FIRST RESPONSE IS FILED WITHIN TWO MONTHS OF THE MAILING 
DATE OF THIS FINAL ACTION AND THE ADVISORY ACTION IS NOT MAILED 
UNTIL AFTER THE END OF THE THREE-MONTH SHORTENED STATUTORY PERIOD, 
THEN THE SHORTENED STATUTORY PERIOD WILL EXPIRE ON THE DATE THE 
ADVISORY ACTION IS MAILED, AND ANY EXTENSION FEE PURSUANT TO 37 
C F R § 3.136(a) WILL BE CALCULATED FROM THE MAILING DATE OF THE 
ADVISORY ACTION. IN NO EVENT WILT, THE STATUTORY PERIOD FOR 
RESPONSE EXPIRE LATER THAN SIX MONTHS FROM THE DATE OF THIS FINAL 
ACTION . 



Any inquiry concerning this communication or earlier 
communications from the examiner should be directed to John Boyd 
whose telephone number is (703) 308-3314. , 

Any inquiry of a general nature or relating to the status of 
this application should be directed to the Group receptionist whose 
telephone number is (703) -•308-'0661 . 




PAliLUEBERMAN 
SUPERVISORY PRIMARY EXAMINER 
ART UNIT 115 



BRIEF ATTACHMENT AS 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479,810 
Filed: June 7, 1995 



Group Art Unit: 1751 
Examiner: M. Kopec 



Docket: YO987-074BZ 



Date: March 1, 2004 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



FIFTH SUPPLEMENTAL AMENDMENT 



Sir: 



In response to the Office Action dated February 4, 2000: 



ATTACHMENT 39 



fir 



Inorganic Chemistry 

AN ADVANCED TEXTBOOK 



THERALD MO£LI£R 



New York • JOHN WILEY & SONS, Inc. 
London - CHAPMAN & HALL, Umited 




COPTRIOHT, 1052 



Br 



John Wojct ^ 8ok8, Inc. 



AU RighU Reserved 

This hook or any pari iherecf must not he 
duoed in amy farm vnihoui the taritten permission 
ef the publisher. 



libr&ty of Congress Oeitalog Number: 62-7487 

PBINTED IN TH£ UNITED GTATE8 OP AMEBICA 



fimphasis up 
quite geaeraUy 
iHtiy, inorganic 
followed by the 
ifltiy, and, sub; 
sfron^jempha 
More recently, 
inorganic chem 
rather than up 
remarkable the 
and continue t< 
podtion that it 

Unfortunate] 
expanded in a ( 
univerrity stud 
their frediman 
courses. Thes 
dents with the 
them of its see 
that is to be d 
they have cone 
tedmol<^. 8 
Sober reflection 
modem and ac 

For a numb< 
semester lectui 
the field from 
esdsting probL 
adyanoed und 
At the gradur 
upon which 11 
chemistry are 
enrollments ar 

Those who] 
suitable textb< 
whence, thej 




au6 

doihx0U eomr 
. Crattni^. In 
oe ctyBtallised 
those of 
e at ordinaiy 
X oomponeats, 
lent to escape. 
Midi the com- 
Dt, OOi, HCN, 

(CJI/)).-SO,, 
gas dements 

ate oompounds 
i of importance 

(iponent. This 
ijBtal together, 
I smtaUe dxe, 

day resalt from 
f the ctjBtalor 

the time ^hen 



iterest but arc 
mUe arrange- 
I lead to them 18 



itoof dftonisUry. 
on bond forma- 
and tt8 appliear 
anical combina- 
departore from 
» not possess the 
B coneiderations 
iOn-fltoidiiometr 

19S0);ReMafi(A, 1, 



Ou6 



Summary qf Bend 7>pe» 



22S 



ric compounds as opposed to the normal Daltonide or stoichiometric 
compounds. As examples, one may cite certain metallic hydrides 
such as VHcu, CeHt.«ff (p. 411); certain oxides such as TIOi.t-l*, 
FeOt.«$<, WOt.«^a.n; euch sulfides, sdenides, and teDurides as CTu^S, 
Cui.^ CulmTc CuFcSi^m; the tungsten bronzes, Na<WO«; eta 
Combinations of these types are particularly common among minerals. 

Lack of true stoiehiometry of this type is assodated with so-called 
defect crystal lattices. Defects in a crystal lattice amount to variations 
frx)m tiie regularity which characterizes the material as a whole. 
They are of two types: 

i« Frenkd d^ecU, in which certain atoms or ions have migrated to 
interstitial portions some distance removed from the ''boles" which 
they vacated. 

2. SchaUky defeeU, in which "holes" are left in random fashion 
throu^out the crystal because of migration of atoms or ions to tiie 
surface of the material 

Althou^ both types of defect probably characterixe crystals of non- 
stoidiiiome^c compounds, the Schottky defects are the more impor- 
tant. Obviously detectable departure from true stoidiiometiic com- 
podtion can result only if serious defects are present. It would f oDow, 
tiierefore^y that many apparenfly stoichiometric compounds are not 
truly BO. n excess metal is present in a crystal, it may also result 
from partial reduction of hi^b-valent cations; whereas if excess non- 
metal is present, hi^ier valent cations or lower valent anions tiian 
those normally present may be respondble. Many instances are 
known of multiple oxidation number in a cin^ crystaL Non- 
stoichiometric cwipounds often diow senurconductivity, fluorescence, 
and centers of color. For a comprdiendve discus&aon of this ratiier 
complex subject, a detuled review*^ should be consulted. 

SUMMARY OF BOND TYPES 

The important linkages ^diich hold together the components of 
crystalline solids and their g^smd diaraeteristics may be summariced 
as foUows: 

1. Ionic UnkoffCB, in which the crystals are made up of regular geo- 
metrical arrangements of podtive and native ions. Such solids 
tend to possess hig^ melting and boiling points, are hard and difficult 
to deform, and tend to be soluble in poUr solvents. When dissolved 
in such solvents or fused, they are excellent conductors. Crystals 

J. S, Anderaon: Ann. RcporU, iS, 104 (1946). 



V 




2i4 



Valency and the Chemical Bond 



overcome. Such cage compoundB have been called tiathrate eovor 
poonds** (Latin dalhralus, endosed by cross bars of a grating). In 
general, they occur ^en mixtures of the oomponeats are oyMallised 
under optimum conditions. Thdr pn^ierties are roughly thoee trf 
the endodng materiaL Such compounds are stable at ordinary 
ten4>eiature8 with leepect to decomposition into thdr components, 
but melting or dissolution penmts the endoeed component to escape. 
Examples are hydioquinonc compounds whidi approach the com- 
position (CJB[/)O. X(X = HO, HBr. HiS, CHiOH, S0„ CO^ HCN, 
etc); amine compounds containing suKurous add, e-g. (p-B[.NC«H«- 
NHO«-H^0t; phenol compounds, e.g. (C«H«0)4'S0i, (C«HiO)c-80t, 
(C«H/))t<X>s; vad cotun compounds of the inert gas dements 

(pp. 382-383). , J 

It is obvious that the coniUtions und« wMch dathrate compounds 
can form are limited and highly spedfic. Among those of importance 
are: 

1. An open crystal structure in the endoaing component. This 
neoesdtates directed linkages holding the molecule and crystal together, 
suffident extenaon of the groups to form a cavity of smtable d«e, 
and a xi^d structure. 

2 Small access holes to tiie endosed cavity. This may result frMn;. 
dther proper <fispoation of groups in the formation of the crystal <w - 
suffident surface area in the endosdnggrwflB. \ 
3, Ready availability of the trapped component at the tmie vfheni 
the cavity is dosed. 

Such comiwunds are of conaderable theoretical Interest but 
Uddng in pnwtical importance. Information on.pof*^® 
ments in dathrate compounds and the structures whidx lead to themi 
to be found in Powdl's discusnons." 

NON-STOICmOMErRIC COMPOUNDS 
The law (rfaefinite proportions is one of the bade tenets of ( 
Its validity is indicated by the restrictions imposed upon bond f c 
tion where dectrons are involved as already ouOined, ai^ Hs r~ 
tion is generally tiie assumed bads for any type of diemical « 
tion. There are, however, many instances of apparent departure 1 
tills rule among «o«a compounds. Such compounds do not pwseraj 
exact compodtiops which are predicted from dectironic oonside 
alone and are commonly referred to as Berthoffide or non-6toiduoi 

H. M. PoweU: /. Chem. Soc, 1M8, 61; Endecamur, «, 154 (1950); Re$earA, J 
353 (1947-1948). 



no com 



Fundamentals 



chemistry 
a 

modern 
introduction 



FRANK BRESCIA 
JOHN ARENTS 
HERBERT MEI&LIGH 
AMOS TURK 

Deparimenl of Chemisiry 
TheCUyCoOegtiffihc 
dfy Umocrsify of New York 



ACADEMIC PRESS 
New York and London 





The text €(f ihu book «a< oel in Monotype 
iroosKif 8a prmtei cmd hovtnd ky The MapU Prt$9 Compa$iy, 
The book it pritUed om Tkor Coic Plate by Beryitrotn Paper 
Company. The hindim^ it Tonero offtU do&K, 
ArkwrtyH-InUHakoi Inc. 

Tke deHyn of ike text and oooer wofi created by BeUy Binne. 
Tke drawmge are by F, W, Taylor, 



dorauoHT ® 1966^ bt ACASBiac niKss ma 
An rie^ts reserved. 

No pari of this hock, may be rqutxlaced in any form, 
bx pbotoeUt^ aiicrofilm, <»- aoy other meano, without 
written permtsstOD from the pabGshers, 

ACADEiffC VSS88 INa 

111 rath ATeaoe, New Totk, New York 10003 

United Eincdom Edition pnUtdaed by 
ACADsaac TBXOB mc (u>ndom) i;rD. 
Betk^y Square House, London W.l 



Library of Conyrtet catalog card number: 65-26049 
First Printing, January, 1966 
Second Printing, April, 1966 

PKtNTED IN THE UNrTED STATES OF AMKRICA 



«a«er.-|fce «t<i«« <^c e&«m^ ttodmg ^Uem remain, eonUant, Thia laur 

" TS^* *^ with the most precise 

H^f^^-J?^.*^ ~ t*"' <l«*»«ty » less tZ^ 

be detected with the best available balance. 

4.2 THE lAW OF DEFINIIE FROPOBnONS 

Analyses of eompouads show that when elements foim a given comDound 
they always combine in the same ratio by weight. For exampkrinde- 
pendently of the source or method of formation. sUioon dioxide. Sia 
contains 46.7% by weight of sOioon and 63.3% of oxygen. This kno^dedt* 
IS summarued in the law o/definiU pnpoHumt: tU toeight composUum^a 
ffwen compound it eontUtnL ' 

EXAMTUsl M^«of.lll«»odu,t,Sl,l.««i*»d««|wlUilOO.Og«f oKygw, a. 
formI«« rfllooa 4l«rfd«. SIO,. How ««y g«m« of SiO. «r« formed .nd h<»w 
UMny enuiu of Qs remain uneombined? 

AMSWKH Since 44^7 « of Si combine, with 55 J ^ of O,, the qu.nUty of 0, rts 
quired per gram of Si is 

4^7 g Si 

and, therefore, for 10.0 g of Si, the quantity of O, reqaired is 



.SSoSgOt 



n-4gO, 



Hence, the weight of SiO, formed Is 10,0 g + U.4 g « ^ «„d the weight of 
uncombincd Oi Is 100.0 g ~ 11.4 g « 88.6 g, 

4.3 THE ATOMIC THEORY 

The weight i«l^tioDships of substaaces participating ia chemical teactioiis 
are cleaiiy explained in terms of the atomic theory. Although John 
Dalton (1803) is general^ reoognixed as the inventor of the theoiy, he 
was anticipated by other scientists, particolaribr William Hig^ns (1789). 
Thus, it appears that the Uw of multqile proportions (Section 4.4) waa 
foreshadowed Higgins and Dalton from tiidr respective atomic 
theories. A verified prediction made by a theory constitutes the strong 
argument m its favor. However, the novd and central point of Dalton's 
activities was the attempt to detennme the i^tive weights of atoms. 
This goal focused attention upon the theory, and revealed a new field of 
human endeavor timt ultimately made chemistry a systematiijed body of 
knowledge. 

The assumptions of the atomic theory were 

(0 The eUmenU are composed of indivUaU par^^ 
(it) AU the atoms of a given element possess identical properties, for 
example, mass. 



70 4. Atoms and molecules 



BRIEF ATTACHMENT AT 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479,810 
Filed: June 7, 1 995 



Group Art Unit: 1751 
Examiner: M. Kopec 



Docket: YO987-074BZ 



Date: March 1 , 2004 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



FIFTH SUPPLEMENTAL AMENDMENT 



Sir: 



In response to the Office Action dated February 4, 2000: 



ATTACHMENT 42 



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BRIEF ATTACHMENT AU 



NEW SUPERCONDUCTIVE COMTOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, AND METHODS FOR THEIR USE AND PREPARATION 

^ =^ 

DESCRIPTION 
Technical Field 



5 This invention relates to a new class of superconducting 

compositions having high superconducting transition 
temperatures and methods for using and preparing these 
compositions, and more particularly to superconducting 
compositions including copper and/or other transition 

0 metals, the compositions being characterized by a 

superconducting phase and a layer-like structure. 



Backj^round Art 



Superconductivity is usually defined as the complete 
loss of electrical resistance of a material at a well- 
defined temperature. It is known to occur in many ma- 
terials, including about a quarter of the elements of 
the periodic table and over 1000 alloys and other 
multi-component systems. Generally, superconductivity 



Y0987-07A;C 



- 1 - 



is considered to be a property of the metallic state of 
a material since all known superconductors are metallic 
under the conditions that cause them to be supercon- 
ducting. A few normally non-metallic materials, for 
example, become superconducting under very high pressure 
wherein the pressure converts them to metals before they 
exhibit superconducting behavior. 

Superconductors are known to be very attractive for the 
generation and energy-saving transport of electrical 
power over long distances, and as materials used to form 
the coils of very strong magnets. These magnets are used 
in, for example, plasma and nuclear physics, nuclear 
magnetic resonance medical diagnosis systems, and in 
connection with the magnetic levitation of fast trains. 
Other potential uses of superconducting materials occur 
in power generation systems using thermonuclear fusion 
where very large magnetic fields must be provided, 
superconducting magnets being the only possible means 
for providing such high fields. In addition to these 
applications, superconductors are known in liigh speed 
switching devices, s.ilch as Josephson type switches, and 
in high density packaging and circuit layouts. Super- 
conductors also arc used in different types of clec- 



Y0987-07Ays 



- 2 - 



tronic instrumentation, such as magn^stic susccptomctcrs 
and magnetometers. 

While the advantages of superconductors are quite obvi- 
ous to scientists and engineers, the common disadvantage 
of all presently known superconductive materials lies 
in their very low transition temperature. This temper- 
ature is often called the critical temperature and 
is the temperature above which superconductivity will 

not exist. Usually T is on the order of a few decrees 

c 

Kelvin. The element with the highest T^ is niobium whose 
T^ is 9.2^K. The composition having the highest previ- 
ously known T is Nb^Ge which exhibits a T of about 23^K 
c 3 c 

at ambient pressure. Transition metal alloy compounds 
of the A15(Nb^Sn) and Bl(NbN) structure have been shown 
to have high superconducting transition temperatures. 
Among the A15 comf>ounds is the aforementioned composi- 
tion Nb^Ge. Some of these compositions are described 
in J. Muller, Rep. Prog. Phys. 43, 663 (1980), and M. 
R. Beasley et al, Phys. Today, 37 (10), 60 (198A), 

It is known in the art that a small number of oxides will 
exhibit superconductivity. Reference is made to D.C. 
Johnston et al. Mat. Res. Bull. 8, 777 (1973), which 
describes high temperature superconductivity in the Li- 



Y0987-074y. 



- 3 - 




Ti*0 system with superconducting onsets as high as 

13.7^K. Tliese materials have multiple crystal lographic 

phases including a spinel structure exhibiting the high 

T . Other metallic oxides, such as the perovskite Ba- 
c 

Pb-Bi-O system^ can exhibit superconductivity due to high 
elect ron-phonon coupling in a mixed valent compound « as 
described by G. Binnig et al, Phys. Rev. Lett., 45, 1352 
(1980), and A.W. Sleight et al. Solid State Communi- 
cations, 17, 27 (1975). 



10 As is evident from the foregoing, superconductors pres- 

ently known require liquid helium for cooling and this, 
in turn, requires an elaborate technology and a consid- 
erable investment in cost and energy. Accordingly, it 
is a primary object of the present invention to provide 

15 new compositions which exhibit high and methods for 

using and producing the same. 

It is another object of the present invention to provide 
new superconducting compositions and methods for using 
and making them wl^re cooling with liquid helium is not 
20 required in order to have superconductive properties in 

the comp>ositions - 



Y0987-074)C 



- A - 



It is another object of tlie present invention to provide 
novel superconductive materials that are mult i-va lent 
oxides including transition metals, the compositions 
having a perovskite-like structure. 

It is a further object of the present invention to pro- 
vide novel superconductive compositions that are oxides 
including rare earth and/or rare earth-like atoms, to- 
gether with copper or other transition metals that can 
exhibit mixed valent behavior. 

It is a still further object of the present invention 
to provide novel superconductive compositions exhibiting 
high T^, where the compositions are oxides including a 
phase having a layer-like structure and including cop- 
per. 

It is a still further object of the present invention 
to provide new superconductive compositions exhibiting 
high T^, where the superconductive compositions include 
layered structures including a rare earth and/or rare 
earth -like element ^nd a transition metal. 

It is another object of this invention to provide a new 
class of superconducting compositions characterized by 



Y0987-074V: 



- 5 - 



a greater than 26 **K, and etethods for making and using 
these compositions. 

It is another object of this invention to provide new 
compositions and methods for using them» where the com- 
positions include a multi-valent oxide of copper and 
exhibit a greater than 26*K. 

The basis for our invention has been described by us in 
the following previously published article: J.G. 
Bednorz and K.A. Muller, Zeitschrift fur Physik B - 
Condensed Hatter, 64, pp, 189-193^ W^KW 

Another article of interest. by us is J.G. Bednorz, K.A. • 
Nuller, M. Takashige, Europhysics Letters, 3(3), pp. 
379-385 (1987). 

Suiranary of the Invention 

This invention relates to novel compositions exiiibiting 
superconductivity at temperatures higher than those ob- 
tained in prior known superconductive materials, and to 
methods for using and forming these comf>ositions . llicse 
compositions can carry supercurrents (i,.e., electrical 



Y0937-07AX 



- 6 - 



currents in a substantially zero resistance state of the 
composition) at ^temperatures greater than 26**K. In 
general y the compositions are cliaracterized as mixed 
transition metal oxide systems where the transition 
iQctal oxide can exhibit multivalent behavior. Tliese 
compositions have a layer-type crystalline structure ^ 
often perovskite*like, and can contain a rare earth or 
rare earth-like element. A rare earth-like element 
(sometimes termed a near rare earth element^is one 
whose properties make it essentially a rare earth ele- 
ment. An example is a group IIIB element of the periodic 
table, such as La. Substitutions can be found in the 
rare earth (or rare earth-like) site or in the transi- 
tion metal sites of the compositions. For example, the 
rare earth site can also include alkaline earth elements 
selected from group IIA of the periodic table, or a 
combination of rare earth or rare earth- like elements 
and alkaline earth elements. Examples of suitable 
alkaline earths include Ca, Sr, and Ba. Tlie transition 
metal site can include a transition metal exhibiting 
mixed valcnt behavior » and can include more than one 
transition metal. A particularly good example of a 
suitable transition metal is copper. As will be appar- 
ent later, Cu- oxide based systems provide unique and 
excellent properties as high superconductors. 



YO987-07AX 



- 7 - 



An example of a superconductive composition having high 

is the cocnposition represented by the formula 
RE-TM-0, where RE is a rare earth or rare earth- like 
eleioenty TH is a nonmagnetic transition metal, and O is 
oxygen. Examples of transition metal elements include 
Cu, Ni, Cr etc. In particular, transition metals that 
can exhibit multi-valent states are very suitable. The 
rare earth elements are typically elcunents 58-71 of the 
periodic table, including Ce, Nd« etc. If an a Ilea line 
earth element (A£) were also present, the 'composition 
would be represented by the general formula RE-AE-TM-0. 

The ratio (A£,RE) : TM is generally approximately 1:1, 
but can vary from this as will be shown by examples where 
the ratio (AE,RE) : TM is 2:1. Of course, the amount 
of oxygen present in the final composition will adjust 
depending upon the processing conditions and will be 
such that the valence requirements of the system are 
satisfied. 

The methods by which these superconductive compositions 
can be made can use known principles of ceramic fabri- 
cation, including the mixing of powders containing the 
rare earth or rare earth-like, alkaline earth, and 

Y0987-074X - 8 - 



transition metal elements, coprccipitation of these ma- 
terials > and heating steps in oxygen or air. 

A particularly suitable superconducting material in ac- 
cordance with tliis invention is one containing copper 

as the transition metal* Copper can exist in a Cu*" or 
3+ 

Cu mixed valence state. Tlxe state(s) assumed by cop- 
per in the overall composition will depend on the amount 
of oxygen present and on any substitutions in the crys- 
talline structure- Very high has been found in Cu- 
oxide systems exhibiting mixed valence states » as 
indicated by conductivity and other measurements. Cop- 
per oxide systems including a rare earth or rare earth- 
like element, and an alkaline earth element, are unique 
examples of this general class of superconducting lay- 
ered copper oxides which exhibit greater than 26^K. 

These and other objects, features, and advantages will 

- - y 

be apparent from the following more particular de- 
scription of the preferred embodiments. 

Brief Description of tlic Dravings 



Y0987-074y 



- 9 - 



FIG. 1 is a schematic illustration of a representative 
circuiv used to measure dc conductivity in the high 
superconductors of this invention. 

FIG. 2 is a plot of the temperature dependence and 
resistivity in the composition Ba La Cu 0^ . for 
samples 'with x(Ba)=l (upper two curves, left scale) and 
x(Ba)=0.75 (lower curve, right scale). Tlie influence 
of current density through the composition is also 
shown . 



FIG. 3 is a plot of t:he low temperature dependence of 

resistivity in the composition Ba La^ Cu^O^,^ , with 

X 5-x 5 5(3-y) 

x(Ba))=l, for different annealing conditions (i.e., 
temperature and oxygen partial press ui;e. 



FIG- A is a plot of the low -temperature resistivity of 

the composition Ba La_ Cu_0^,^ ^ with x(Ba)= 0.75. 

X 5-x 5 5(3-y) ' * 

recorded for different densities of electrical current 
through the compos ition, 

Description of the Preferred Embod iments 



Y0987-07Ay 



- 10 - 



V 

The superconductive compositions of this invention are 

transition metal oxides generally having a mixed valence 

and a layer-like crystalline structure* and exhibit T 's 

c 

higher than those of previously known sui>erconducting 
materials. These compositions can also include a rare 
earth site in the layer-like structure where this site 
can be occupied by rare earth and rare earth- like atoms » 
and also by alkaline earth substitutions such as Ca» Sr, 
and Ba. The amount of oxygen present will be such that 
the valence requirements of the system are satisfied^ 
the amount of oxygen being somewhat a function of the 
processing steps used to make the the superconductive 
compositions* Non -stoichiometric amounts of oxygen can 
be present in these comi>ositions. The valence state of 
the elements in the oxide will be determined by the final 
composition in a manner well known to. chemists • For 

example, the transition metal Cu may be present in some 

2+ 3+ 
compositions in both a Cu and a Cu state. 

An example of a superconductive compound having a 
layer-type structure in accordance with the present in- 
vention is an oxide of the general composition RE^TMO^, 
where RE stands for the rare earths ( lanthaaidcs) or 
rare earth-like elements and TM stands for a transition 
metal. In these compounds the RE portion can be par- 



YO987-07AX 



- 11 - 



tially substituted by one or more members of the 
alkaline earth group of elements. In these particular 
compounds, the oxygen content is at a deficit.- 

For example, one such compound that meets this general 
description is lanthanum copper oxide La^CuO. in which 
the lanthanum - which belongs to the 1 1 IB group of 
elements - is in part substituted by one member of the 
neighboring IIA group of elements, viz. by one of the 
alkaline earth metals (or by a combination of the mem- 
bers of the IIA group), e.g., by barium. Also, the ox- 
ygen content of the compound can be incomplete such that 
the compound will have the general composition 
La^-x^^x^^^A-y' x < 0.3 and y < 0.5. 

Another example of a compound meeting this general for- 
mula is lanthanum nickel oxide wherein the lanthanum is 
partially substituted by strontium, yielding the general 
formula ^'^2-x^'^x'^^^A-y * ^^i^l another example is cerium 
nickel oxide wherein the cerium is partially substituted 

by calcium, resulting in Ce^ Ca NiO, 

2-x x A-y 

Tlie following description will mainly refer to barium 

as a partial replacement for lanthanum in a La CuO 

2 A 

compound because it is in the Ba-La-Cu-0 system that 



Y0987-07AX 



- 12 - 



many laboratory tests Iiave been conducted. Some com- 
pounds of the general Ba-La-Cu-0 system have l>een de- 
scribed by C. Michel and 6. Raveau in Rev. Chiro. Min* 
21 (1984) 407, and by C. Michel, L. Er-Raklio and B. 
Raveau in Mat. Res. Bull., Vol. 20, (1985) 667-671. They 
did not, however, find or try to find superconductivity. 
These references and their teachings regarding 
perovskite-like layered oxides of mixed valent transi- 
tion metals, and their preparation, are herein incorpo- 
rated by reference. 



Experiments conducted in connection with the present 
invention have revealed that high-T^ superconductivity 
is present in compounds where the rare earth or rare 
earth- like element is partially replaced by any one or 
more of the members of the IIA group qf elements, i.e., 

the alkaline earth metals. Actually, the T of 

c 

2+ 

La^CuO, with the substitution Sr is higher and its 
2 4-y ^ 

superconductivity- induced diamagnet ism larger than that 

2+ 2+ 
found with the substitutions Ba and Ca 

Tlie Ba-La-Cu-0 systiani can exliibit a number of 

crystal lographic phases, namely with mixed -va lent copper 

constituents which have itinerant electronic states be- 

3+ 2+ 
tween non-Jahn-Tel ler Cu and Jahn-Teller Cu ions. 



Y0987-074X 



- 13 - 



Tliis applies likewise to systems where nickel is used 

34- 

in pldce of copper, with Ni being the Jahn-Tcller 

2+ 

constituent, and Ni being the non-Jahn-Tcller con- 
stituent. The existence of Jahn-Teller polarons in 
conducting crystals was postulated theoretically by K.H. 
Hoeck, H. Nickisch and H. Tliomas in Helv. Phys. Acta 56 
/ i"ioc*a\ /o-iV Polarons have large electron-phonon inter- 



actions and, therefore, are favorable to the occurrence 
of superconductivity at higher critical temperatures. 



10 Samples in the Ba-La-Cu-0 system, when subjected to X- 

ray analysis, revealed three individual crystal lographic 
phases, viz. 

• a first layer-type perovskite-like phase, related 
to the 

15 K^NiF^ structure, with the general composition 

La^ Ba CuO, , with 
X « 1 and y > 0; 



• a second, non-conducting CuO phase; and 

• a third, nearly cubic perovskitc pliase of tlie 
20 general composition La^^^Ba^CuO^ which appears 

to be independent of the exact starting composi- 
tion. 



Y0987-07AK 



- lA - 



Of these three phases the first one appeared to be re- 
sponsible for the observed high-T^ superconductivity, 
the critical temperature showing a dependence on the 

2+ 

barium concentration in that phase. Obviously, the Ba 

2+ 

substitution caused a mixed*valent state of Cu and 
Cu to preserve cliargc neutrality. It is assumed that 
the oxygen deficiency, y, is the same in the doped and 
undoped crystallites - 

In this application, the terms transition metal oxide, 
copper, oxide, Cu-oxide, etc. are meant to broadly in- 
clude the oxides which exhibit superconductivity at 
temperatures greater than 26®K. Tlius, the term copper 
oxide can mean, among other things, an oxide such as 

CuO- in the mixed oxide comedos it ion La^ Ba CuO, 
H-y 2-x X 4-y 

Both La^CuO^ and LaCuO^ are metallic conductors at high 
temperatures in the absence of barium. Actually, both 
are metals like LaNiO^. Despite their metallic charac- 
ter, the Ba-La-Cu-0 type materials are essentially ce- 
ramics, as are the other compounds of the RE^TMO^J^ type, 
and their manufacture generally follows the known prin- 
ciples of ceramic fabrication, Tlie preparation of a 
superconductive Ba-La-Cu-0 compound, for example, in 



Y0987-07A/ 



- 15 - 



accordance with the present invention typically invol 
the following manufacturing steps: 



• Preparing aqueous solutions of the respective 
nitrates of barium, lanthanum and copper and 
coprecipitation thereof in their appropriate ra- 
tios, 

• adding the coprecipitate to oxalic acid and 
forming an intimate mixture of the respective 
oxalates. 

• decomposing the precipitate and causing a solid- • 
state reaction by heating the precipitate to a 
temperature between 500 and 1200^C for one to eight 
hours. 

• pressing the resulting product at a pressure of 
about 4 kbar to form pellets, 

• re-heating the pellets to a temperature between 
500 and 900^C for one half hour to three hours for 
sintering. 



YO987-07AX 



- 16 - 



It will be evident to those skilled in the art that if 
the partial substitution of lanthanum by another 
alkaline earth element, such as strontium or calcium, 
is desired, the particular nitrate thereof will have to 
be used in place of the barium nitrate of the example 
process described above. Also, if the copper of this 
example is to be replaced by another transition metal, 
the nitrate thereof will obviously have to be employed. 
Other precursors of metal oxides, such as carbonates or 
hydroxides, can be chosen in accordance with known 
principles. 

Experiments have shown that the partial contents of the 
individual compounds in the starting composition play 
an important role in the formation of the phases present 
in the final product. While, as mentioned above, the 
final Ba-La-Cu-0 system obtained generally contains the 
said three phases, with the second phase being present 
only in a very small amount, the partial substitution 
of lanthanum by strontium or calcium (and perhaps 
beryllium) will result in only one phase existing in the 
final La Sr CuO or La Ca CuO, , respectively, 

j\. jv ^ y ^""X X y 

provided x i< 0.3. 



Y0967-07AK 



- 17 - 



With a ratio of 1:1 for the respective (Ba, La) and Cu 
contents, it is expected that the three phases will oc- 
cur in the final product. Setting aside the secondi 
phase, i.e. the CuO phase whose amount is negligible, 
the relative volume amounts of the other two phases are 

dependent on the barium content in the La^ Ba CuO, 

2-x X A-y 

complex. At the 1:1 ratio and with an x = 0.02, the 
onset of a localization transition is observed, i.e., 
the resistivity increases with decreasing temperature, 
and there is no superconductivity. 

With X = 0.1 at the same 1:1 starting ratio, there is a 
resistivity drop at the very high critical temperature 
of 35^K. 

With a (Ba, La) versus Cu ratio of 2:1 in the starting 

composition, the composition of the La2CuO^:Ba phase, 

which appears to be responsible for the 

superconductivity, is imitated » with the result that now 

only two phases are present, the CuO phase not existing. 

With a barium content of x = 0,15, the resistivity drop 

occurs at T = 26^K. 
c 

Tlie method for preparing tliese Ba-La-Cu-0 sample com- 
plexes used two lieat treatments for the precipitate at 



YO987-074X 



- 18 - 



3i\ elevated temperature for several hours. In tlie ex- 
periments carried out in connection with the present 
invention it was found that best results were obtained 
at 900^C for a decomposition and reaction period of 5 
hours, and again at 900^C for a sintering period of one 
hour. These values apply to a 1:1 ratio composition as 
well as to a 2:1 ratio composition. 

For the 2:1 ratio composition, a somewhat higher tem- 
perature is permissible owing to the higher melting 
point of the composition in the absence of excess copper 
oxide. However, a one*phase compound was not achieved 
by a high temperature treatment. 



Y0987-07A/ 



- 19 - 



Conductivity Measurements (FIGS. 

\^ 

Tlie dc conductivity of represcntntive Ba-La-Cu-0 com- 
positions was measured to determine their low temper- 
ature behavior and to observe their high T . Tliese 

c 

measurements were performed using the well known four- 
point probe technique, which is schematically illus- 
trated in FIG. 1, Rectangular shaped samples 10 of 

^^xX'^S-xVF^^S^SO-y) ^^^^ sintered pellets » and 

provided with gold sputtered electrodes 12A and 12B, 
about 0.5 microns thick. Indium wires 14A and 14B con- 
tact electrodes 12A and 12B, respectively. The saii^>le 
was contained in a continuous flow cryostat 16 
(Leybold-Hereaus) and measurements were made over a 
temperature range 300-41^K. 

Electrodes 12A and 12B are connected in a circuit in- 
cluding a current source 18 and a variable resistor 20. 
Indium leads 22A and 22B are pressed into contact with 
sample 10 and fixed with silver paint 24, Leads 22A, 
22B are connected to a voltage reading instrument 26. 
Since the current and voltage arc accurately determined, 
the resistivity of the sample 10 is then known. In the 
configuration used for these measurements, a computer 
was used to provide a computer -con trolled fully- 



YO987-074X. 



- 20 - 



20 



automatic system for temperature variation, data acqui- 
sition and processing. 

In FIG. 2, the low temperature dependence of resistivity 
^Utf^^ measured in ohm-ctns) in the composition 

Ba^La^_^Cu^O^^^_^j is plotted for two different values 
of X, For the upper two curves, the value of x(Ba) is 
1 and the left side vertical scale is used. For the 
lower curve, the value of x is 0.75, and the resistivity 
scale on the right hand side of the figure is used. Tlie 

10 data is taken for different values of current density: 

2 2 
0.25 A/ cm for the top curve and 0.50 A/cm for the 

middle and bottom curves. 



For barium-doped samples with x(Ba) < 1.0, for example 

2 

with x < 0.3, at current densities of 0.5A/cm , a high- 
15 temperature metallic behavior with an increase in 

resistivity at low temperatures was found as depicted 
in FIG. 2- At still lower temperatures, a sharp drop 
in resistivity (> 90%) occurred which for higher current 
densities became partially suppressed (FIG. 1 upper 
curves, left scale). Tliis characteristic drop was 
studied as a function of the annealing conditions, i.e. 
temperature and oxygen partial pressure as shown in FJG. 
2. For samples annealed in air, the transition from 



Y0987-07AX 



- 21 - 



itinerant to localized behavior , as indicated by the 
minimum in resistivity in the 80**K range, was not found 
to be very pronounced. Annealing in a slightly reducing 
atmosphere, however, led to an increase in resistivity 
and a more pronounced localization effect. At the same 
time, the onset of the resistivity drop was shifted to- 
wards the 30^K region. Curves A and 5 (FIG. 3), recorded 
for samples treated at 900 **C, show the occurrence of a 
shoulder nt still lower temperatures, more pronounced 
in curve 6, At annealing temperatures of 1040**C, the 
highly conducting phase has almost vanished. Long 
annealing times and/or high temperatures will generally 
destroy the superconductivity. 

Tlie mixed-valent state of copper is of importance for 
electron-phonon coupling. Tlierefore, the concentration 
of electrons was varied by the Ba/La ratio, A typical 
curve for a sample with a lower Ba concentration of 0,75 
is shown in FIG. 2(right scale). Its resistivity de- 
creases by at least three orders of magnitude, giving 
evidence for the bulk being superconducting below 13°K 
with an onset arounct 35^K, as shown in FIG. 4 on an ex- 
panded temperature scale. FIG. A also shou's the influ- 
ence of the current density, typical for granular 



YO987-074X 



- 22 - 



compounds. Current densities of 7.5, 2.5, and 0.5 A/cm 
were passed through the superconducting composition. 

When cooling the samples from room temperature, the 
resistivity data first show a mctal-like decrease. At 
low temperatures, a change to an increase occurs in the 
case of Ca substituted compounds and for the Ba- 
substituted samples. Tliis increase is followed by a 
resistivity drop, showing the onset of superconductivity 
at 22 ± 2*^K and 33 ± 2^ K for the Ca and Ba compounds, 
respectively. In the Sr compound, the resistivity re- 
mains metallic down to the resistivity drop at 40 ± l^K. 
The presence of localization effects, however, depends 
strongly on alkaline*earth ion concentration and sample 
preparation, that is to say, on annealing conditions and 
also on the density, which have to be optimized. All 
samples with low concentrations of Ca, Sr, and Ba show 
a strong tendency to localization before the resistivity 
drops occur - 

Apparently, the onset of the superconductivity, i.e. the 
value of the critical temperature T^, is dependent on, 
among other parameters, the oxygen content of the final 
compound. It seems that for certain materials, an oxy- 
gen deficiency is necessary for the material to have a 



Y0987-074X 



- 23 - 



high"T^ beliavior. In accordance with the present in- 
vention, the method described above for making the 
La^CuO^rBa complex is complemented by an annealing step 
during wltich the oxygen content of the final product can 
be adjusted. Of course, what was said in connection with 
the formation of the La^CuO^rBa compound likewise ap- 
plies to other compounds of the general formula RE^TMO^ 
: AE (where AE is an alkaline earth element) » such as» 
e.g. Nd^NiO^rSr. 

In the cases where a heat treatment for decomposition 
and reaction and/or for sintering was performed at a 
relatively low temperature, i.e., at no more than 950^C, 
the final product is subjected to an annealing step at 
about 900*^0 for about one hour in a reducing atmosphere. 
It is assumed that the net effect of this annealing step 
is a removal of oxygen atoms from certain locations in 
the matrix of the RE^TMO^ complex, thus creating a dis- 
tortion in its crystalline structure. The 0^ partial 
pressure for annealing in this case may be between lo"^ 
and 10 ^ bar. 

In those cases where a relatively high temperature 

i 

(i.e., above 950 C) is employed for the heat treatment, 
it might be advantageous to perform the annealing step 



Y0987-074X 



- 2A - 



in a slightly oxidizing atmosphere. This would make up 
for an assumed exaggerated removal of oxygen atoms from 
the system owing to the high temperature and resulting 
in a too severe distortion of the system's crystalline 
structure. 

Resistivity and susceptibility measurements as a func- 
tion of temperature of Sr^"*" and Ca^'*^-doped La CuO 

2 4-y 

ceramics show the same general tendency as the 
2+ 

Ba -doped samples: a drop in resistivity p (T), and a 
crossover to diamagnetism at a slightly lower temper- 
ature. The samples containing Sr^^ actually yielded a 
higher onset than those containing Ba^^ and Ca""^. Fur- 
thermore, the diamagnetic susceptibility is about three 

times as large as for the Ba samples. As the ionic ra- 

2+ 1+ 
dius of Sr nearly matches that of La , it seems that 

the size effect does not cause the occurrence of 

superconductivity. On the contrary, it is rather ad- 

2+ 

verse, as the data on Ba and Ca indicate, 

Tlie highest T^ for each of the dopant ions investigated 
occurred for those concentrations where, at room tem- 
perature, the REj-x^x^A-y structure is close to the 
or thorhombic- tetragonal structural phase transition, 
which may be related to the substantial electron -phonon 



Y0987-07Ay - 25 



interaction enhanced by the substitution. Tlie 
alkaline-earth substitution of the rare earth metal is 
clearly important, and quite likely creates TM ions with 
no e^ Jahn-Tellcr orbitals. Tlierefore, the absence of 
these Jahn-Teller orbitals, that is, Jahn-Teller holes 
near the Fermi energy, probably plays an important role 



in the T enhancement. 

.c 



While examples have been given using different transi- 
tion metal elements in the superconducting compositions, 
copper oxide compositions having mixed valence appear 
to be unique and of particular importance, having 
superconducting properties at temperatures in excess of 
26''K. Tliese mixed valent copper compositions can in- 
clude a rare earth element and/or a rare earth-like el- 
ement which can be substituted for by an alkaline earth 
element. The amount of oxygen in these compositions 
will vary depending upon the mode of preparation and 
will be such as to meet the valence requirements of the 
composition. These copper-based compositions have a 
layer-like structure, often of a perovskite type. For 
a more detailed description of some of the types of 
crystal lographic structures that may result, reference 
is made to the aforementioned publication by Michel and 



Y0967-07A>< 



- 26 - 



Kaveau in Rev. Chim. Min. 21, A07 (1984), and to C. 
Michel et al. Mat. Res. Bull.. Vol. 20, 667-671 (1965). 

While the invention has been described with respect to 
particular embodiments thereof, it will be apparent to 
those of skill in the art that variations can be made 
therein without departing from the spirit and scope of 
the present invention. For example, while the range of 
compositions includes rare earth elements and transition 
metal elements, the ratios of these elements can be 
varied because the crystalline structure can accommodate 
vacancies of these elements and still retain a layer- 
like structural phase exhibiting superconductivy. 

Further, the stoichiometry or degree of non- 
stoichiometry of oxygen content (i.e., oxygen deficit 
or surplus) of these compositions can be varied by using 
reducing or oxidizing atmospheres during formation of 
the compounds and by using different doping amounts in 
the rare eorth and transition metal sites of the crystal 
structure. TIUs type of distortion of the crystal 
structure and the many forms that it can encon.pass are 
readily apparent from reference to the a foremen Lioned 
Michel and Raveau publications. Thus, the invention 
broadly relates to mixed (doped) transition metal oxides 



Y0987-07A >< 



- 27 - 



having a layer- like structure that exhibit supercon- 
ducting behavior at temperatures Ln excess of 26**K. 
these materials, a mixed copper oxide having multi- 
valent states provides high and favorable supercon 
ducting properties. 



¥0987-074^, 



- 28 - 



CLAIMS 



Having thus described our invention what we claim as new 
and desire to secure as Letters Patent, is: 

1. A superconductive composition having a transition 

temperature greater than 26*K, the composition in- 
cluding a rare earth or oioai^are earth- like ele- 
ment, a transition metal element capable of 
exhibiting multivalent states and oxygen, and in- 
cluding at least one phase that exhibits 
superconductivity at temperature in excess of 26**K. 



2. Tlie composition of claim 1, further including an 

alkaline earth element substituted for at least one 
atom of said rare earth or rare earth- like element 
in said composition. 



3. The composition of claim 2, where said transition 

i 

metal is Cu . 



Y0987-074X 



- 29 - 



1 A. The composition of claim 3, where said alkaline earth 



5 



. clement is selected from the group consisting of 



jt) 3 ^ Ca, Ba, and Sr. 



I 5. Tlie composition of claim 1, where said transition 
5 metal element is selected from the group consisting 

3 of Cu, Ni, and Cr» 



1 6. The composition of claim 2, where said rare earth 
^ or rare earth- like element is selected from the 

3 group consisting of La, Nd, and Ce. 



f 7. The composition of claim 1, where said phase is 
^ crystalline with a perovskite-like structure. 



8. Tile composition of claim 2, where said phase is 
crystalline with a pcrovskitc- like structure. 



i 9. The composition of claim 1, where said phase exhibits 
^ a layer- like crystalline structure. 



Y09S7-074X 



- 30 - 



10. Tlie composition of claim 1, where said phase is a 
mixed copper oxide phase. 

11. The composition of claim 1, where said composition 
is comprised of mixed oxides with alkaline earth 
doping. 

12. A superconducting combination^ including a 
superconductive composition having a transition 
temperature > 26**K, 

means for passing a superconducting electrical 
current through said composition while said compo- 
sition is at a temperature > 26**K., and 

cooling means for cooling said composition to a 
superconducting state at a temperature in excess 
of 26**K. 

13. Tlic combination of claim 12, where said 

superconductive composition includes a transition 
metal oxide. 



Y0987-074y 



- 31 - 



« 14. 



The combination of claim 12, where said 
superconductive composition includes Cu-oxide. 



I 15. The combination of claim 12, where said 

^ superconductive composition includes a multivalent 

3 transition metal, oxygen, and at least one addi- 
U 

• tional element. 

I 16, The combination of claim 15, where said transition 

^ metal is Cu. 

/ 17. Tlie combination of claim 15, where said additional 
element xs a rare earth or rare earth- like element. 

I 18. The combination of claim 15, where said additional 
element is. an alkaline earth element. 

I 19. The combination of claim 12, where said composition 

^ includes a perovskite-like superconducting phase. 



Y0987-074;>< 



- 32 - 




1 




20. Tlie combination of claim 12, where said composition 



includes a substituted transition roetal oxide. 



21. TIte combination of claim 20, where said substituted 



22. The combination of claim 20, where said substituted 
transition metal oxide is an oxide of copper. 

23. The combination of claim 20, where said substituted * 
transition metal oxide has a layer-like structure. 

2A. A method including the steps of forming a transition 
metal oxide having a phase therein which exhibits 
a superconducting state at a critical temperature 
in excess of 26^ K, 



transition metal oxide includes a multivalent 



transition metal element. 




superconducting state in said phase, and 



Y0987-074X 



- 33 - 



passing an electrical supercurrcnt through said 
transition metal oxide while it is in said super- 
conducting state. 

25. The method of claim 24, where said transition metal 
oxide is comprised of a transition metal capable 
of exhibiting multivalent states. 

26. The method of claim 24, where said transition metal 
oxide is comprised of a Cu oxide. 

27. A superconducting composition having a transition 
temperature in excess of 26^K, said composition 
being a substituted Cu-oxide including a supercon- 
ducting phase having a structure substantially 
close to the orthorhombic- tetragonal phase transi- 
tion of said composition. 

28. The composition of claim 27, where said substituted 
Cu-oxide includes a rare earth or rare earth- like 
element. 



Y0987-074X 



- 34 - 



I 29. Tlic composition of claim 27-, where said substituted 
Cu-oxide includes an alkaline earth element. 



/ 30. Tlie composition of claim 29, where said alkaline 
^ earth element is atoroically large with respect to 

3 



Cu. 



I 31. The composition of claim 27, where said composition 

^ has a crystalline structure which enhances 

3 electron-phonon interactions to produce 

V superconductivity at a temperature in excess of 



26"K, 



i 32, The composition of claim 31, where said crystalline 

^ Wm>^ *^ structure is layer-like, enhancing the number of 

Jahn-Teller polarons in said compocite^ Cou< J>c»:.*i+i0i1 

I 33. A superconducting composition having a supercon- 

5 ducting onset temperature in excess of 26**K. , the 

3 composition being comprised of a copper oxide doped 

' with an alkaline earth element where the concen- 



Y0987-074)C 



- 35 - 



S tration of said alkaline earth element is near to 

^ the concentration of said alkaline earth element 

"7 where the superconducting copper oxide phase in 

2 said composition undergoes an orthorhorabic to 

I tetragonal structural phase transition. 



I 34. A sui>erconducting composition having a supercon- 
^ ducting onset temperature in excess of 26**K» the 

^ comi>osition being comprised of a mixed copper oxide 

3*4* 

Y doped with an element chosen to create Cu ions 

^ in said composition. 



/ 35. The composition of claim 34, where said doping el- 
*i ement includes an alkaline earth .element . 



j 36. A combination comprising: 

<^ a composition having a superconducting onset tem- 

^ pcrature in excess of 26**K, said composition being 

U comprised of a substituted copper oxide exhibiting 

^ mixed valence states and at least one other element 

^ in its crystalline structure, 



Y0987-074X. 



- 36 - 



? 

'a. 



means for passing a superconducting electrical 
current through said composition while said compo- 
sition is at a temperature in excess of 26**' 



fcooli! 



Ling means for cooling said composition to a 
superconducting state at a temperature in excess 
of 26*** 



37. The combination of claim 36, where said at least 
one other element is an alkaline earth element. 

Tlie combination of claim 36, where said at least 
one other element is an element which creates Cu' 
ions in said composition. 



/ 38, 



/ 39. The composition of claim 36, where said at least 
^ one other element is an element chosen to create 



3 2+ 3+ 
the presence of both Cu and Cu ions in said 

V com{x>s i t ion . 



Y0987-074X 



- 37 - 



AO. A superconductor exhibiting a superconducting onset 
at a temperature in excess of 26**K, said supercon- 
ductor being comprised of at least four elements ^ 
none of which is itself superconducting. 

41. Tlie superconductor of claim 40, where said elements 
include a transition metal and oxygen. 

42. A superconductor having a superconducting onset 
temperature greater 26^K, said superconductor being 
a doped transition metal oxide, where said transi- 
tion metal is itself non-superconducting. 

43. The superconductor of claim 42, where said doped 
transition metal oxide is multivalent in said 
superconductor . 



44. Tlie superconductor of claim 42, further including 
an element which creates a mixed valcnt state of 
said transition metal. 



Y0987-074)C 



- 36 - 



I A5. Tlic superconductor of claim 43, where said transi- 
^ tion metal is Cu. 



/ 46, A superconductor having a supMsrconducting onset 
^ temperature greater than 26®K, said superconductor 

^ being an oxide having multivalent oxidation states 

/J(M^>*H^ y and including a metal, said oxide liaving a crys- 

i talline structure which is oxygen deficient. 



J 47. The superconductor of claim 46, where said transi- 
oL tion metal is Cu. 



/ 48. A superconductive composition comprised of a tran- 

^ sition metal oxide having substitutions therein, 

J the amount of said substitutions being sufficient 

y to produce sufficient electron-phonon interactions. 

^ in said composition that said composition exhibits 

^ a superconductittg onset at temperatures greater 

-J than ao^'K. 



Y0957-074 



- 39 - 



Tlie conijx)sition of claim 48, where said transition 
metal oxide is multivalent in said composition. 

Tlie comFK>sition of claim 48, where said transition 
metal is Cu. 



/ 51. The composition of claim 48, where said substi- 
OL tutions include an alkaline earth element. 

Tlie composition of claim 48, where said substi- 
tutions include a rare earth or rare earth-like 
element. 



A superconductor comprised of a copper oxide having 
a layer-like crystalline structure and at least one 
additional element substituted in said crystalline 
structure, said structure being oxygen deficient 
and exhibiting a superconducting onset temperature 
in excess of 26*^K. 



/ 49. 



/ 50. 



3 



/ 53. 
J 

y 
r 

6 



Y0987-07A 



- AO - 



The superconductor of claim 53, where said addi- 
tional element creates a mixed valent state of said 
copper oxide in said superconductor. 



/ 55. 



J 
f 

r 



y 
s 



A combination, comprising: 

a transition metal oxide having an oxygen defi- 
ciency, said transition metal being non- 
superconducting and said oxide having multivalent 
states, 

means for passing an electrical superconducting 
current through said oxide while said oxide is at 
a temperature greater than 26 



cocxl4ng-mean6 — for_i::QQljLiig_sa id oxide in a super - 
xmnHiirtinf> 5staff> iKt — a.-JLcOTpef at4i ro greater th an 



The combination of claim 55, where said transition 
L is Cu. 





Y0987-074K 



- 41 - 



57, A combination including; 

a superconducting oxide having a superconducting onset 
temperature in excess of 26**K and containing at least 3 
non-superconducting elements, 

means for passing a supercurrent through said oxide 
while said oxide is maintained at a temperature greater 
than 26**K, and 

means for maintaining said oxide in a superconducting 
state at a temperature greater than 26**K. 

58. A combination, comprised of: 

a copper oxide superconductor including an element which 
creates a mixed valent state in said oxide, said oxide 
being crystalline and having a layer-like structure, 

means for passing a supercurrent through said copper 
oxide while it is maintained at a temperature greater 
than 26**K, and 



Y0987-07AX 



- U2 ' 



? means for(ccK>lin^said copper oxidc^to^a superconduct 
^ state at a temperature greater than 26**K. 



I 59. A combination, comprised of: 



a superconducting ceramic- like material having an 
onset of superconductivity at a temperature in ex- 



Y cess of 26**K., 



' ^ means for passing a supercurrent through said 

^ superconducting ceramic* like material while said 

y ceramic-like material is maintained at a temper- 

^ ature in excess of 26**K. , and 

^ means for[coolingjpaid superconducting ceramic-like 

material a superconductive state at a teroper- 
ature greater than 26**K- 



^ 60. A superconductor comprised of a transition metal 
^ oxide, and at least one additional element, said 

^ superconductor having a distorted crystalline 

structure characterized by an oxygen deficiency and 



Y0987-074X 



- A3 - 



exitibiting a superconducting onset temperature in 
excess of 26**K, 

61. Tlie superconductor of claim 60, where said transi- 
tion metal is Cu. 

62. A superconductor comprised of a transition metal 
oxide and at least one additional element, said 
superconductor having a distorted crystalline 
structure characterized by an oxygen excess and 
exhibiting a superconducting onset temperature in 
excess of 26*K. 

63. The superconductor of claim 62, where said transi- 
tion metal is Cu. 

64. A combination, comprising: 

a mixed copper oxide composition having enhanced 
polaron formation, said composition including an 
element causing said copper to have a mixed valent 



YO987-074-/s 



- AA - 



J) state in said composition, said composition further 
^ having a distorted octahedral oxygen environment 
^ leading to a greater than 26**K. , 



^ means for providing a supercurrent through said 
(y^*^^ ^ comj>ositxon at temperatures greater than 26^K.^^nd— . 



^0 cooing- nneans - for^-ooolMg-ca^i^-compQsilLiQn to a 
// temperature-greater than 26**Kr^ 



^ 65 • A- superconducting composition exhibiting 
^ superconductivity at temperatures greater than 

^ 26^K, said composition being a ceramic-like mate- 

y rial in the RE-AE-TO-0 system, where RE is a rare 

^ earth or near rare earth element,. AE is an alkaline 
(a earth element, TM is a multivalent transition metal 

element having at least two valence states in said 
composition, and O is oxygen, the ratio of the 
amounts of said transition metal in said two va- 



7 
/ 



lence states being determined by' the ratio RE : AE. 



/ 66. A superconductive composition having a transition 
oi temf>eraturc greater than 26**K, the composition in- 



¥0987-074^. 



- 45 - 



J eluding a multivalent transition metal oxide and 
y at least one additional element, said composition 

having a distorted orthorhombic crystalline struc- 

ture. 

I 67. Tlie composition of claim 66, where said transition 
metal oxide is a mixed copper oxide. 

/ 68. The composition of claim 67, where said one addi- 
^ tional element is an alkaline earth element. 

/ 69. A superconductive combination, comprising: 

^ a superconducting corafK>sition exhibiting a super- 

J conducting transition temperature greater than 

y 26**K, said composition being a transition metal 

5 oxide having a distorted orthorhombic crystalline 

^ structure, and 

^ means for passing a superconducting electrical 

P current through said composition while said conipo- 

f sition is at a temperature greater than 26**K- 



Y0987-074X 



- 46 - 



J 70. 
0. 



TIic combination of claim 69, where said transition 
metal oxide is a mixed copper oxide. 



/ 71. The combination of claim 70, where said mixed copper 
^ oxide includes an alkaline earth element. 



y 72. The combination of claim 71, where said mixed copper 
oxide further includes a rare earth or rare earth- 



like clement - 



j 73. A method for making a superconductor having a 
^ superconducting onset temperature > 26**K, said 

J method including the steps of: 

y preparing powders of oxygen-containing compounds 

of a rare earth or rare earth-like element, an 
^ alkaline earth element, and copper. 



7 



mixing said compounds and firing said mixture to 
^ create a mixed copper oxide composition including 

^ said alkaline earth element and said rare earth or 
rare earth- like element, and 



Y0987-074y, 



- 47 - 



/ / annealing said mixed copper oxide composition at 
an elevated temperature less than about 950**C in 

/ 3 an atmosphere including oxygen to produce a super- 
conducting composition having a mixed copper oxide 

IS^ phase exhibiting a superconducting onset temper- 

/(^ aturc greater than 26**K, said superconducting com- 

/y position having a layer-like crystalline structure 

/ ^ after said annealing step, 

j 74. The method of claim 73, where the amount of oxygen 

^ incorporated into said composition is adjusted by 

J said annealing step, the amount of oxygen therein 

y affecting the critical temperature of the 
superconducting composition. 

I 75. A method for making a superconductor having a 

^ superconducting onset temperature greater than 

J 26''K, said superconductor being comprised of a rare 

y earth or rare earth-like element (RE), an alkaline 

S*^ earth element <AE) , copper (CU), and oxygen (0) and 

6 having the general formula RE-AE-CU-0, said method 

y including the steps of combining said rare earth 

jp or rare earth-like element, said alkaline earth 



Y0987-074X 



- 48 - 



7 element and said copper in the presence of oxygen 

lo to produce a mixed copper oxide including said rare 

// earth or rare earth-like element and said alkaline 

/pL- earth element therein, and 

lieating said mixed copper oxide to produce a 
yj^ superconductor having a crystalline layer-like 

structure and exhibiting a superconducting onset 
temperature greater than 26**K, the critical tran- 
jy sition temperature of said superconductor being 

dependent on the amount of said alkaline earth el- 
ement therein. 

J 76. Tlie method of claim 75, where said heating step is 
^ done in an atmosphere including oxygen. 

I 11. A combination, comprising: 

^ a mixed copper oxide composition including an 

^ alkaline earth element (AE) and a rare earth or 

rare earth- like element (RE), said composition 
^ having a layer-like crystalline structure and 
^ raulti-valent oxidation states, said composition 



Y0987-074K 



- 49 - 



lo 

II 

19. 



I 78. 



/ 79. 

tin ^ 



/ 80. 



exhibiting a substantially zero resistance to the 

r ^ 

flow of electrical current therethrough when[cool«d 



a superconducting state at a temperature in ex- 
cess of 26**K, and 

electrical means for passing an electrical super- 
cutrent through said composition when said compo- 
sition exhibits substantially zero resistance at a 
temperature greater than 26**K. 

The combination of claim 77, where the ratio 
(AE,RE) : Cu is substantially 1:1. 



Tlie combination of claim 77, where the ratio 
(AE,RE) : Cu is substantially ^ 1 . 

Tlic combination of claim 77, where said crystalline 
structure is perovskitc- like . 




YO987-07A X 



- 50 - 



.1 



f 81- Tlie combination of claim 77, where said mixed copper 
oxide composition has a non -stoichiometric amount 
^ of oxygen therein. 



/ 82. A method for making a superconductor having a 
^ superconducting onset temperature greater than 26**, 

^ said superconductor being comprised of a rare earth 

y or rare earth-like element (RE), an alkaline earth 

^ element (A£) , a transition metal element (Tlf), and 

oxygen (0) and having the general formula 
"7 RE-AE-TM-0, said method including the steps of 

^ combining said rare earth or rare earth-like ele- 

^ ment, said alkaline earth element and said trans i- 

^ 0 tion metal element in the presence of oxygen to 

produce a mixed transition metal oxide including 
said rare earth or rare earth-like element and said 
/ ^ alkaline earth element therein, and 

/y heating said mixed transition metal oxide to 

0^ 



/3 produce a supcrcoductor having a crystalline 



A 



layer- like structure and exhibiting a supercon- 
/y ducting onset temperature greater than 26**K, said 

superconductor having a non-stoicliiomctr ic amount 
of oxygen therein. 

YO987-07A)( - 51 - 



I 83. 



TIic cnctliod of claitn 82, where said transition metal 



is copi>er. 



j 84. A superconducting combination, comprising: 

a mixed transition metal oxide composition con- 

^ taining a non-stoichiometric amount of oxygen 

^ therein, a transition metal and at least one addi- 

) tional element, said composition having substan- 
tially zero resistance to the flow of electricity 

-y therethrough whenGooled to^ superconducting state 

^ at a temperature greater than 26®K, and 

^ electrical means for passing an electrical super- 

l(j current through said composition when said corapo- 

// sition is in said superconducting state at a 

/ temperature greater than 26**K. 

/ 85, The combination of claim 84, where said transition 

^ metal is copper. 

/ 86. A method, comprising the steps of: 



Y0987-074>^ 



- 52 - 



3 

If- 



^ forming a composition including a transition metal, 
a rare earth or rare earth-like element, an 
alkaline earth element, and oxygen, where said 
^ composition is a mixed transition metal oxide hav- 
^ ing a non -stoichiometric amount of oxygen therein 
'J and exhibiting a superconducting state at a tern- 
^ perature greater than 26**K, 

4 7 (cooling \said composition jtoT said superconducting 

state at a temperature greater than 26**K, and 

h passing an electrical current through said corapo- 
/^L sition while said composition is in said supcrcon- 
^3 ducting state. 



/ 87. Tlie method of claim 86, where said transition metal 



iS copper. 



I 88- A method, including the steps of: 

forming a composition exhibiting a superconductive 
state at a temperature in excess of 26^K, 




Y0987-07AX 



- 53 - 



' ^Dolingjjsaid composition |toy a temperature in excess 

^ of 26^K at which temperature said composition ex- 

h hibits said superconductive state, and 

^ passing an electrical current through said compo- 

^ sition while said composition is in said 

y superconductive state. 

/ 89. The method of claim 88, where said composition is 

ot^ comprised of a metal oxide. 

/ 90, Tlie metal of claim 88, where said composition is 
comprised of a transition metal oxide. 



Y0987-07AX 



- 54 - 



BRIEF ATTACHMENT AV 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479,810 
Filed: June 7, 1 995 



Group Art Unit: 1751 
Examiner: M. Kopec 



Docket: YO987-074BZ 



Date: March 1 , 2004 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. 80x1450 
Alexandria, VA 22313-1450 



FIFTH SUPPLEMENTAL AMENDMENT 



Sir: 



In response to the Office Action dated February 4, 2000: 



ATTACHMENT 6 



r 



fw: $ ^ 2 -5 O 5: 
X 5 w X as K ^ 
^ ^ h: aw a ^ 0 




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/J S 5r q, ^ (jt u 
O ^ X 5/F ^ J: ^ 

5? g i)t 5t: fl< «: 

V« Ci -'r = • 



-jf ci -5 = 
^^t-- 2 5? '■J 55 a: 



jew 



CO fc 



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fee CD O < JTr ^ 



-c 




ii M Ht 



jgs m fti 

et tt 

ns; «f ^^ 

u S 



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^ £ 9 <^ 




E 



P fc 



^ ^ 



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f 



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{5 m w o 
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ft z: o X 
o nr fc 

^ jsr (c «i 
<o n ^ 

> mtxx 

CD u: w 



from ASAHI SHIlft:UN 

International Satellite Edition 
28. 11. 1986 (London) 



\ 



DISCOVERY OF NEW SUPERCONDUCTING MATERIAL 

" CERAMIC WITH SUFFICIENT SUPERCONDUCTIVE POWER IN 
HIGH TEMPERATURE REGION " 

A new ceramic with a very high T^ of 30K of .the superconducting 
transition has been found. The possibility of high T - super- 
conductiylty has been reported by scientists in Switzerland in 
thxs spring. The group of Prof. Shojl TANAKA, Dept. Appl.Phys. 
Faculty of Engineering at the University of Tokyo confirmed in 

TllZlT: '''' "<="^ °' -P«-n<lucting mater i- 

thL 20K Z 7 " application till now are lower 

ina T.' '"^^ "^""^ ^^^-id He for cool- 

i . NO e that the price of liquid He is very expensive. But 
With this new ^etterial we can use cheaper liquid H, for cooling. 

a inea^Tt ^° '"^^ appu'cations such 

as linear motorcars, electricity transport systems, etc. 

The ceramic newly discovered l«! an ^^tA 

•with Ba wh<nh ». «°°^e>^ed, is an oxide compound of La and Cu 

Tb.« .r, . lot ot possmutUs for pr.otlc.l .ppUo.tlo„, of 

~Mucti„, coll.,,tc. But o„. handicap U that i, oTL 
in each material ue kno» till now ° 

record ..a not .ea." ^^^r "' """"^ 

ot 30K, we can not only use liquid h h,,^ =1 . = 

boiling point of 27k: ^ »>^t also liquid Ne with a 

virrstrl'''''"''°" °' superconductors to many fields, such as 
incL: -chmes.etc. siow rapid 

co::::::::; ir:::: s™ctivity is hig^. 



TOTAL PAGE. 005 ** 



BRIEF ATTACHMENT AW 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479,810 
Filed: June 7, 1995 



Group Art Unit: 1751 
Examiner: M. Kopec 



Docket: YO987-074BZ 



Date: March 1 , 2004 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



FIFTH SUPPLEMENTAL AMENDMENT 



Sir: 



In response to the Office Action dated February 4, 2000: 



ATTACHMENT 23 



COPPER OXIDE 
SUPERCONDUCTORS 



Charles P. Poole, Jr. 
Timir Datta 
Horacio A. Faradi 

with help from 

M. M. Rigncy 
C. Sanders 

Department of Physics and Astronomy 
University of South Carolina 
Columbia, South Carolina 




WILEY 

A Wiley-Inicrscicace PabUcation 
JOHN WILEY & SONS 

New York • Chichester • Brisbane • Toronto • 



Cofxyiight €> 1988 by John Wilqr&Sooi, Inc. 



All rights reserved. Published simulianeously in Canada. 

Reproduction or transtatioa oC anv part of this work 
bcTOod that permitted by Section 107 or 108 of the 
1976 United States Copjnight Act without the permisMon 
of the copyright owner is unlawful. Requests for 
permissioo or further information should be addressed to 
the Permissions Department. John Wiley & Sons* Inc. 

Library of Congress Cataiogimg m Fubticatiom Data: 
Poole. Charles P. 

Copper oxide supcrconducton - Charles P. Ptoolc, Jr.. Timir Dalia. 

and Horacio A. Farach: with help from M. M. Rigncj- and C. R. Sanders. 

p. cm. 

-A Wilcy-lntcrsctence publication.*' 
Biblfographj: p. 
Includes index. 

1. Copper oxide supercunductors. I. Oalta, Timir. II. farach 
Horacio A. III. Title, 

QC611.98.C64P66 1988 
S39.6'23-dc 19 88-18569 CIP 
ISBN 0-471^2342-3 

Printed in the United States of America 

10 987654321 




PREFACE 



The unprecedented worldwide effort in superconductivity ies«th*.that has 
taken placeoverthc past twoyears has produced an enormous amount of expcri- 
mcntai data on the properties of the copper oxide type materials that cxhfcit 
superconductmty above the temperature of Hquid nitrogen. The time b now ripe 
to bnng to^er ,n one place the results of this research effort so that scienti^ 
woricmg m thu field can better acquire an owrall perspective, and at the same 
tune have available in one place a collection of detailed experimental data This 
volume reviews the experimental aspects of the field of oxide superconductivitv 
with transition temperatures from 30 K to above 120 K. from the time of its 
d^covery by Bedno„ and Mttller in April 1986 until a few months after the 
award of the Nobel Pnze to them in October 1987. During this period a consis- 
tent experimental description of many of the properties of the principal suocr- 
conducting compounds such as BiSrCaCuO. LaSrCuO. TIBaCaCuO and YBa- 
CuO has emccgcd. At the same time there has been a continual debate on the 
extent to which the BCS theoryand the electxon-phonon interaction mechanism 
appty to the new materials, and new theoreticai models are periodically pro- 
posed. We ducuss these matters and. when appropriate, make comparisons 
with transition metal and other previously known superconductors. Many of the 
experimental results are summarized in figures and tables 

The field of high-temperature superconductivity is still' cvolring, and some 
|deas and explanations may be changed by the time these notes appear in print 
Nevertheless, it is helpful to discuss them here to give insights into work now in 
progress, to give coherence to the present woric. and to provide guidance for 
future work It is hoped that in the not too distant future the field will settle 
down enough to permit a more definitive monograph to be written. 



yi PREFACE 



The literature has been covered almost to the end of ICM? 
.work has been discussed. This has been an e^m^o'li a^J^. 
>u,yom.ss,ons ia the citing and discussion of articles ' 

wo^^^J!^ B 'r'':?**"^"^ '"'^'^ ^''^^ notice about their 

B. StHdzker. S. Ts^^'J't^'^-^!^' Si 
ypreaate comments on the manuscript from S. Mu^^cU(^^n ^ 

Charles P, Poole, Jr, 
TiMiR Datta 
HoRAcio A. Farach 

Columbia, South Carolina 
Jufyim 



Hi 



•«ts of the BCS theory, however. 

'^^treatmentoftheprop. i 

«e the extent to which they con- 

nttrL"^.«'»*<>f*« other 
"these two chapters. I 



V 



PREPARATION AND 
CHARACTERIZATION OF SAMPLES 



A. INTRODUCTION 

Copper oxide superconductors with a purity sufficient to exhibit zero resistivity 
or to demonstrate levitation (Early) are not difficult to synthesize. We believe 
that this is at least partially responsible for the explosive worldwide growth in 
these materials. Nevertheless, it should be emphasized that the preparation of 
these samples does involve some risks since the procedures are carried out at 
quite high temperatures, often in oxygen atmospheres. In addition, some of the 
chemicals are toxic, and in the case of thallium compounds the degree of toxicity 
is extremely high so ingestion, inhalation, and contact with the skin must be 
prevented. 

TTie superconducting properties of the copper oxide compounds are quite 
sensitive to the method of preparation and annealing. Multiphase samples con- 
taining fractions with above liquid nitrogen temperature (Monec) can be syn- 
thesized using rather crude techniques, but really high-grade single-phase speci- 
mens require careful attention to such factors as temperature control, oxygen 
content of the surrounding gas, annealing cycles, grain sizes, and pelletizing 
procedures. The ratio of cations in the final sample is important, but even more 
critical and more difficult to control is the oxygen content. However, in the case 
of the Bi- and Tl-based compounds, the superconducting properties are less sen- 
sitive to the oxygen content. 

Figure V-1 illustrates how preparation conditions can influence supercon- 
ducting properties. It shows how the calcination temperature, the annealing 
time, and the quenching conditions affect the resistivity drop at Tc of a BiSrCa- 
CuO pellet, a related copper-enriched specimen, and an aluminum-doped coun- 



59 



60 PREPARATION AND CHARACTERIZATION OF SAMR^ 




0 100 ^ ^ 200 300 



Fig. V-1. Effects of heat treatments on the resistivity transition BiSrCaCuOM Ul 
calcined at 860*C, ib) caJdncd at 885*»C, (c) calcined at 901 (d) aiunimuniHkpc^ 
sample calcined at 875**C, prolonged annealing, (e) copper-rich sample calctacd « 
S60^C. if) aluminum-doped sample calcined at 885^C, slow quenching and (g) caldad 
at 885*^0, prolonged annealing, and slow quenching (ChuzS). 



terpart (ChuzS). These samples were all calcined and annealed in the same tem- 
perature range and air-quenched to room temperature. 

Polycrystalline samples are the easiest to prepare, and much of the early wod 
was carried out with them. Of greater significance is work carried out with thk 
films and single crystals, and these require more specialized preparatioo tech- 
niques. More and more of the recent work has been done with such samples. 

Many authors have provided sample preparation information, and oCbcfS 
have detailed heat treatments and oxygen control. Some representative teck- 
ciques will be discussed. 

The beginning of this chapter will treat methods of preparing bulk supcfflw- 
ducting samples in general, and then samples of special types such as thin Bm 
and single crystals. The remainder of the chapter will discuss ways of checkifll 
the composition and quality of the samples. The thermodynamic or subsoBd* 
phase diagram of the ternary Y-Ba-Cu oxide system illustrated in Fig. V-2 cot 
tains several stable stoichiometric compounds such as the end-point oiUt 
Y2O3. BaO, and CuO at the apices, the binary oxides stable at 950*, (BajCoOJ 
BaiCuOj, BaCuOi, YzCujOs. Y4Ba309. Y2Ba04. and (Y2Ba407). along th 
edges, and ternary oxides such as (YBajCu207), the semiconducting green ph«f 
Y^BaCuOs, and the superconducting black solid YBa2Cuj07^ in the inlcrio 
(Beye2, Bour3. Capol, Eagll. Frase. Hosoy, Jonel, Kaise, Kurth. Ku^ 
Leez3, Lianl, Malil. Schni. Schnl. Schul, Takay, Torra. Wagnc). Compooii^ 
in parentheses are not on the figure, but are reported by other worVcfS. 
existence of a narrow range of solid solution was reported (Panso), and the 
argued against (Wagne) by the same group. 




300 



ransition of BiSrCaCuOy^ (a) 
t 901 **C, (d) alumbum-doped 
•pper-rich sample caldned at 
ow quenching and (g) caldned 
iz5). 



annealed in the same tem- 

Jid much of the early work 
TOrk carried out with thin 
ciaJized preparation tech- 
lone with such samples, 
information, and others 
>omc representative tech- 
preparing bulk supercon- 
al types such as thin fdms 
discuss ways of checking 
tnodynamic or subsoiidus 
Justrated in Fig. V-2 con- 
as the end-point oxides 
table at 950^(Ba3CuO4), 
id (YzBa^Oy). along the 
liconducting green phase 
a^CujO;^ in the interior 
, Kaise, Kurth, Kuzzz. 
ra, Wagne). Compounds 
1 by other workers. The 
orted (Panso), and then 



METHODS OF PREPARATION 



CoO 



BaO 




Compound 


Stowly cooled 
to room temperature 


123 




O7 


143 


-YBa^CujO^,, 


O9 


365 




O1S 


152 


■YBasCuzOasw 


O9 


211- 


YjBaCuQs 








Ql3 



other compounds are shown in thVJnterior X^Z^^i^^^' " 



B. METHODS OF PREPARATION 

In this section three methods of preparation will be de^-rii^H . . 
more competence in analytical procedures P"^*""" ^'^"''^ 

«*^l'rt:;;r;;— ^^^^^^^ 



62 PREPARATION AND CHARACTERIZATION OF SAMPLES 

these room4emperatu«.stabfesalte Jre^^^^^^^^^ P^**^"- Then 

nod(«20hr)at elevated tem,^^t^rS^^^C^>^«^^^^ 

several times, with P"lveriri„g and mixin/^t^L^rSiir^"'^'^^^ 
each step. As the reaction pro«eds ^T^orJlt ^1'^ ^''"^ "^^riaJ at 
usually ends with a final a;!^Ill5LlH k T ^'"^^^^ The process 

temperature of the powderTwS^ 1^^^** ^ ' «^o^ n>on, 

cold or hot press. Sfaterini b r^*"*^' ""^^ri-g m " 

transport and other measu«me^ hT^y^ "^^'"^ ^r 
«ed. A number of researchoTw ^.L^^^T* *° *^ "^^'^ PeUet- 
action app„«ch (e.g.. ^^S^G^'T'^V^'' «>Iid.state re- 
Herrm. Hikal. Hirab. Ja^. ^cnlM^l2!S'S''^'^'^^^'^'^tan. 
Qadri. Rhyne. R„zic. Saito. S^rL^rlL^^^iu''^"^' ^ollc 

Some of theearlierworks on foils ^"^)- 
suspension of the calcined pTd^t T^^^^ ~^«°es employed a 

product was obtained by conv^Tion^S T"'^ desired 

spraying, or coating. "d^stnal processes such as extruding 

arep^lrbj-':^^^ 

1^7. Wang2). L the adl^t!^!?^™ ^" S- ^sela. Bedno 

scale. In addition the pre^p ^rmTfo™ ^T"^'*"-*^ an atomS 
be controlled, which <Sn dSninSe Jme ^ttel "''"^ «^an 

been dried, calcining can begin i L ttTsold If J?"" P'^P^^*^ ^as 
vantage of this method, at S^lf 'T'^ P^^^re. A disad- 

t-st is concerned, is that H requ^^^^ ^^7^11^^^!^ " ™ 

Another procedure for obtainine the^^rt ..I i "n chemical procedures, 
•n which an aqueous sciutiT^^t^CtZ^ 

nitrates is emulsified in an orgaTrhrLd th*^ ^"i °' ^' ''"^ ^ 
the addition of a high-molec^wS^tfnH '^P''^ ^« «<^"ed by 

acid. This p„>cesslas inmS^^^ltZX'^r'^'''^^^-^' 
fected for YBaCuO as well (cJTmm) ""^ P«- 

^X''<^ZTo^^;l^Z'T- " ^^""^^^ P- 
mill is recommended. G^S^ amL f T.^"'" ^"^^ P«t'«= « « ball 

are thoroughly mixed and pC i^Tpul^^^ 

be taken to ensure the com^atiWit^^o? tte ^ " """st 
obviate reaction and corrosion p5»?J^' -"'^ ""e chemicals to 

TypiXL'S^^^^^^^^ 

900OC for 15 hr. During ^^^tX^cla '^^g^" «~"nd 

green Y.BaCuO, phasf to the da^k' YBa Cu o" ''^^ ^''^ 

charge ,s taken out. crushed, and scanSd wrth v ' '-* """PO""^- "Hien the 
warranted by the powder pat^e» X-^y ^an J 'J^^' *° <'etermine its purity. If 
Often, at this stage the materia ?s l^l o^'^ :T''"'T P"^" " ^^P^^'^''- 

very oxygen poor, and electrically it is semi- 



BRIEF ATTACHMENT AX 





IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479.810 
Filed: June?, 1995 



Group Art Unit: 1751 
Examiner: M. Kopec 



Date: March 1, 2004 



Docket: YO987-074BZ 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



FIFTH SUPPLEMENTAL AMENDMENT 



In response to the Office Action dated February 4, 2000: 



ATTACHMENT 3 



© Springcr-Verlag 1986 



Possible High Superconductivity 
in the Ba-La-Cu-O System 

J.G. Bcdnorz and K.A. Muller 

IBM Zurich Research Laboratory, Ruschlikon. Switzerland 
Received April 17. 1986 

Metallic, oxygen-dcfident compounds in the Ba-La-Cu-O system, with the composi- 
tion Ba^s-xCuaOjo-^ have been prepared in polycrystallinc form. Samples vnth 
x = 1 and 0.75, y>0, annealed below 900 *C under redudng conditions, consist of three 
phases, one of them a perovskitc-likc mixed-valent copper compound. Upon cooUng, 
the samples show a linear decrease in resistivity, then an approximately logarithmic 
increase, interpreted as a beginning of localization. Finally an abrupt decrease by up 
to three orders of magnitude occurs, reminiscent of the onset of percolative superconduc- 
tivity. The highest onset temperature is observed in the 30 K range. It is markedly 
redu<^ by high current densities. Thus, it results partially from the percolative nature, 
bute possibly also from 2D superconducting fluctuations of double perovskitc layers 
of one of the phases present. 



I. IntroductioD 

"At the extreme forefront of research in supercon- 
ductivity is the empirical seardi for new materials" 
[1]. Transition-metal alloy compounds of A 15 
(NbaSn) and ^ 1 (NbN) structure have so far shown 
the highest superconducting transition temperatures. 
Among many A IS compounds, careful optimization 
of Nb— Ge thin fihns near the stoichiometric compo- 
sition of NbjGc by Gavalev ct al. and Testardi ct al. 
a decade ago allowed them to reach the highest r^= 
23.3 K i^rted until now (2, 3]. The heavy Fermion 
systems with low Fermi energy, newly discovered, arc 
not expected to reach very high T/s [4]. 

Only a small nimiber of oxides is known to exhibit 
superconductivity. High-temperature superconduc- 
tivity in the Li-Ti-O system with onsets as high 
as 13.7 K was reported by Johnston el al. (5). Their 
x-ray analysis revealed the presence of three different 
cryslallographic phases, one of them, with a spinel 
structure, showing the high T, [5]. Other oxides hke 
perovskites exhibit superconduciivity despite their 
small carrier concentrations, n. In Nb-doped SrTiOj, 
with n = 2x 10^**cm"\ the plasma edge is below the 
highest optical phonon. which is therefore unshielded 



[6]. This large electron-phonon couphng allows a 
of 0.7 K [7] with Cooper pairing. The occurrence of 
high electron-phonon coupling in another metallic 
oxide, also a perovskitc, became evident with the dis- 
covery of superconductivity in the mixed-valent com- 
pound BaPbi -xBixOa by Sleight et al., also a decade 
ago (8]. The highest in homogeneous oxygen-defi- 
dent mixed crystals is 13 K with a comparatively low 
concentration of carries /i=2-4 x 10^* cm"^ (9]. Flat 
electronic bands and a strong breathing mode with 
a phonon feature near 100 cm"*, whose intensity is 
proportional to T^, exist (lOJ. This last example indi- 
cates that within the ECS mechanism, one may find 
still higher T/s in perovskite-type or related metallic 
oxides, if the electron-phonon interactions and the 
carrier densities at the Fermi level can be enhanced 
further. 

Strong electron-phonon interactions in oxides 
can occur owing to polaron formation as well as in 
mixed-valent systems. A superconductivity (metallic) 
to bipolaronic (insulator) transition phase diagram 
was proposed theoretically by Chakraverly [11]- A 
mechanism for polaron formation is the Jahn-TeHer 
effect, as studied by Hock el al. (12). Isolated Fc^\ 
Ni^* and Cu** in octahedral oxygen environment 



190 



show strong Jahn-Tclkr (J.T.) cficcU (13}. While 
SrFc(VI)03 is distorted pcrovskite insulator, 
LaNi (111)03 is a J.T. undislorted metal in which the 
transfer energy of the J.T. electrons is suffidently 
large fl4] to quench the J.T. distortion. In analogy 
to Chakravcrty's phase diagram, a J.T.-type polaron 
formation may therefore be expected at the border- 
line of the metal-insulator transition in mixed perovs- 
kites. a subject on which we have recently carried 
out a series of investigations [15). Here, we report 
on the synthesis and electrical measurements of com- 
pounds within the Ba— La— Cu— O system. This sys- 
tem exhibits a number of oxygen-defident phases 
with mixed-valent copper constituents [16J, i.e., with 
itinerant clccUonic states between the non-J.T. Cu^* 
and the J.T. Cu^* ions, and thus was expected to 
have considerable eJectron-phonon coupling and me- 
tallic conductivity. 



n. Experimental 

1, Sample Preparation and Characterization 

Samples were prepared by a copredpitation method 
from aqueous solutions [17] of Ba-, La- and Cu-ni- 
trate (SPECPURE IMC) in their appropriate ratios. 
When added to an aqueous solution of oxalic add 
as the predpitant, an intimate mixture of the corre- 
sponding oxalates was fonned. The decomposition 
of the predpitatc and the solid-state reaction were 
performed by heating at 900 X for 5 h. The product 
was pressed into pellets at 4 kbar, and reheated to 
900 for sintering. 



2. X'Ray Analysis 

X-ray powder difiractograms (System D500 SIE- 
MENS) revealed three individual crystaUographic 
phases. Within a range of 10* to 80** (2^, 17 lines 
could be identified to correspond to a layer-type per- 
ovskite-like phase, related to the KaNiF^ structure 
(a=3.79 A and c=13.21 A) [16]. The second phase 
is most probably a cubic one, whose presence depends 
on the Ba concentration, as the line intensity de- 
creases for smaller x(Ba). The amount of the third 
phase (volume fraction > 30% from the x-ray intensi- 
ties) seems to be independent of the starting composi- 
tion, and shows thermal siabihty up lo 1,000 X. For 
higher temperatures, this phase disappears progres- 
sively, giving rise to the formation of an oxygen-defi- 
deni perovskite (La.,Ba3Cu<,0,^) as described by Mi- 
chel and Raveau [16). \ 



J.G. ronora and KJ., MGlkr: Ba-U-Qi-O System 



0i>6 
0.05 

i 

I 0.03 
0.02 



OjOI 



• 0.25 A/cm» 

• 0,50 A/Cfn» 
- 0.50 A/cm^ 



L 



100 



0O20 



0.016 



0.012 



C 
Q. 



0.008 



0.004 



T(K) 



200 



300 



Fig. I.Tcmperaturedcpciidcnccor resistivityin Ba,Laj_,Cu,05„._, 
for samples with x(Ba)= 1 (upper curves, left scale) and x{Ba)= 
0,75 (lower curve, right scale). The first two cases also show the 
innuencc of current density 



3, Conductivity Measurements 

The dc conductivity was measured by the four-point 
naethod. Rectangular-shaped samples, cut from the 
sintered pellets, were provided with gold clecUodes 
and contacted by In wires. Our measurements be- 
tween 300 and 4.2 K were performed in a continuous- 
flow cryostat (Leybold-Hereaus) incorporated in a 
computer-controlled (IBM-PC) fully-automatic sys- 
tem for temperature variation, data acquisition and 
processing. 

For samples with Jc(Ba)<1.0, the conductivity 
measurements, involving typical current densities of 

0. 5 A/cm^, generally exhibit a high*temperature me- 
tallic behaviour with an increase in resistivity at low 
temperatures (Fig. 1). At still lower temperatures, a 
sharp drop in resistivity (>90%) occurs, which for 
higher currents becomes partially suppressed (Fig. 1 : 
upper curves, left scale). This characteristic drop has 
been studied as a function of annealing conditions, 

1. e., temperature and Oj partial pressure (Fig. 2). For 
samples annealed in air, the transition from itinerant 
to localized behaviour, as indicated by the minimum 
in resistivity in the 80 K ranee, is not very pro- 
nounced. Annealing in a slightly reducing atmo- 
sphere, however, leads lo an increase in resistivity 
and a more pronounced localization c^^cci. At the 
same time, the on.sei of the resistivity drop is shifted 



0.04 



0.01 




0.03 



0.02 



30 40 

IT , , 

0.2xlO-^bar(cu^S,rS"^^ ©) and 



191 



0.010 



OjOOS 



0.006 



Oj004 



0.0021 



• 7.5 A/cm2 
" 2-5 A/cm? 

• 0^ A/cm^ 



10 



20 



50 



60 



30 40 
Fic 3 In ^ 



towards U>e 30 K region. Curves © and ® recorded 
for samples treated at 900 »r .iT .i! '^™«a 
of a sho'uMer atlJlflo^ L^.^^ ^SeT" 

a! <=on<lucting phase has almost 

for a sample with a lower Ba conc^S 
ofa75 u shown m F.g. l (rfght scale). Its lesistivitv 

evidence for the bulk being superconSuctmg g^w 
on an expanded temperature scale THp i,. J r- ' 
also shows ,he i„„„e„^ of ■b.S^^^ ';'S"cS 

for granular compounds. lypicaj 

ni. Discussion 

The resistivity behaviour of our samples Fic 1 
qua unvelv very similar ,o .he one'reporS' in 
L. T.-O system, and in superconducting 



a logarithmic type^fSS^3', tT"" ^i^^"^' 
transition to stjSconS ; ot"co"f 
speculate that in our <flm,>iJ "=°"«e. 
tuial phase tran Ji?on^ ^^^^^ 
The s£ft S in^?^ of Phases, 

density (Fia 3) hoL? ^ <=""ent 
withsi<^^-2;^;^-- -^^^ explain 
pretation that wc obs^^' s^PPom our inter- 

vity of per^iruJ^^" of s«pexcond«:ti- 

BaPb, So lit * " ^^'^''^^ beJow. In 
been ^ale^a^^i^e^^^™ "^^s 

n:^tK£s^sT:^~'-^^^^^^^ 

grain boundarie or ISn d^p"^ "'^ PO^ycry.^.^, 
with interpenetratrn^Tr *^ry^«allinc phases 

The onseT can a S^b^reTo? " " ^" " « ^V--. 
conducting wave func^on° fl"ctuat.ons .„ ,he super- 
Ba-La-Cu-O nh! 1 ^""^ o*" '^c 

Therefore. unde?.he ai"e '''^ 
a.35K.obser.;^:i^-XS.^!?S7S 



192 



to be Identified as the sUrt to superconductive coop- 
erative pbcnomena in ihc isolated grains. It should 
be noted that in granular AI, Cooper pairs in coupled 
grains have been shown to exist already at a point 
where^(r) upon cooling has decreased by only 20% 
of 1^ highest value. This has been proven quahtaUve- 
y 119J and more recently also quantitatively 1201 by 
the negauvc Ireouency shift occurring in a microwave 
«vjty. In ml aims, a shoulder in the frequency 
shift owing to 2D fluctuations was observed abovi 
the 7; of the grains. In our Ba-U-Cu-O system, 
a senes of kycr-Uke phases with considerable van^ 
in compoMCons arc known to exist (16. 21], and 
therefore 2£)correlaUons can be present 

The granularity of our system can be justified 
from the structural information, and more quantita- 
tively from the normal conductivity behaviour. From 
the foimcr, we know that more than one phase is 
pr«ent and the question arises how large are the 
grams. This can be inferred from the logarithmic 
fingerprint m resistivity. Such logarithmic increases 
are usuaUy associated witii beginning of localization 
A most recent example is the Anderson transition 
ui granular Sn fihns [22]. Common for the granular 
Sn and our samples is alsb the resistivity at 300 K 
lying ,n the range of 0.06 to 0.02 Hem, which is nca^ 
the microscopic critical resistivity of = 10 jL,nie^ 
for localization. From the latter formula, an inter- 
atomic distance 1^ in the range of 100 A is computed 
thus a size of superconducting grains of this orde^ 
of nwgmtude must be present. Upon coohng below 
7,. Josephson junctions between the grains phase- 
lock progressively [23] and the bulk resistivity «adu- 

^ ^ "™ o*" magnitude, for 

sample 2 (Fig. 1). At larger current densities the 
weaker Josephson junctions switch to normal resistiv- 
i^. resultmg m a temperature shift of the drop as 
Aown m Fig. 3. The plateau in resistivity occurring 
below the 80% drop (Fig. 1) for the higher current 
denaty of 0.5A/cm^ and Fig. 2 curve ®) may be 
ascnbed to switching of junctions to the normal state 
TTie way the samples have been prepared seems 
to be of cruaal importance: Michel et al (211 ob- 
tamed a angle-phase perovskite by mixing the oxides 
of La and Cu and BaCO, in an appropriate ratio 
and subsequent annealing at 1 .000 'C in air. We also 
applied this annealing condition to one of our sam- 
ples, obtained by the decomposition of the corre- 
sponding oxalates, and found no superconductivity 
Thus, the preparation from the oxalates and anneal- 
ing below 950 •€ are necessary to obtain a non-pcr- 
ovskiie-type phase with a limited temperature ranee 
of stability exhibiting this new behaviour. The fonna- 
tion of this phase at comparatively low temperatures 
IS favoured by ihe intimate mixture of the compo- 



nents and the high reactivity of the or^u. 

to the evolution of large amounts of H o 

during decomposition. ^'^ ^'^^^ ^O, 

IV. Conclusion 

^tion upon coohng. Samples annSlTrZT^^'r 
under reducmg conditions show features asLSateS 

S K ^eT'i °' ^P«^«>nductivirn2^ 
WK. The system consists of three phases r 
them having a metallic perovsk£-S^; °rL-. 
sUucture^Thecharacterizati^oftheniTappSi^^ 

tion of that phase may aUow growing of sinrie crv^ 
^^t^ZV^' ""'"^'^ effec'andS^^ 
EuXt"ti"t;.^°" 



References 



1. Tinkham. M.. Bcasky. M.R.. Lart>ale«.er DC Qark A F 

«S. BaralofT. A, Binnig. G.: Physics 108 B 1335 fiogn 
^'n -^T^^'' " '^^-^ Medals. Pro«cd 

' £r^:535^sr' """'^ ^-^^ 
'ii:t^7^r:'^iS't''' ^-"^ ^"'^ 

Bajlogg. B.: Physica 126 B, 275 (I9M) 

4227(r98Tr- '^'^-^ 

" mwrnn'" «• 
'' "iumi"' " ""^ -'^ 

cI^tTf",- '"k.^*" J^hn-TcUer EfTcct in Molecules and 
M G^I K "^'^ '^'o^'^ Wiley I„,crsciencc 197: 
I^.Goo^onoogh. J B.. Longo. M.. Magnetic and o.he, properties 
of oxide and related compounds. In: Undoli-BoernMein Nc« 



nving 
CO2 



unds 

high 

Dcal- 

0*C 

atcd 

acar 

2 of 

like 

ntly 

ica- 

rys- 

ting 



J.G. Bedoofzand Muller: Ba-U-Cu-O System 

Scrie*. Vol III/4a: OysU] and solid sutc physics. Helhvegc. 
KJi-. HcOwcgc, A.M. (eds.). p. 262, Fig. 73. Berlin, Hciddbcrg. 
New York: Sprioger-Veriag 1970 

15. Boinorz, J.G., MulIcr, Kj\.: (in preparation) 

16. Michel, C, Raveau, B.: Chim. Min, 21, 407 (1984) 
n.Bcdnorz, J.G., MQJler. K.A., Arcnd, H., Granicher, H.: Mat 

Res. Bull. 18 (2). 181 (1983) 

18. Suzuki. M.. Murakami, T., Inamura, T.: Shinku 24, 67 (1981) 
(in Japanese) 

Enomoio. Y.. Suzuki, M., Murakami, T., Inukai. T.. Inamura, 
T.: Jpn. J. Appl. Phys. 20. L66I (1981) 

19. Muller. Pomerantz, M., Knoedter. CM.. Abraham, D 
Phys. Rev. Leti. 45, 832 (1980) 

20. Siockcr, E., Buiui. J.: Solid State Commun. 53, 915 (1985) 



193 

^' 0^^ ^. 667 

^ (m6?'"^^^"*' ^ ' Bruynseraede. Y.: Phys. Rev. B 33. ,684 

23. Deutsdier, G„ Enun-Wohlman, O., Fishman, S.. Shapira Y - 
Phys. Rev. B 21, 5041 (1 980) ^napira, Y. 



J.G. Bcdnorz 
K-A. Muller 

IBM Zurich Research Laboratory 
Saumerstrassc 4 
CH-8803 Ruschlikon 
Switzerland 



ting 

tens 
inu- 



Uv- 
) 

ys. 



d- 
1- 
s- 



Not« Added in Proof 

Chemical analysis of the bulk composition of our samples revealed 
a dcviaiion from the ideal La/Ba ratios of 4 and 5.66 The actual 
ratios arc 16 and 18. respectively. This^ is in agreement with an 
idcniificaiion of the third phase as CuO. 



BRIEF ATTACHMENT AY 



Introduction 



Page 1 of 3 



Exploring Superconductivity 
Georg Bednorz 

In 1987, Georg Bednorz shared the Nobel Prize in Physics with his partner and mentor, K. Alex Muller 
"For their important breakthrough in the discovery of superconductivity in ceramic materials." Their 
breakthrough, accomplished in an IBM research lab in Switzerland, centered around the fabrication of a 
new copper-oxide compound that was superconducting at temperatures high enough to dramatically 
extend the applications of superconductors. To comprehend the significance of Bednorz's work, one r 
must first understand the history of research in superconductivity . 

Early investigations of superconductors that operate at temperatures higher then 23.2° K focused on 
metallic compounds that are good conductors of current at room temperature. In 1957 John Bardeen, 
Leon N. Cooper, and J. Robert Schriefifer (Nobel Prize in Physics, 1972) of the University of Illinois 
presented a new theory of superconductivity that changed the focus of research. In ordinary conductors 
some energy is lost to resistance because the conducting electron s scatter off impurities and vibrating 
atoms, known as phonons. According to the BCS theory (named for the initials of its originators), 
superconducting current is carried by pairs of electron s. This pairing keeps individual electron s from 
scattering off impurities, thus preventing resistance and establishing the superconducting state. 
Furthermore, it is the interaction between the electrons and the atomic structure of the superconductor 
that is responsible for the electron pairing. 

With this new theory, the search for high-temperature superconductors shifted from metals and metal 
alloys to materials that display a strong interaction between the electron pairs and the imderlying atomic 
structure. Scientists tumed to oxides, which are normally insulators . . 

The initial research led to modest advances. In 1973 David Johnston at the University of California at 
San Diego discovered superconductivity in lithium-titanium oxide at 13.7° K. In 1975 Arthur Sleight at 
Du Pont Research observed barium-lead-bismuth oxide superconducting at 13° K. X-ray analysis 
indicated the presence of significant interaction between electron s and the vibrations of the structural 
atoms (phonons). This fit the BCS theory and suggested that fiirther research on metal oxides might 
prove rewarding. 

In 1983 Alex Muller, who had been conducting research on insulator s , proposed that Bednorz 
collaborate with him in a search for high-temperature superconductors in metal oxides . Bednorz agreed 
because he felt the combination of Miiller's vision and his expertise in solid-state physics would lead to 
success. 

They first experimented with nickel oxides, but had disappointing results. Progress was slow and the 
amount of time and energy they could devote to this work was limited because it was not a major focus 
at the IBM research facility. The two men persevered, however, because they knew that oxide materials 
satisfied the requirements of the current BCS theory and that under the proper conditions such a material 
should prove to be superconducting at high temperatures. 



Click here W To hear Georg Bednorz describe their early work. 



Introduction 




Page 2 of 3 



Then in the fall of 1985 Bednorz read a paper by Claude Michel, L. Er-Rakho, and Bernard Raveau 
(from the University of Caen) that described their work with copper-oxide compounds. Bednorz 
immediately realized that a mixture of copper and barium would have the properties he was seeking, and 
on that very day he fabricated the new compound, a ceramic insulator composed of lanthanum, barium, 
and copper oxide. Since he could not duplicate the exact conditions under which the French scientists 
prepared their compound, he used a different preparation scheme. As it tumed out, that "chance" 
modification led to the Nobel Prize. 

Click here To hear Georg Bednorz describing the results of their modification. 

In January 1 9^6 the new materia] was tested and the resistance analysis indicated that it was 
superconducting. Bednorz recalls that "when it happened, I didn't trust my eyes." The fabrication 
scheme he used had a different amount of oxygen and a more moderate heating process than the original 
French one; this tumed out to be a key to its superconducting character. Bednorz's compound-and all 
subsequent metal-oxide superconductors-contained very thin sheets of copper oxide separated by layers 
of other metal oxides . There appears to be a direct correlation between the number of copper-oxide 
layers in a superconductor and its critical temperature . In gener al, the greater the number of copper- 
oxide layers, the higher the critical temperature . By varying the barium content and heating conditions, 
Bednorz was able to produce a material that was superconducting at temperatures as high as 30° K, 
seven degrees higher than the existing record. 

When Bednorz's laboratory detected the initial data supporting the high-temperature superconductivity 
of the copper-oxide ceramic material, Bednorz and MiiUer had to make a difficult decision. There had 
been many unsubstantiated and overrated claims of high-temperature superconductors, and they 
wondered if they should publish their results immediately in a prominent journal or wait until they 
substantiated their results with the more rigorous magnetic tests (to detect the Meissner effect ). Delays 
at this stage would mean that others working on similar projects could publish their findings first and 
receive the credit. They decided to submit their results at once to a journal that would not have many 
specialists as readers. They also wanted a journal with a fair amount of time between submission and 
publication, which would allow them to complete the magnetic testing before the article appeared. Their 
initial results were submitted to the Swiss Journal Zeitschrift fiir Physik on April 17, 1986, and were 
published in the September issue. The paper received little attention, and by mid-October they had final 
confirmation of superconductivity . 

Click here ^ To hear Georg Bednorz describing their thoughts on publishing their resxilts. 

Bednorz and Milller announced their discovery to the physics community, which was initially skeptical. 
Their colleagues questioned the validity of the data, and many laboratories throughout the world set out 
to verify their claims. After confirmation by the University of Tokyo, the University of Houston, and 
Bell Laboratories, the scientific community began to realize that their claim of high-temperature 
superconductivity was valid. 

Attention in the scientific community then focused on raismg the temperature, and by the end of 1986 
Bednorz raised the critical temperature of the barixmi-lanthanum-copper oxide system to 40*^ K by 
replacing barium with strontium. Researchers from the University of Houston and the University of 
Alabama, led by Paul Chu, then found that they could raise the compound's critical temperature to 52° K 
by applying pressure to the present metal oxide superconductor. This connection between compression 
of a crystal and an elevated critical temperatur led Paul Chu to replace lanthanum with a smaller atom, 
yttrium. On February 16, 1987, his research group established the critical temperature of yttrium- 



1 A/n/Ar 



Introduction 



Page 3 of 3 



barium-copper oxide at 92° K. This advance was particularly significant because this compound could 
be cooled with cheap and readily available liquid nitrogen. These new materials were dubbed high- 
temperature superconductors. 

The newest members of the superconductor family contain bismuth or thallium. On January 22, 1988, 
Hiroshi Maeda of Tsukuba Laboratories of the National Research Institute of Metals discovered a 
critical temperature of 105° K for a bismuth-calcium-strontium-copper oxide compound. On January 26, 
1988, Paul Chu reported a critical temperatur of 120° K for the same system. On February 22, 1988, 
Zhengzhi Sheng and Allen Hermann of the University of Arkansas announced that a compound of 
thallium-calcium-barium-copper oxide exhibited an onset critical temperature of 120° K. Many research 
groups are now working diligently to find new materials that display even higher critical temperature . 

It is worth noting that there is no accepted theory to explain the high-temperature behavior of this type 
of compound. The BCS theory, which has proven to be a useful tool in understanding lower-temperature 
materials, does not adequately explain how the Cooper pairs in the new compounds hold together at 
such high temperatures. When Bednorz was asked how high-temperature superconductivity works, he 
replied, "If I could tell you, many of the theorists working on the problem would be very surprised." 



Back to Interactive Learning Studio 



BRIEF ATTACHMENT AZ 



"A Snapshot View 
of 

High Temperature Superconductivity 

2002" 



Ivan K. Schuller', Arun BansiP, Dimitri N. Basov^ Malcolm R. 
Beasley^ Juan C. Campuzano"*, Jules P. Carbotte^, Robert J. Cava^, 
George Crabtree'', Robert C. Dynes\ Douglas Finnemore^, 
Theodore H. Geballe', Kenneth Gray'', Laura H. Greene*, Bruce N. 
Harmon^, David C. Larbalestier*, Donald Liebenberg^°, M. Brian 
Maple*, WilUam T. Oosterhuis*° Douglas J. Scalapino", Sunil K. 
Sinha^ Zhixun Shen^ James L. Smith*^, Jerry Smith*'', John 
Tranquada", Dale J. van Harlingen^, David Welch*^ 

'University of California, San Diego, ^Northeastern University, 
^Stanford University .'^Argonne National Laboratory, ^McMaster 
University, ^Princeton University, ^Ames Laboratory, ^University 
of Illinois, ^University of Wisconsin, *\J.S. Department of Energy, 
* 'University of California, Santa Barbara, '^Los Alamos National 
Laboratory, '^Brookhaven National Laboratory 



1 




Table of Contents 

I. Summary 

IL Structure, Bonding and New Systems 

1 . Synthesis and Fabrication 

a) Bulk 

b) Thin films 

c) Doping in the Cuprate Superconductors 

2. Other Topics of Interest; 

a) Applied pressure 

b) , Spin, laftice, and.charge correlation^ 

3. Conclusion 

in. Electronic structure and quasiparticle dynamics 

1 . Techniques 

a) Electron Tunneling 

b) Angular Resolved Photoemission Spectroscopy (ARPES) 

c) Infrared Spectroscopy 

2. Magnetism, Competing Order, and Phonons 

a) Magnetism and Spin Fluctuations 

b) Competing Orders 

c) Phonons and Electron-Phonon Interactions 

IV. Vortices 

1 . Single Vortex Physics 

a) Confinement 

b) Pseudovortices and Vortex Core States 

c) Hybrid Materials 

2. Multivortex Physics 

a) Disordered Glassy and Liquid States 

b) Dynamic Phases 

c) Josephson Vortices and Crossing Lattices 

3. Instrumentation 

V. Proximity and Interface Effects 

VI. Nonequilibrium Effects 

VIL Theory 

1. Preamble 

2. Phenomenological Approach 

a) Status 

b) Key issues and opportunities 

3 . Numerical Studies of Hubbard and t- J Models 

a) Status 

b) Key issues and opportunities 

4. Electronic Structure 

a) Status 

b) Key issues and opportunities 

Vin. Defects and Microstructure with an Eye to Applications 



2 



I. Summary 

This report outlines the conclusions of a workshop on High Temperature 
Superconductivity held April 5-8, 2002 in San Diego. The purpose of this report is to 
outline and highlight some outstanding and interesting issues in the field of High 
Temperature Superconductivity. The range of activities and new ideas that arose within 
the context of High Temperature Superconductors is so vast and extensive that it is 
impossible to summarize it in a brief document. Thus this report does not pretend to be 
alj-inclusive and cover all areas of activity. It is a xestricted snapshot and it only presents 
a few viewpoints. The complexity and difficulties with "high temperature 
superconductivity is well illustrated by the Buddhist parable of the blind men trying to 
describe "experimentally" an elephant. These very same facts clearly illustrate that this is 
an extremely active field, with many unanswered questions, and with a great fiiture 
potential for discoveries and progress in many (sometimes unpredictable) directions. 

It is very important to stress that independently of any current or futxire 
applications, this is a very important area of basic research. 



High Superconductivity 




Fig. 1 Status of High Temperature Superconductivity. [1] 



3 




Basic research in high temperature superconductivity, because the complexity of 
the materials, brings together expertise from materials scientists, physicists and chemists, 
experimentalists and theorists. Much of the research in High Tc superconductivity has 
spilled over to other areas of research where complex materials play an important role 
such as magnetism in the manganites, complex oxides, two and one dimensional 
magnets, etc. Applications could greatly benefit from the discovery of new 
superconductors which are more robust and allow easier manufacturing. Perhaps this is 
not possible since a naive inspection of superconductors seems to indicate that the higher 
the Tc the more complex the material. An excellent review where many target needs for 
applications have been outlined is an NSF report (^I-S years ago. Many of the comments 
made there regarding ^plied needs, are still validpj. 

It is important to realize that this field is based on con^)lex materials and because 
of this materials science issues are crucial. Microstructures, crystallinity, phase 
variations, nonequilibrium phases, and overall stmctural issues play a crucial role and can 
strongly affect the physical properties of the materials. Moreover, it seems that to date 
there are no clear-cut directions for searches for new superconducting phases, as shown 
by the serendipitous discovery of superconductivity in MgB2. Thus studies in vAAch the 
nature of chemical bonding and how this arises in existing superconductors may prove to 
be fruitful. Of course, "enlightened" empirical searches either guided by chemical and 
materials intuition or systematic searches using well-defined strategies may prove to be 
fiuitfiil. It is interesting to note that while empirical searches in the oxides, gave rise to 
many superconducting systems, similar (probable?) searches after the discovery of 
superconductivity in MgBj have not imcovered any new superconductors. Anyhow, this 
illustrates that superconductivity is pervasive in many systems and thus fiiture work 
should not be restricted to a particular type of materials systems. See Chapter II. 

Research in the electronic properties of High Tc superconductors has proven to be 
particularly fniitfiil. This has lead to improvements in electronic structure techniques 
which unquestionably have an effect on other fields. The improvement on real and 
reciprocal space resolution uncovered many interesting properties. However, it is not 
clear at the present time whether many of these properties are related in some essential 
way to superconductivity or they are just accidentally present. It seems that the presence 
of competing phenomena is present in most high temperature superconductors. Thus it is 
natural to investigate systems which are close to some form of instability such as the 
metal-insulator transition, magnetic phases, electronic instabilities such as stripe phases, 
etc. Comparisons of classical infrared spectroscopy, and photoemission measurements 
with tunneling may prove to be fruitfiil. In particular, mapping with high resolution (in 
real and reciprocal space) the electronic structure may prove to hold some of the keys to 
the mechanism of superconductivity. To make these usefxd, issues such as surface 
contamination, surface segregation, and in general heterogeneity of the materials close to 
surfaces or interfaces must be addressed, and are particularly important in these very 
short coherence length superconductors. This is particularly important for surface 
sensitive probes such as photoemission. Several techniques such as Raman scattering, 
NMR and muon spin depolarization are not addressed in this snapshot, although they give 



4 




valuable information and are heavily researched. Complementary measurements are 
particularly useful if a whole battery of tests, in the same sample, which are structurally 
characterized in detail, are performed. The "quality" of samples on the other hand, must 
be well established by structural criteria which are well defined "a-priori" and not based 
on circular or theoretical argximents. See Chapter III. 

The properties of High Temperature Superconductors in a magnetic field have 
proven to be particularly interesting. A myriad of new phases have been uncovered in the 
vortex system and have lead to the establishment of a very complex phase diagram the 
details of which are still being established. The presence of many phases and the 
interaction/cGinpetitiort^loseness to magnetic phases allows for much new research using 
artificially structured pinning. New lithography and preparation techniques allow 
modifications and confinement of these materials in length scales approaching the 
superconducting coherence length and certainly the penetration depth. Moreover, novel 
imaging techniques are arising which can give detailed microscopic images of the vortex 
system. This of course can provide the microscopic picture of the magnetic state of high 
temperature superconductors and will probably also help improvements on their xise. See 
Chapter IV. 

Many basic research studies and a large number of applications require the High 
Temperature Superconductors to be in proximity with other materials. Thus issues of 
proximity effects, spatial variations close to an interface or surface, structural and 
materials variations are particularly important in thin film and/or nanoscopic structures. 
For this purpose it is important to investigate the mutual interaction between 
superconductors and other materials. This requires carefiil preparation and detailed 
characterization of inhomogeneous materials, together with superconducting 
measurements as a fimction of well-defined structural parameters. This may also allow 
addressing issues such as the importance of the proximity to other ordered phases such as 
magnetic and electronic inhomogeneities which are naturally existent or are artificially 
engineered. It is not even clear in the various models of high temperature 
superconductivity or even experimentally how the proximity effect occurs. What is the 
dependence of the order parameter in an ordinary or magnetic metal, or a low 
temperature superconductor when in proximity with a d-wave superconductor? See 
Chapter V 

Contrary to low temperature superconductors, high T^ ones have received very 
little attention under nonequilibrium (time dependent, strongly driven, exposed to varying 
radiations, etc.) conditions. This may prove to be a very interesting and novel direction 
for ceramic oxides. These types of studies may hold important cluies to the mechanism of 
superconductivity, may unravel new physics and are important in many apphcations. For 
instance, simple issues such as the microscopic nature or even existence of critical 
slowing down close to the superconducting phase transition has not been firmly 
established. See Chapter VI. 

The theory of high temperature superconductivity has proven to be elusive to 
date. This is probably as much caused by the fact that in these complex materials it is 



5 




very hard to establish uniquely even the experimental phenomenology, as well as by tiie 
evolution of many competing models, which seem to address only particular aspects of 
the problem. The Indian story[l] of the blind men trying to characterize the main 
properties of an elephant by touching various parts of its body seems to be particularly 
relevant. It is not even clear whether there is a single theory of superconductivity or 
whether various mechanisms are possible. Thus it is impossible to summarize, or even 
give a complete general overview of all theories of superconductivity and because of this, 
this report will be very limited in its theoretical scope. The general view point 
(determined by "majority vote") seems to be that low temperature superconductors are 
phonon mediated whereas high T^ ones are somehow "imconventional** and anisotropic, 
although the origin of the anisotropy remains controvei'sial. Beciause of this, numerical 
studies in well-defined theoretical models may prove to be particularly illuminating and 
may help uncover the essence of superconductivity. Particularly, understanding and 
further developing the t-J model looks like a promising nimierical direction. Electronic 
structure calculations combined with well developed methodologies seem to explain 
quantitatively many aspects of superconductors with moderate T^s. How far can these 
type of approaches be pushed? Coxild they in fact explain ab-initio superconductivity in 
some of the cuprates? Moreover, first principle electronic calculations may be very usefiil 
in providing parameters for model hamiltonians. Another approach which at least allows 
parametrizing in some usefiil way the properties of superconductors has also been used. 
How far can these type of models go and how universally can they explain the 
(superconducting or normal) properties is not clear at this stage. There are several 
important issues which must be kept in mind. It may be that there is a theoretical model 
which has the essence of the problem in it and it either has not yet been developed or has 
not yet percolated to the conscience of the community. Moreover, it seems that to date no 
theory has been developed which has predictive power as far as materials system are 
concerned. Since purely theoretical approaches have difficulties so far in identifying a 
clear avenue for search, empirical studies in which materials parameters and properties 
are correlated with superconducting properties may prove usefiil[3]. This may serve at a 
later stage as a test ground for theories. Comparisons of theoretical ideas which rely only 
on the layered material of high Tc ceramics, with artificially engineered layered 
superiattices should not be neglected and may prove to be useful. See Chapter VII. 

Finally, there seems to be still much work needed to understand in detail the 
connections, control and effect of defects on high temperature superconductivity. This of 
course is very important for applications, particularly those which require high critical 
currents such as power applications. Moreover, the intrinsic brittleness highlights that 
understanding and controlling the mechanical properties while not directly related to 
superconductivity, is a very important and promising new area of research, especially in 
connections with large scale applications. See Ch^ter VIII. 

In the rest of this paper we will expand on these issues and attempt to outline 
some well defmed promising directions of research. The focus is mostly on basic research 
challenges and opportunities, which hold back progress. 



6 





II. Structure, Bonding and New Systems 

The discovery of new superconducting materials has played an important role in 
the advancement of the field of superconductivity research since its inception[4-7]. This 
was perhaps most dramatically displayed by the discovery of the high Tc cuprates in 
1986. The influence of new superconducting systems continues to this day, for example 
through the discovery in 2001 [8] of MgB2. Thus far, the existence of a totally new 
superconductor has proven impossible to predict from first principles. Therefore their 
discovery has been based' largely on empirical approaches,* intuitioii, and even 
serendipity. This unpredictability is at the root of the excitement that the condensed 
matter community displays at the discovery of a new material that is superconducting at 
high temperature. New systems can be found by either bulk methods or thin film 
methods, each of which has its own advantages, disadvantages, challenges and 
opportunities. The search for new materials has always been[9], and remains an important 
area of research in flie field of superconductivity. 



Fig. 2 The crystal structure of MgBa. The graphite-like array of boron (shown in black) 
is critical to the occurrence of high temperature superconductivity in this compound. 

Also important for the development of potentially practical materials and the 
understanding of the complex physical phenomena which occur in superconducting 
materials has been the use of chemical doping or manipulation to influence the electronic 
and magnetic properties of the superconducting systems. An example of the former 
chemical doping is the introduction of small flux pinning chemical precipitates in 
conventional intermetallic superconductors and 123-type superconductors. Examples of 
the latter are found in the "lightly doped" cuprates and other perovskite structure 
transition metal oxides where the concepts of charge and orbital ordering have recently 
emerged as important considerations in attempts to understand magnetic and electroruc 
properties. These cooperative states join other such states stich as charge density waves 
and spin density waves as critically influential in determining the xdtimate electroruc 




7 



ground state of complex materials. Chemical doping has played an essential role in these 
areas. Importantly, it allows for the systematic variation of electronic properties as a 
function of variables such as lattice size, carrier concentration, and magnetic or non- 
magnetic disorder, providing a basis for the development of theoretical models. This area 
of research is highly active in the field of superconductivity, and will continue to be of 
great importance in the future. 

1. Synthesis and Fabrication 

a) Bulk 

In the high density of states conventional intermetallic superconductors, the BCS 
coupling through the lattice may be viewed as a general lattice phenomenon. In more 
recently discovered superconductors, such as MgB2, it has been found that one particular 
phonon mode - an in-plane boron mode that modulates bond lengths and angles within 
the flat B honeycomb lattice in the case of MgB2 - is responsible for coupling to the 
conduction electrons and is the driving force for superconductivity [10, 1 1]. Conclusions 
about the nature of the phonons and electrons that are responsible for the 
superconductivity in a particular material can be arrived at nowadays by sophisticated 
experimental study and theoretical analysis. In particular the band-structure experts can 
calculate the effect that a particular phonon has on the electrons at the Fermi energy in a 
particular superconductor by doing "frozen phonon calculations". Such calculations are 
highly instructive for superconducting materials like MgB2. 

This analysis is after the fact, unfortunately, for people whose interest is in 
finding the new superconductors in the first place. So given the fact that undirected 
combinatorial chemistry will never get through all the possible element/treatment 
combinations in a search for superconducting materials, one important issue to be 
resolved in future research is to translate the physics of superconductivity into a set of 
chemical hypotheses to guide the search for new ones. Tlie era of finding new high 
temperature superconductors in intermetalUc compounds like NbaGe appears to be long 
gone. The new breed of high Tc superconductors is quite different - even beyond the 
cuprates, which are their own special case. The difference hes in the type of chemical 
bonding these superconductors display, even in what look like classic intermetallic 
compounds such as MgB2 and LuNi2B2C[12]. Thus one important issue for future 
research is to explore how the nature of the chemical bonding present influences the 
superconductivity in "conventional" intermetallic compounds. 

Initially promising reports of electronic doping through charge injection into a 
variety of organic and inorganic compounds in FET device structures have recently been 
called into question[13]. Nonetheless, conceptually they point out that another area of 
future research in new superconducting systems should be that non-thetmodynamic 
synthetic methods should be actively pursued. Modulation doping, the chemical analogue 
of charge injection, for transferring charge between layers in fine scaled multilayerd 
films, has potential which is yet to be exploited. Other methods for non-thermodynamic 
synthesis with high potential for success include quenching from high pressure or from 



8 




the vapor, epitaxial thin film layer by layer or block-by-block growth, photodoping, 
electrochemical synthesis at low temperatures, ion exchange, fi^amework stabilization of 
structures, and electrochemical intercalation. 

b) Thin Films. 

There are many examples of stabilization of non thermodynamic compounds in 
thin films in both the cuprate superconductors and in dielectric or ferroelectric materials 
by using epitaxy with substrate or buffer layers. In the most extreme examples of this 
type of metastable material it may be a single atomic layer or even an interface that has 
the desired properties. On such short length scales, chemical bonding is the predominant 
influencing factor. Different physical and chemical methods of growth influence the 
behavior of surfaces and very thin layers. Great progress has been made in 
characterization after growth - such as Transmission Electron Microscopy (TEM) and X- 
ray probes, but a great deal more may be gained in the future by incorporating techniques 
that can be used in situ to characterize surfaces during growth. 

Of particular interest in the search for new materials is the "phase spread method" 
used with success by some materials physicists. In this method, thin films are made by 
intentionally introducing composition gradients, for example by having three atomic 
sources in a triangular geometry, such tiiat their deposition areas only partially overlap. 
The film thus fabricated contains mixtures of the source atoms in systematically varying 
ratios depending on proximity of substrate to one or another of the source. Annealing of 
such composition spreads under different conditions can be employed to search 
significant areas of phase space. 

Photoexcitation provides another non-thermodynamic method to perform doping 
studies on thin films in a reproducible way without changing material, thus avoiding the 
inherent difficulties with controlling stoichiometry, uniformity, and homogeneity of the 
saniples[14, 15]. Persistent photoexcitation has been performed in many cuprate 
superconductors and on the magnetic manganites at low temperatures below lOOK. Large 
changes in conductivity. Hall effect, mobility, and superconducting transition 
temperatures have been observed. In the best model for this process, light generates an 
electron hole pair and the electron is trapped in a defect thus changing the hole doping in 
the electronically active layer providing a potentially useful way to trim device properties 
and "write" artificial nanostructures without need for lithography. 

c) Doping in the Cup-ate Superconductors. 

The properties of the cation-substituted and oxygen-doped high-temperature 
superconductors have been studied in detail since 1987. In general, the physical 
properties (temperature-dependent resistivity, superconducting transition temperature. 
Hall effect, etc.) and the structural properties of the HTS cuprates behave quite 
differently as a function of substitutions in comparison to convOTtional superconductors. 
Doping and ion-induced disorder have shown ttiat a small change in physical structure 
can induce a dramatic change in the electronic structure in these materials. This was one 



9 



of the first indications that they were unconventional superconductors. The details of the 
effects of atomic substitutions or doping are not yet fully understood in the cuprate 
superconductors, and this represents an active area of current research. Concentrating on 
YBa2Cu307-6 (YBCO) for example, some of these issues are: 

i) Doping on the Y-site. 

Doping with the heavy Rare Earth (RE) ions on the Y-site, even with Gd, does not 
affect Tc, except for substitutions of the Y with Pr The effects of Pr-doping remain 
controversial. 

ii) Doping on the CuO chains. 

Substitutions of 3+ ions (e.g., Al, Co, Fe) primarily replace Cu in the CuO chains. 
Extra oxygen is simultaneously incorporated into the chain layer, the c-axis lattice 
constant increases, and an orthorhombic to tetragonal transition occurs. Since the extra 
oxygen compensates for the valence of the substituted cation, it remains an open question 
as to whether the resulting doped materials are underdoped or overdoped. Also, it has 
long been knovm that not only is the Tc of YBCO dependent on the oxygen 
concentration, but also on how the oxygm is ordered. Open issues remain, such as why 
do the chain oxygens need to be ordered to maximize the Tc? 

Hi) Doping in the CUO2 planes. 

Both Ni and Zn predominately replace copper in the CUO2 planes without 
significant structiual change. However, Tc falls faster in tiiese cases than it does with 
increased 3+-cation doping on the chains or oxygen doping on the chains. That is an 
indication that the loss of structural continuity of the CUO2 plane is more detrimental to 
the superconducting transition temperature than the lattice changes that occur due to 
doping on the CuO chains. There are interesting data comparing the Ni and Zn-doping: 
Tc falls faster with increasing the Zn doping than with increasing the Ni doping. 
Conversely, the room temperature resistivity increases faster and the Relative Resistance 
Ratio (RRR) [R(300) / R(0)-extrapolated] reduces faster with increasing Ni doping than 
increasing Zn doping. Therefore, Zn destroys the superconducting phase faster and the Ni 
destroys the normal metal phase faster. Remaining issues are: Why do Ni and Zn 
substitution reduce Tc so dramatically? and Why does Zn suppress the superconducting 
state faster than Ni, while Ni suppresses the normal state faster than Zn? 

iv) The Role of the Charge Reservoir Layers, 

The cuprates containing Hg, Tl and Bi ions in their charge reservoir layers have 
unusually high TcS. These ions are known to charge disproportionate, which makes them 
negative U-centers, Under some circumstances it is known that negative U-centers can 
be superconducting pairing centers. It is of great interest to determine whether 
superconducting pairing on the charge reservoir layo-s is responsible for the enhanced TcS 



10 



of the Hg, Bi and Tl cuprates, and if so whether the negative U approach can be turned 
into a general method for finding and enhancing superconductivity. 

2. Other Topics of Interest 

a) Applied Pressure. 

The investigation of high temperature superconductors under high pressure has 
the advantage that the basic interactions responsible for superconductivity can be 
changed without introducing disorder into the system as encountered in alloying 
experimaits. The drawback is that one has to deal with massive higji pressure cells, small 
sample sizes, and technical difficulties that increase with the higher the pressure range of 
interest. Measurements of the pressure dependence of Tc are the most straightforward 
since this can be accomplished through measurements of the electrical resistivity and the 
ac magnetic susceptibility under pressure. The electrical resistivity in the normal state, 
which can be accessed even below Tc by suppressing superconductivity with a magnetic 
field, yields complimentary information about phonons and magnetic excitations that are 
responsible for the superconductivity. Other types of measurements such as NMR and 
specific heat have been made under pressure. It would be usefiil to develop techniques for 
making other types of measurements under pressure and extending the range of pressures 
curraitly accessible. 

b) Spin, Lattice, and Charge Correlations, 

"Doping" generally refers to the introduction of charge carriers into the 
conduction or valence bands of a material. However, because of the large coupling 
between charge, spin and lattice in the cuprate superconductors and other transition metal 
oxides, doping of these materials with charge carriers can also be accompanied by the 
formation of static and dynamic spin and/or charge ordered phases on a microscopic 
scale. These "stripe phases," have recently been observed in many perovskite based 
transition metal oxides, including several cuprates, and may be a general feature of 
transition metal oxides[I6, 17]. The role these microscopic inhomogeneous spin or 
charge phases play in high temperature superconductivity, magnetism, and other effects 
that have been attributed to them, is, however, unclear at tfiis time. 

The comprehensive understanding of spin/charge self-organization in oxides is a 
challenging task. This is a new viewpoint in the survey of strongly correlated phenomena 
in solids - a field that until recently has been primarily focused on the properties of 
nominally homogeneous systems. Intrinsically inhomogeneous spin and charge systems 
in transition metal oxides call for both original theoretical approaches and for the 
development of novel experimental tools suitable to deliver important information. 
Existing experimental information on the electronic and lattice properties of stripes 
systems is incomplete and therefore many fundamental problems related to spin/charge 
ordered regime in solids remain unresolved. 



11 



3* Conclusion 



We believe that the opportunities for new materials to greatly influence the future 
of superconductivity research remain large, both from the point of view of fundamental 
science and the development of practical superconducting materials. We believe that 
chemical doping, non-thermodynamic synthesis, the discovery of totally new materials, 
the investigation of strongly correlated charge and electronic systems, and the use of 
chemical principles to help answer questions about the nature of superconductivity are 
exciting areas for future research. • • : 

III. Electronic Structure and Quasiparticle Dynamics 

High-Tc superconductivity is achieved when a moderate density of electrons or 
holes is introduced in antifenomagnetic (AF) Mott-Hubbard insulator hosts by chemical 
or field-effect doping. Gross features of the evolution of the electronic structure as doping 
progresses from Mott insulator to d-wave superconductor are known from tfie systematic 
transport, photoemission and optical studies[ 18-21] . The doping-driven phase diagram of 
high-Tc systems is exceptionally rich owing at least in part to the fact that at the verge of 
the metal-insulator transition boundary magnetic, electronic, lattice and orbital degrees of 
freedom are all characterized by similar energy scales. Optimally doped cuprates (having 
highest Tc for a given series) reveal a well-defined Fermi surface in close agreemait with 
the resiilts of the band structure calcuIations[22], Nevertheless, the dynamics of charge 
carriers appears to be highly anomalous defying the grounding principles of the Fermi 
liquid theory. Numerous attempts to describe the electronic properties using strong 
coupling Eliashberg theory have been only partially successfiil[23-25]. Using this 
approach it became possible to find a consistent description of many of the featxires 
established through a combination of txmneling, photoemission, optical and neutron 
scattering measurements for YBCO and the Bi2212 families of materials. However, 
many other systems of cuprates fail to follow the same pattems[26, 27], Moreover, 
because of the extremely strong inelastic scattering established for most high Tc 
superconductors the concept of strongly interacting quasiparticles underlying the 
Eliashberg formalism is in question. 

Early on it became established that superconducting currents in cuprates are 
carried by pairs of holes or electrons similar to that of convenrional BCS 
superconductors. However, a viable description of the pairing interaction is yet to be 
found. Numerous experimental results indicate that the process of the condensate 
formation in cuprates is much more complex than the BCS picture of a pairing instability 
of the Fermi gas. One example of a radical departure from the BCS scenario is that the 
opening of the superconducting gap in cuprates is preceded by the formation of a partial 
gap (pseudogap)[28]. There is still a debate as to whether this pseudogap is related to the 
superconductivity. The pseudogap ^pears to be strongly anisotropic around the Fermi 
surface mirroring the anisotropy of the superconducting gap. These observations 
prompted the "precursor to superconductivity" scenarios for the pseudogap. Within this 



12 



view, the formation of pairs precedes the development of global phase coherence 
betv^een paired states[29]. Observations of vortex-like excitations [30] as well as of finite 
superfluid stiffhess[31] at T>Tc are in accord with the preformed pairs hypothesis. The 
process of the superconducting condensate formation in high-Tc cuprates also appears to 
be notably different from the BCS scenario. In particular, the energy scales involved in 
the formation of the superconducting condensate are anomalously broad and exceeds the 
magnitude of the superconducting energy gap by more than one order of magnitude[32, 
33]. These latter results inferred from optical spectroscopy are consistent with the view 
that the kinetic energy is lowered in the superconducting state. Similar conclusions also 
emerged from the detailed analysis of the photoemission spectra[34]. The electronic 
properties ofothe highlTc superconductors have been probed by several complementary 
techniques. These techniques have shown substantial technological improvements in part 
driven by the need for higher energy and k resolution. In addition tiiere is a growing 
belief that these materials may have real space inhomogeneities and so that a high 
resolution real space probe is desirable. Among the techniques that have revealed 
substantial insight because of technical improvemaits, we discuss electron txinneling, 
angular resolved photoemission spectroscopy, and infrared spectroscopy. 

1. Techniques 

a) Electron Tunneling, 

Electron tunneling (both quasiparticle and Josephson tunneling) has been a 
powerful technique to probe the excitation spectrum, the superfluid density and the pair 
wave function phase of conventional superconductors. With high Tc cuprates, the 
technique has been no less informative. Currently, much of our understanding of the 
order parameter symmetry has come from Josephson effect studies[35] and the non-BCS 
nature of the excitation spectnmi that comes about from the symmetry has been clearly 
observed[36]. C-axis and a-b plane quasiparticle tuimeling have illustrated the extreme 
anisotropy of these superconductors and shown that surfaces are very different with 
possible bound states due to the broken symmetry at the a-b interface[37]. Intrinsic c-axis 
tunneling[38] has attempted to address the relationship between the superconducting gap 
and the pseudo gap. The debate over whether the pseudogap and the gap are intrinsically 
coupled continues. 

STM studies offer an important additional feature that has already yielded some 
surprises. STM quasiparticle turmeling has allowed both microscopy and spectroscopy 
with good energy resolution and the spatial resolution to study the gap parameter on a 
length scale smaller than tiiie superconducting coherence length[39]. Some of the current 
thinking on the high Tc superconductors concludes that there are intrinsic 
inhomogenieties (especially in the underdoped limits) in the superconducting properties. 
Coupling the high energy resolution with the high spatial resolution, along with the 
recently developed superconducting STM[40] will allow direct spatial studies of the 
energy gap, bound states and the superfluid density. Recent investigations have 
illustrated the local effects of non-magnetic and magnetic impurities[41] in the high Tc 
materials and a background periodicity in the electronic density[42] (charge density wave 



13 



or spin density wave?) which requires further investigation. It is not clear whether this 
periodicity in the electronic density is associated with the superconductivity in these 
materials. Finally, the combination of high resolution quasiparticle spectroscopy and 
Josephson probe will allow quantitative investigation of spatial variations of the order 
parameter and superfluid density around impurities, at interfaces and proximity junctions. 
In conventional superconductors these two quantities are related but with spatial 
inhomogeneities, it is no longer required. For the high Tc materials, some theoretical 
models require inhomogeneities that would result in the superfluid density having 
different behavior than the energy g^. This will allow us to address both fundamental 
issues and applications. For example, ciurent studies show that a magnetic impurity does 
not suppress the energy gap[31]. It has been concluded that superconductivity is not 
affected but the superfluid density has not yet been investigated. In addition, much is still 
to be learned about the proximity effect at the interface between the high Tc materials and 
other metals. Tunneling will allow us to probe this interface. 

bj Angular Resolved Photoemission Spectroscopy (ARPES). 

ARPES experiments have contributed to our understanding of the electronic 
structure and superconducting properties by revealing the Fermi surface information,[43] 
and a large superconducting gap anisotropy that is consistent with d-wave pairing 
state. [44] 

Recent improved resolution, both in energy and in k have resulted in 
unprecedented data which allow us to map the electronic dispersion curves (E vs. k) for 
bands below the Fermi level Bp [45, 46]. Angle resolved photoemission studies are now 
mapping the dispersion curves for several cuprates (and other perovskite oxides). As a 
result of the enhanced energy and k resolution, it has bera demonstrated that in addition 
to E and k, the linewidths A£ (related to scattering rate j/) and Aifc (related to the 

inverse mean free path i) can also be determined. While mapping these quantities over 

an extensive phase space of E and k is still to be done, these measurements have revealed 
some very important insight already. Close to Ef an electron mass enhancement[47-49] 
(E vs. k measures the velocity and hence the effective mass m*) is observed in the 
dispersion curves which is both energy and temperature dependent. These measurements 
can be thought of as directly probing the self-energy of the carriers with all their 
dressings as a result of the interactions the carriers experience. In conventional 
superconductors, these interactions and mass enhancements are a result of the electron- 
phonon interaction; the mechanism responsible for superconductivity in the simple 
materials. Indeed, for many in the field it was the measurement of the strength of the 
electron-phonon interaction (via tuimeling for example) which confirmed the phonon 
mechanism of superconductivity. The measurements of ARPES are being carried out in 
several laboratories in the U.S. and elsewhere and the mass renormalization effects are 
observed at several facilities and in several materials. 

There is still disagreeinent as to some of the details of these measurements and to 
their interpretation[48, 50, 51]. Electron-phonon interactions, electron-spin interactions 
and electron-electron interactions have all been suggested and all result in enhanced mass 



14 



due to the interactions. Temperature dependent studies also illustrate that these 
interactions are at low energy and result from strong interactions. 

It is clear that mapping of these dispersion curves over a wider volume of the E-k 
phase space is important. It is especially critical with the high Tc cuprates because of the 
large electronic anisotropy of the materials. Furthermore, because of the synmietry of the 
order parameter, mapping of the self energy effects as a function of k around the Fermi 
surface is especially critical. If these observed renormalizations are the signature of the 
mechanism responsible for superconductivity in the high Tc materials, an extensive map 
of the electronic renormalized map will be valuable if the analogy with low Tc 
superconductors is relevant. In the case of low Tc materials the renormalized mass 
m* = /72(l + a) where k =electron-phonon interaction averaged over the Fermi surface. 

Current ARPES measurements could be determining quantitatively the strength of 
the interaction and the mechanism of superconductivity. As a final caveat, it must be 
remembered that both APRES and tunneling are surface probes. 

In this connection, inelastic X-ray scattering (IXS), which is not sensitive to 
surfaces or defects, is a valuable probe of bulk states. For high momentum and energy 
transfers IXS directly measures the ground state momentum density of electrons, wiiile 
spin density is measured in magnetic IXS scattering, with improved resolution that has 
been achieved with synchrotron light sources, IXS has revealed surprising electron 
correlation effects with simple metals and has been extended to study the electronic 
excitations of the present compound of high Tc superconductors. Its application to 
ceramic superconductors would be most worthwhile. [52, 53] 

c) Infrared Spectroscopy. 

Infrared (IR) and optical spectroscopy is ideally suited for the studies of 
superconductivity because of the ability of these techniques to probe such fundamental 
parameters as the energy gap and the super fluid density [54]. Notably, IR spectroscopy 
allows one to investigate the anisotropy in these parameters through measurements 
performed with the polarized light[55]. Because IR/optical information is representative 
of the bulk and measurements can be performed on the micro-crystals, these studies allow 
one to examine common patterns of a large variety of materials which may not be 
suitable for examination with other techniques. Optical techniques offer means to probe 
strong coupling effects in the response of quasiparticles. In this context IR, tunneling and 
ARPES results are complimentary to each other. It is therefore desirable to "map" 
renormalization effects using a combination of several spectroscopic methods. Charge- 
and spin-ordered states in solids can be conveniently examined through the analysis of 
the IR-active phonon modes. The latter circumstance is important for the investigation of 
self-organization effects which dominate the dynamics of charge carriers at least in 
under-doped cuprates. 

IR measurements can be performed in high magnetic field. Present work in the 
use of IR in high field experiments is restricted to a few experiments but several groups 



15 



are actively involved into adapting IR instrumentation for these challenging 
measurements. These studies promise to yield detailed information on dynamics of both 
pancake and Josephson vortices. More importantly, DC fields currently available in 
optical cryostats (up to 33 T) are sufficient to destroy superconductivity thus giving 
spectroscopic access to the normal state properties at T«rc. Transport measurements in 
strong magnetic field highlighted anomalies of the normal state in LaSrCuO (LSCO) 
series of cuprates[56]. Spectroscopic measurements will be instrumental in distinguishing 
between (conflicting) interpretations of these results and will also help to unravel generic 
trends of the normal state behavior at T«Tc between several classes of superconductors. 

2. Magnetism, Competing Order, ai^d Phonons 

a) Magnetism and Spin Fluctuations, 

As discussed earlier, superconductivity in the cuprates is achieved by doping 
holes or electrons into an antiferromagnetic-insulator state. The magnetism is essentially 
an electronic effect, as it results from strong Coulomb repulsion between pairs of 
conduction electrons on the same Cu atom, together with the Pauli exclusion principle. 
Considerable knowledge of antiferromagnetism (AF) and spin fluctuations in the 
cuprates[57, 58]. has been obtained experimentally using neutron scattering, nuclear 
magnetic resonance (NMR), and muon spin rotation (^iSR) spectroscopy. The general 
significance of antiferromagnetic correlations and spin fluctuations in theoretical 
mechanisms of high-temperature superconductivity is motivated by this experimental 
work. 

In hole-doped cuprates, 2% holes doped into the Cu02 planes are generally 
sufficient to destroy AF long-range order, but a minimum of 5-6% are necessary to 
induce superconductivity. Considerable attention has been devoted to characterizing the 
evolution of the AF spin fluctuations with doping. The bandwidth of the magnetic 
excitations, --300 meV in the ordered AF, appears to change relatively little with doping. 
In LSCO, the low-energy spin fluctuations become inconunensurate as doping increases, 
with a characteristic wave vector displaced from that of the AF by an amount 8. Similar 
incommensurability has been observed in YBCO, but additional features are the presence 
of a gap in the low-energy fluctuation spectrum followed by a commensurate "resonance" 
peak. The gap and peak energies both increase with hole concentration up to optimum 
doping, at which the resonance-peak energy is - 40 meV. Recent results on other 
families of superconducting cuprates indicate that the resonance peak is a common, 
although not universal, feature[59]. 

Electron doping has a weaker effect on the AF state, with a transition directiy 
from AF order to superconductivity occiuring at an electron concentration near 12%. 
Initial neutron measurements indicate that the AF spin fluctuations remain commensurate 
in the superconducting phase. Studies over a broad energy range are made challenging 
by the presoice of crystal-field excitations from the rare-earth ions. 



16 



Progress in the characterization of spin fluctuations has been enabled by the 
development and improvement of techniques for growing large single crystals and by 
forming large-volume mosaics of small crystals. Neutron scattering studies of hole- 
doped cuprate systems other than LSCO and YBCO are in early stages, and considerable 
progress is likely in the next few years. Improvement in llie homogeneity of large 
underdoped YBCO crystals would be helpful for some of the issues discussed below. 
The availability of sufficient access to appropriate neutron scattering facilities may also 
be a limiting factor. 

b) Competing Orders, 

A phenomenon known as "stripe" order has been observed by neutron and X-ray 
diffraction in several variants of the LSCO family [60, 61]. Spin-stripe order is indicated 
by the appearance of elastic magnetic superlattice peaks at the same incommensurate 
wave vectors at which the low-energy spin fluctuations occur. These are usually 
accompanied by the observation of another set of superlattice peaks split about 
fundamental Bragg points, indicative of charge-stripe order. The presence of stripe order 
is generally (although not always, as in the case of La2Cu04+y) associated with a 
reduction in the superconducting transition temperature. However, there is also a linear 
correlation between Tc and the incommensurability of the spin fluctuations in the absence 
of stripe order. 

There is also some evidence of stripe correlations in YBazCuaOe^^ O chains. The 
temperature dependence of the associated superlattice intensities suggests a coupling to 
electronic correlations, and possibly to charge stripes[62]. Certain spin fluctuations have 
been found to have an incommensurability similar to tiiat found in LSCO; however, the 
cause of the incommensurability is controversial. 

The recent scanning timneling microscope (STM) observations of spatial 
modulations of the electronic drasity of states (DOS) in the Cu02 planes of BSCCO has 
stimulated considerable speculation. The observed period of 4a (a, the in-plane lattice 
constant) suggests a connection with the charge and spin stripes found in LSCO. Clearly, 
a combination of tunneling and scattering studies is needed to clarify Ae nature of the 
modulations. 

There are many unresolved issues associated with the problem of stripes. Is stripe 
order a type of electronic instability, like conventional charge-density-wave order, that 
only competes with and limits superconductivity? Is it possible for a stripe-liquid phase 
to exist? Are stripe correlations conunon to all superconducting cuprate families, or do 
they only occur in special cases? Are spin stripes always associated with charge stripes, 
or are these distinct types of order? Do stripes (or possibly another type of 
inhomogeneity) exist in electron-doped cuprates? Studies with a wide range of 
techniques will be needed to answer these questions. Stripes are but one kind of order that 
has been proposed to have a connection witfi the various "pseudogap" phenomena that are 
observed in underdoped cuprates[63], A number of theories have put forward the 
hypothesis that a new order parameter appears in the pseudogap regime. Two particular 



17 



examples are quadrupolar orbital currents , and the staggered flux phase or d-density- 
wave (DDW) state. In both cases, orbital currents result in local magnetic moments that 
shoiild be, in principle, detectable by neutron scattering. So far, neutron scattering 
experiments have been unable to find evidence for such phases, which predict no 
breaking of translational synunetry; however, the presence of quadrupolar currents 
provides a possible explanation for the recent observation of time-reversal-symmetry 
breaking by photoemission[64]. The possible existmce of orbital moments remains an 
open issue. 

c) Phonons and Electron-Phonon Interactions. 

The role of electron-phonon interactions in the cuprates has been the subject of 
renewed interest, motivated in part by a recent interpretation of ARPES data [28] An 
important technique for characterizing phonon dispersions and densities of states is 
inelastic neutron scattering. (Note that neutron measurements of the phonon DOS in 
MgB2 provided an important validation of the theoretical evaluations of electron-phonon 
coupling in that system.) Dispersion anomalies in the Cu-0 bond-stretching modes, 
clearly associated with some kind of electron-phonon coupling, have been the subject of 
controversy for several years. The experiments are constrained by weak scattering cross 
sections and limited crystal size. Further experimental studies, together with serious 
theoretical analysis, are necessary in order to make real progress in this area Inelastic X- 
ray scattering has also been xised recently to study optical phonons in a cuprate. 




superoondufdlirig 



Figure 3. Schematic 
representation of excitations 
and collective modes in high- 
Tc superconductors. A 
remarkable variety of effects 
in these materials have typical 
energy scales of about 50-70 
meV, including: phonons, 
magnetic resonance, 
superconducting gap and 
pseudogap as well as "kinks" 
in the ARPES spectra. 
Competition, interplay and 
interdependence between 
these effects are responsible 
for complexity of the strongly 
correlated state in these 
materials. 



momentum 



18 



IV. Vortices 



Most of the electromagnetic properties of Type II superconductors are determined 
by vortices in static and dynamic configurations. Rapid progress in manipulating and 
measuring vortices in recent years has greatly expanded the limits of known and 
imaginable vortex phenomena. This chapter outlines several research directions that are 
now within reach and that will develop new concepts and strategies for fundamental 
science and applications. 

1. Single Vortex Physics. 

a) Confinement. 

Advances in micro- and nano-scale patterning and in high sensitivity 
measxirements now enable studies of single vortices, allowing a wide range of new 
physics to be explored. Vortices enter mesoscopic samples[65-68] one-at-a-time at field 
intervals determined by flux quantization, AH Oq/L^ where is the flux quantum and 
L the sample dimension. The entry of each vortex produces a step change in the 
magnetization, corresponding to a first order phase transition. In circular disks, vortices 
are predicted to configure in shell pattems[69] reminiscent of electrons in atoms and 
leading to magic nimibers of high stability. At certain fields a collection of discrete 
Abrikosov vortices transforms to a single giant vortex containing the same number of 
flux quanta and a circulating current at the outer edge of the sample. This phase 
transition is reminiscent of Wigner localization in electronic systems. In lower synunetry 
disks such as squares, vortices and antivortices coexist to simultaneously satisfy flux 
quantization and rotational symmetry[67]. 

Studies of confined vortices can be extended to layered superconductors such as 
NbSe2 and the cuprates, where the superconducting coherence length ^ and the magnetic 
penetration depth Xare quite different, and to other experimental probes like STM that 
directly image die superconducting order parameter. Confinement need not be limited to 
a single disk. Arrays of disks, each containing confined vortices, can interact through a 
superconducting substrate. Confinement in a line geometry[65] allows motion of 
confined vortices to be studied(70]. Confined disks connected by lines offer many 
analogies to single electron behavior including the Coulomb blockade and single electron 
tuimeling. 

Individual vortices in an array can be manipulated by imposing an artificial 
mesoscopic template. One approach is to lithographically pattem a superconducting film 
with an array of holes, or antidots, each of which traps one or more vortices[71-74]. 
Trapping vortices one-by-one has practical implications: it can dramatically enhance the 
piiming effectiveness and critical current, and it can lead to extremely sharp switching 
effects at matching fields. These switching features ofifer the potential for three terminal 
devices, where the supercurrent across the antidot array is modulated by a control 
magnetic field operating near the matching field. Antidots are predicted to trap vortices 



19 



with multiple flux quanta if the hole size is large compared to the coherence length. The 
properties of these multiquanta vortices are largely unexplored. Such antidots, for 
example, could enable the construction of information storage devices operating with 
integer rather than conventional binary bits. 

Mesoscopic templating can be extended in several exciting directions. The 
technique can be applied to cuprate high temperature superconductors[75], where the 
nanoscale coherence length enables many tens of flux quanta to be trapped in a single 
mesoscopic hole. Unlike low Tc superconductors, the cuprates have clearly defined 
lattice, liquid, and glassy phases that will react quite differently to the imposed order of 
the templates First brder vortex lattice melting, for example, is expected to be 
fundamentally modified by commensurate or incommensurate templates. Aperiodic 
templates provide another new direction. The vortices trapped in the holes create 
aperiodic scattering centers for free interstitial vortices whose dynamics will be quite 
different from those in ordered or random pinning arrays. Templates created to date have 
been limited by lithography to lattice spacings slightly less than one micron, putting the 
first matching field at about 20 Gauss. Electron beam and self-assembly techniques, for 
example based on diblock copolymers [76] anodic aluminum oxide[77] or inverse 
micelles[78], can be used to make templates with nanometer lattice constants. This much 
smaller spacing puts the commensurate vortex lattice in the strong interaction limit where 
collective effects dramatically alter its behavior, llie one study on dense templates 
reported so far[79] shows that strong piiming persists well below Tc. High density 
templates bring the first matching field up to the kG range, much more interesting for 
applications than the tens of Gauss range accessible to lithographic templates. High 
density templates offer an intriguing new strategy for piiming the vortex liquid, where 
eliminating shear motion requires one pin site per vortex. In BSCCO and YBCO this 
opens large areas of the H-T phase diagram to practical use, 

b) Pseudovortices and Vortex Core States. 

The observation of unusual thermomagnetic effects in the underdoped region of 
LSCO above the superconducting transition temperature and below the pseudogap 
temperatiu*e[80] suggests that vortex-like excitations may be associated with the 
pseudogap state. The properties of these pseudovortices are still under examination and 
may hold important insights into the underdoped state. Pseudovortices may be 
observable as fluctuations using experiments with short time scales and local resolution, 
such as magnetic resonance or muon spin rotation. 

The suppression of the superconducting energy gap in the vortex core creates a 
natural potential well that captures observable boimd states in cuprate 
superconductors[81, 82]. These bound states provide a window on the nature of pairing, 
because they are sensitive to the presence of nodes in the gap that distort the core 
potential. STM sees not only the bound state, but also the anisotropy of the energy gap 
around the core, providing direct information on the nodal structure. These experiments 
would be particularly valuable if performed systematically for under and over doped 
regimes, where the nature of the normal and superconducting states changes 



20 





continuously. In other organic and heavy fermion superconductors where the order 
parameter is a complex vector, the core states will display subtle details reflecting the 
exotic pairing. These core states are within reach experimentally but remain unexplored. 

In the vortex core the superconducting order parameter is suppressed, providing a 
fascinating opportunity to search for competing types of order without physically altering 
the material. Indications of spin daisity waves[42] and pseudogaps[83] in the cores of 
BSCCO suggest a strong interplay of these types of order with superconductivity. The 
same approach could be employed to search for competition with antiferromagnetism[84] 
charge stripes, and other proposed ordered states. 

The existence of two superconducting gaps[85] in MgB2 raises fimdamental 
questions about their effect on the core states. Strong variations in the core potential and 
the bound states are expected as the relative strength of the two gaps varies with 
temperature and field. This fascinating area is now within reach and is virtually 
unexplored- 

c) Hybrid Materials. 

We are now entering a new era of materials sophistication allowing studies of 
superconductors exposed to internal magnetic fields. Such internal fields arise in 
magnetic/superconducting hybrid structures[86], including naturally occurring 
RuSr^GdCu^Og [87] and the magnetic borocarbides[88, 89], and artificial hybrid 
structures containing patterned magnetic and superconducting layers[90]. There are 
fimdamental questions regarding how superconductors respond to internal magnetic 
fields: the conventional mechanisms of Meissner shielding and vortex penetration for 
external fields are not necessarily adequate. 



Fig 4. Superconductor/magnet bilayer. The vortex field polarizes the magnet locally, 
producing a radial magnetic texture. 

In bilayer hybrids, the field of an individual vortex in the superconducting layer 
locally polarizes the adjacent magnetic layer creating a tiny magnetic texture.[9l] Fig 4 
shows a radial magnetic texture, where the vertical arrows represent the vortex magnetic 




21 



field and the horizontal arrows the induced polarization of the magnetic layer. The 
coupled vortex-magnetic texture pair is a new compound object whose static and 
dynamic properties are virtually unexplored. One important element is the interaction 
between pairs, which is mediated by dipole and exchange interactions in the magnetic 
layer, Lorentz forces in the superconducting layer, and magnetostatic interactions 
between the layers. The resultant interaction potential is distinctively more complex than 
the simple repulsive potential of bare vortices. Dynamics brings in yet another element, 
the de-polarization and re-polarization of the magnetic layer that is required if a vortex in 
the superconducting layer is to move. Beyond the new physics of vortex-texture pairs, 
there is an additional attractive feature. The properties of the hybrid can be tuned by 
selecting the materials (e.g., the easy direction and the anisfttropy in^the magnetic layer), 
the relative thickness of the two layers, and the magnetic field direction. In multilayer 
hybrids with parallel applied field, an array of Ji-Josephson vortices can be formed, while 
tipping the field away fi-om the layers induces Abrikosov-texture pairs. 

There are equally fascinating possibilities in hybrids composed of magnetic dots 
deposited on a superconducting layer. Here the magnetic dot is a pin site that is isolated 
from the superconductor, avoiding deleterious effects of the pinning defect on current 
flow. Recent work on superconducting/magnetic dot hybrids[92-94] has defined several 
important issues, such as (i) the spontaneous creation of vortices and antivortices in zero 
^plied field, (ii) the annihilation of antivortices by external field-generated vortices, (iii) 
the nature of matching field effects, (iv) the effect of magnetic dot repolarization at high 
field, and (v) the dynamics of dot-gaierated vortices under a driving Lorentz force. 
These basic unexplored issues become even more fascinating when the scale of the 
magnetic dot array is reduced from present day lithographic dimensions to much smaller 
self-assembled dimensions. The interaction of flexible and compressible vortex lattices 
with rigid pinning geometries has many analogies in epitaxial growth, absorption of 
noble gases on surfaces and even plasma physics in confined geometries. Thus progress 
in this area has broad relevance well beyond tiie field of superconductivity. 

2* Multivortex Physics 

a) Disordered Glassy and Liquid States. 

The collective behavior of vortices is much like that of atoms: their mutual 
interaction energy creates lattices, quenched disorder by random pinning produces 
glasses, and thermal disorder melts the lattice or glass to a novel liquid state. The liquid 
and glassy states of vortex matter offer major challenges for understanding the magnetic 
properties of superconductors. Two kinds of glassy state have been proposed, the vortex 
glass[95] for disorder by point defects, and the Bose glass[96] for disorder by line 
defects. While experiments confirm the second order Bose glass melting transition, the 
tilt modulus and the resistive behavior of these disordered systems are at odds with each 
other and with tfieoTy[97]. For point disorder, even the voltage-current scaling behavior 
expected at melting is not observed[98] . Experimentally, lattice and glassy melting 
coexist in the same phase diagram[99-101], sometimes accompanied by novel "inverse 
melting" regions. Quasi crystals are another disordered phase of vortex matter, triggered 



22 



by pentagonal or decagonal boxindaries. The thermodynamics of melting in this phase 
intermediate between lattice and glass will be fascinating. 

The vortex liquid shows equally fascinating behavior arising from thermal 
disorder rather than quenched disorder Recent specific heat measurements[102] reveal 
two liquid phases separated by a second order phase transition. Understanding the nature 
of these two phases and the transition between them is a challenge not only for vortex 
matter but also other line liquids like polymers and liquid ciystals. The vortex liquid 
offers another promising opportunity, to study the interplay of thermal and quenched 
disorder. The addition of quenched disorder to the liquid shifts the fi-eezing transition up 
for columnar^efects, 4own for point defects. The effect of the two kinds^ of quenched 
disorder on liquid state thermodynamics and on its driven dynamics is ripe for incisive 
experiments. Disordered vortices offer a rich complexity that is easily accessible 
experimentally yet so far defies theoretical description Their behavior is fimdamental to 
applications of superconductivity, and to the basic science of condensed matter systems 
goierally. 

b) Dynamic Phases, 

The rich equihbrium phase diagram of vortices is matched by its driven dynamic 
behavior. The onset of motion at the critical current is a complex dynanwc process 
governed by the distribution of pirming strengths, the vortex-vortex interactions, the 
temperature, and die driving Lorentz force. The plastic motion that normally 
accompanies depinning can now be directly observed through Lorentz microscopy[103] 
and magneto-optical imaging[104]. This emerging spatio-temporal resolution opens 
possibilities for systematic experimental studies to characterize the depinning process as 
a fimction of the basic variables. Such previously hidden onset phenomena as vortex 
channeling, vortex hopping from pin site to pin site, and the distinction between 
avalanche and continuous onset are becoming observable. This wealth of experimental 
information drives new theoretical descriptions of the depinning process. The plastic 
motion inherent in depinning makes its description in terms of partial differential 
equations of hydrodynamics challenging. However, statistical descriptions in terms of 
time dependent position and velocity correlation functions can be created that break new 
ground for describing the onset of plastic motion. Beyond depinning, there are a host of 
dynamic phenomena that are now amenable to observation, including vortex creep, 
thermally assisted flux flow, hysteresis in I-V curves, and memory effects. The concept 
of vortex focusing and rectification through the ratchet effect is especially 
interesting[105]. A fimdamental microscopic understanding of these phenomena would 
lead to better engineered superconducting devices where stabiUty and high depinning 
forces are crucial [106]. 

c) Josephson Vortices and Crossing Lattices. 

Highly layered cuprates such as BSCCO support naturally occurring Josephson 
vortices, where the absence of a core and the large lateral penetration depth 
fundamentally alter the behavior typical of Abrikosov vortices. The two kinds of vortices 
co-exist and interact in the pres^ce of a tilted applied field, where the perpendicular field 



23 



induces a pancake vortex lattice and the parallel field induces a Josephson vortex lattice. 
The two crossing lattices interact to produce a complex phase diagram[107], containing 
spontaneous vortex stripes and intricate melting behavior for fields very close to the ab 
plane[108]. Advances in scanning Hall probe technology [109] and magneto-optical 
imaging[l 10] now allow these crossing lattice states to be imaged, directly illuminating 
these phase transitions in real space. The dynamic properties of Josephson lattices are 
also fascinating. Because they have no core and no conventional pinning, Josephson 
vortices can be driven at veiy high speeds. They are predicted to undergo a dynamic 
phase transition, from a highly distorted hexagonal structure at low speed to a stacked 
configuration at high speed[lll]. The most remarkable prediction is that the high speed 
Josephson lattice emits Terahertz radiation witb a frequency inversely proportional to the 
transit time for one lattice constant[l 12]. This offers the appealing possibility to create a 
new class of Terahertz radiation sources from dc components, with an adjustable 
frequency determined by the driving current and applied magnetic field. 

3. Instrumentation. 

Advances in STM, scanning Hall probes, magneto-optical imaging, Loraitz 
microscopy, high sensitivity specific heat and magnetization have driven recent and rapid 
progress in vortex physics. Further advances in instrumentation are on the horizon. 
Lorentz microscopy of vortex systems has recently been achieved at 1 MeV, showing 
unexpected changes in vortex orientation in BSCCO films[113] and dynamic structure in 
apparently static crossing lattices[114] Magneto-optical imaging can now see single 
vortices[104], opening a new window on real space dynamics. Higher resolution can be 
achieved with development of near field magneto-optical imaging, an advance that is 
within reach using available techniques. Specific heat experiments are ripe for much 
higher saisitivity using MEMS (micromachines) to eliminate addrada corrections and 
innovative temperature sensing. This new instrumentation will drive not only vortex 
physics but also will advance many other areas of condensed matter physics. 

V. Proximity and Interface Effects 

The superconducting proximity effect involves the mutual influence of 
neighboring superconducting and non-supeirconducting materials across an 
interface[115]. Such mutual influences can be profound. They can affect greatly the 
physical properties of botfi materials and are important in any application or scientific 
measurement that involves interfaces. Related effects occur at vacuum interfaces at the 
surface of a superconductor. The proximity effect is central to the physics of the 
coupling of superconductivity across non-superconducting barriers that make possible the 
Josephson junctions used in high-Tc superconducting electronics[116] and the grain 
boundary interfaces that are presently the primary factor limiting current flow in high- 
current superconducting tapes[117]. Hie proximity effect is also central to the broader 
application of the extremely powerful but surface sensitive techniques of photoemission 
spectroscopy and the growing arsenal of scarming local probes to these materials. The 
importance of grain boundaries as current liming factors in HTS tapes is also discussed in 



24 



Chapter VII of this report. And the importance of surface effects in the application of 
ARPES and scanning probes is discussed in Chapter III. 



To all of this must be added the possibility of surface doping through the use of charge 
transfer from deposited over-layers or the electrostatic field effect The recent 
determination of scientific misconduct in some reported results using field-effect doping 
to induce high-temperatures superconductivity does not undermine the basic scientific 
rationale for such work. Indeed, field effect doping (both capacitive[118] and 
ferrolectric[l 19]) has a long history that continues up to today. The situation has been 
reviewed recently [120]. Clearly, charge transfer and field-effect doping remain 
potentially elegant approaches to creating new superconductors and developing model 

systems for studying two-dimensional superconductivity. 

For all these reasons mastery of the proximity and interface effects in the high 
temperature superconductors is essential to progress in the field. 

In conventional, low-Tc superconductors the understanding of the proximity effect 
is relatively well developed for interfaces with normal metals[121]. The reasons are the 
power of BCS theory along with the simplification provided by the generally long 
superconducting coherence lengths typical of low-Tc materials (and conventional normal 
metals). These long coherence lengflis tend to average out and temper interface effects 
and thereby pennit the use of simple, phenomenological boundary conditions for most 
purposes. The proximity effect with a ferromagnet is qualitatively dififeralt, however, and 
its understanding remains under developed. The new twist here is that the pair wave 
function has an oscillatory decay in the ferromagnetic (FM) material[122], in contrast to 
the simple exponoitial decay found in the normal-metal case. 

High-Tc superconductors are very different. The very short coherence lengths 
characteristic of these materials make them much more susceptible to the influence of 
neighboring materials and internal defects virtually at the atomic level. Hence, the use of 
phenomenological boundary conditions is problematic, and microscopic theory will have 
to play a larger role. Of course, there is no well developed microscopic theory of the 
hi^-Tc superconductors. In addition, the strong doping dependence of the cuprate 
superconductors makes them sensitive to charge transfer at interfaces, where there is a 
tendency to form npn-like junctions[123], introducing further new complexity. The d- 
wave nature of the pairing also leads to new features in the proximity effect (and the 
related Andreev scattering process at interfaces) that have not been fully explored. One 
now well-accepted example is the reduction of the pair wave function to zero at surfaces 
whose normal points along the direction of the nodes in the energy gap[124]. 

There are also intriguing experimental results that suggest new physics is 
operating in the proximity effect witii the high-Tc superconductors. The anomalous 
normal state properties of the cuprates, particularly in the pseudo-gap regime at low 
doping, seems incompatible with the use of the conventional theory (based on low-Tc 



25 



superconductors and normal metallic behavior) to describe the proximity effect with 
these phases. In addition, various systematic studies of the proximity Josephson coupling 
of the ab-planes of the cuprate superconductors across these normal phases imply 
characteristic lengths of the proximity coupling that are larger than can be readily 
explained v^th conventional ideas[125]. The alternative possibility that longer coherence 
lengths are possible in the normal planes and/or that the range of the proximity effect 
with conventional normal metals on the c -axis of BSCCO is shorter than can be readily 
explained with conventional ideas[126] is intriguing. 

From the theoretical perspective, understanding of the proximity effect with a 
material near a quantum phase transition (sucA as the superconductor/ insulator or 
metal/insulator transitions) with their associated quantum fluctuations is lacking even in 
the case of conventional superconductivity. It is presumably even more challenging in 
the case of the cuprates, which exhibit several such transitions as a function of doping, 
due to their highly correlated nature. In addition, there are speculations that negative U 
centers in the blocking layers are playing a role in the high-Tc of some cuprates in a kind 
of internal proximity efifect[127]. 

Finally, the ability to exploit widely the powerful but inherently surface sensitive 
electronic probes of the high-Tc superconductors such as ARPES and the various 
emerging scanning probes will depend on dealing somdiow with their complicated 
surface chemistry and altered doping of the Cu02 planes near tiie surface due to the lack 
in general of a charge neutral cleavage plane in the unit cell of the cuprates, with the 
notable exception of Bi2Sr2CaCu20x (2212 BSCCO). 

Key to understanding proximity and interface effects is the controlled preparation 
and characterization at the atomic level of the various interfaces of interest. Only by 
creating and understanding such model interfaces can the necessary phenomenology be 
developed that can guide applications (with their real, more complicated interfaces) and 
painit unambiguous scientific study of these materials with surface sensitive techniques. 

Fortunately, recent advances in the controlled thin film deposition of highly 
refined interfaces of various kinds have be^ developed for the high-Tc superconductors 
and complex oxides more generally [128]. Atomic layer (or block by block) epitaxial 
growth has been achieved in some cases. Grading of individual layers as a film is built 
up may be necessary and likely is possible. The same techniques may also be useful in 
preparing the surfaces of bulk single crystals for study by ARPES and/or scanning 
probes. 

The techniques capable of such refined interface preparation involve the 
combination of very well controlled deposition techniques with various in-situ means of 
monitoring the growth. These include Molecular Beam Epitaxy (MBE), Pulsed Laser 
Deposition (PLD) and sputtering. The need for an oxidizing atmosphere presents 
technical problems, but these are increasingly under control. In-situ Reflection High 
Energy Electron Diffraction (RHEED) is now commonly available for structural 
characterization and techniques to measure in-situ and in real time the temperature and 



26 



composition of a growing film are likely to become available. Such instrumentation will 
greatly facilitate progress. Ex-situ, post-deposition characterization is necessary, 
however, in order to confirm the structure away from the growth conditions. 

At the same time, techniques for preparing well-defined grain boundaries of 
various types for physical study in both crystals and thin films have been developed. 
Advances in electron microscopy have also been developed that permit not only the 
structural characterization of the grain boundaries but also determination of the spatial 
dependence of the electric potential (and therefore the distribution of charge) across the 
boundary, at least on average. Such information will greatly facilitate progress in 
imderstanding the electrical properties of these grain boundaries. Still needing 
development are probes capable of characterizing the lateral dependence of the structure 
and properties of these interfaces (particularly electrical transport). Presumably local 
scanning probes can be brought to bear usefully on these questions. Similarly, techniques 
need to be developed that can reveal the point defects present near the boundaries that are 
not visible in TEM and may be playing a significant role in achieving charge neutrality 
near the boundary. 

In concert with better sample preparation and more thorough physical study will 
need to be the systematic development of phenomenological theories that incorporate 
appropriately the known physics of the high-Tc superconductors and the realities of the 
materials themselves. First principle predictive value is probably not possible nor is it 
necessary from the point of view of furthering the science. Phenomenological models 
may provide usefiil models of interfaces for applications and guide the empirical process 
of materials optimization. 

In summary, study of the proximity effect is a critical element in the evolving 
study of the high temperature superconductors. The key issues are: developing the model 
materials systems that will enable understanding at the reqmred atomic level; developing 
tools to make and measure such interfaces, in particular scanning probes; surface doping 
and charge transfer studies, developing a unified theory of tiie proximity effect that deals 
with the materia] realities and the novel physics of the high-Tc superconductors; and 
applying all this knowledge in surface sensitive studies of these materials. 

VI. Noneqiiilibrium Effects 

A very general case of nonequilibriiun dynamics in an electronic system starts by 
creating a high-energy electron (e.g., by optical absorption) followed by a cascade of 
excited states with smaller and smaller energies until the excess energy can escape the 
system, generally by phonons. In superconductors, noneqmlibrium effects also occur 
with a transport current, for example, at interfaces exhibiting proximity effects, including 
grain boundaries (see Ch^ters V and VIII). The nonequilibriimi effects of cxuraits are 
especially important when magnetic vortices appear either from applied fields or the self- 
field of the current. The excitation energies are not too large (<kBTc) in these cases, 
which are discussed in the dynamic phases of vortices part of Chapter IV and under 
pinning in Chapter VIII. 



27 



Returning to the cascade processes mentioned at the start, these are indicated 
schematically in Fig. 5. They include electron-phonon and electron-electron scattering 
and are relatively fast, being --10*^^ sec to achieve thermal energies[129]. The eventual 
loss of excess energy results from the escape of phonons from a finite sized sample and it 
is much slower, being generally --10*^ sec, due to the small velocity of soxmd and 
significant phonon-electron scattering. In tfxe case of a superconductor, this strongly 
affects the final relaxation step, the recombination into Cooper pairs and escape of the 
excess energy by phonons. In superconductors, scattering between electron-like and 
hole-like branches (see Fig. 5) only occurs after *themialization' to energy scales of order 
of the energy gap. tn hi^-temperature superconductors (HTS), the d-wave energy gap 
depends on the momentum direction, exhibiting nodes along tiie (ji, jc) wave vectors. 
Thus a new element of nonequilibrium processes in HTS is the relaxation of momentum 
around the Fermi surface. 



hole-like electron-like 




Fig. 5. Energy, E, versus momentum, k, for quasiparticle excitations in a 
superconductor with energy gap. A, showing electron-like (k>kF) and hole-like 
(k<kF) excitation branches. Also shown schematically are possible relaxation 
cascade processes for an initial electron-like excitation of energy, E»A. Energy 
relaxation occurs by emission of a phonon, scattering off another quasiparticle or 
breaking a Cooper pair. Relaxation between the electron-like and hole-like 
branches occurs preferentially when E-A. The final step (not shown) is the 
relaxation of the excess quasiparticle density back to Cooper pairs and the 
conconwtant escape of a phonon with energy --ZA. 

Progress has been made to understand the fast scattering rates in HTS using thermal 
Hall conductivity [130], microwave absorption[131] and optical pump-probe 
experiments[132-136], but crucial pieces are missing. Tliese include systematic studies 

28 



that cover a wide spectrum of pump and probe frequencies, other complementary 
experiments and connections to theoretical predictions. Less attention has been paid to 
the traditional nonequilibrium studies[137, 138] in LTS that have addressed a wide range 
of effects of excess quasiparticle densities and/or branch imbalances between electron- 
like and hole-like quasiparticles. The opportunities in the latter case are exotic, numerous 
and largely untapped. 

It is quite interesting that the scattering times derived from thermal 
conductivity [130], microwave absorption[131] and optical pump-probe experiments [132] 
exhibit a very similar magnitude and temperature dependence. While the first two probe 
nodal quasiparticles at the (it, n) points of the k-<l^ pendent d-wave density of states at an 
energy scale of --keT, most pump-probe experiments excite the HTS with 1.5 eV photons 
whose energy is -200 keTc and the cascade can include all k states. In addition, the 
probe response, which measures the reflectivity changes after optical pumping, varies 
dramatically with probe frequency (even changing sign) so the specific property of the 
nonequilibrium distribution being addressed is less clear. One expects that tiiese probe- 
frequency dependencies will reflect features of the electronic system such as the plasma 
frequency as well as the changes due to these nonequilibrium states. For example, the 
temperature dependence of the amplitude of the 90 meV probe energy response to a 1.5 
eV pump energy[133], shows a strong correlation with the amplitude of the neutron 
resonant spin excitation[139]. The resolutions of these fascinating mysteries promise a 
rich new field of research that can bring considerable insight into non-thermal processes 
in electronic oxides and possibly into the mechanism of HTS. For these experiments, it 
seems that much could be answered if another probe, Uke tunneling, could be done on 
such fast time scales (-10 psec) to complemoit the optical data 

The eventual recombination and energy transfer to phonons has been addressed in 
mm-wave absorption measurements that probe the reflectivity at a frequency of -0.3 
meV. The authors find relaxation times in tiie 1 0"^ sec range and intuit a more significant 
bottleneck than LTS due to the unique properties of the 'nodal quasiparticles. They also 
suggest an analogy to the T relaxation process[140] found for He. The long relaxation 
time means that the traditional nonequilibrium effects foimd in LTS, which have 
addressed the effects of excess quasiparticle densities and/or branch imbalances between 
electron-like and hole-like quasiparticles, should be observable in HTS. Such 
nonequilibrium effects in high-temperature superconductors (HTS) comprise a research 
area that is ready for exploitation. 

Numerous effects of perturbations by tunnel-junction injection of quasiparticles 
(unpaired electrons), microwave or optical illumination, etc, are readily observed in low 
Tc superconductors (LTS) and these have been understood in terms of electron-phonon 
scattering[137, 138]. This is consistent with the electron-phonon coupling mechanism 
for these superconductors. Occasionally the effects of direct electron-electron (Coulomb) 
scattering must also be considered. In HTS the situation is potentially much more 
interesting for at least two reasons. The d-wave symmetry of the order parameter admits 
a momentum-dependence to the quasiparticle energy spectrum and there are additional 
spin and charge excitations that have been suggested as potential candidate bosons for the 



29 



attractive interaction. The latter excitations are seen by neutron scattering and would be 
expected to interact with quasiparticles. By studying the relaxation processes in 
nonequilibrium it may be possible to address the importance of these excitations if their 
effects on the relaxation of nonequilibrium quasiparticle distributions can be identified, 

Nonequilibrium states are here classified as those states for which the quasiparticle 
(or, e.g., phonon) distribution exhibits an energy profile different from tfiermal 
equilibrium No matter how high the energy of the fundamental excitation process, in a 
fairly short time the excess energy of the perturbation relaxes, predominantly, into a state 
for s-wave superconductors in which it resonates between phonons of energy 2A and 
quasiparticle? of ener^ --A. This is due to the high daisity of quasiparticle' states near A 
in the BCS density of states and it results in a bottleneck for the escape of the 2A 
recombination phonons into the thermal bath since they are resonantly reabsorbed by the 
high density of Cooper pairs. This increases the effective recombination time above the 
bare value (typically by one to two orders-of-magnitude). 

The observations of many diverse nonequilibrium effects observed in low Tc 
superconductors (LTS) benefit from the long time constants for the ultimate 
recombination into Cooper pairs. This is due to the 2A-phonon bottleneck and the small 
energy scale of A in LTS also contributes to a long bare recombination time due to the 
small phase space available in the decay channel via phonons (density of phonon states 
-o)^). Nonequilibriiun studies in LTS have discovered new effects, like energy gap 
enhancement by microwave or tunnel-junction injection, branch or charge imbalance and 
new applications, like weak-link Josephson devices, superconducting three-terminal 
devices and particle detectors. See Ref 9 for more complete reviews of these topics. 
The greater richness of the interactions in HTS, together with the nonconventional order 
parameter, large energy gap and the naturally layered structure can be anticipated to 
provide additional phenomena and applications. Examples include the coupling of ac 
Josephson oscillations to phonons or the possibility of terahertz oscillators enabled by the 
coupling of coherent Josephson vortex flow in BSCCO to Josephson plasmons to produce 
electromagnetic radiation. For instance, in the latter case, one can test predictions of the 
occurrence of dynamically stabilized vortex configurations and the interaction with 
Josephson vortices with Josephson plasmons. In addition, the large energy gap in HTS 
cuprates make them attractive candidates to extend the frequency range of turmel- 
junction mixers beyond that of LTS junctions. Alftough energy g^ enhancement, by 
microwave illumination[141, 142] or tunnel junction injection[143], is well established in 
LTS, the discovery of photoinduced superconductivity in underdoped cuprates is unique 
and unexpected — it produces substantial increases in Tc that are persistent[14]. 

TTie large A© in HTS, compared to LTS, may be expected to lead to shorter bare 
recombination times, but under many circumstances nonequilibrium effects can still 
occur. For example, the longer effective relaxation time due to resonant 2A-phonon 
adsorption mentioned above is largely a geometrical escape factor that may be quite 
similar[134] to that found in LTS. This resonant adsorption is usually referred to as 
phonon trapping since the nonequilibrium perturbation energy must be converted into. 



30 



and carried away by, phonons. Phonons can be expected to play that same role in HTS, 
since, e.g., spin and charge excitations cannot leave the electronic system. But also, an 
additional trapping mechanism may occur due to the nodes of the d-wave order 
parameter. This proposed effect is the momentum-space analogy of tiie real-space 
quasiparticle traps devised for LTS superconductive detectors [144]. In such detectors, 
Cooper pairs in a large volume of superconductor (with a relatively large gap, A^) interact 
strongly with incident irradiation to produce excess quasiparticles. The detector is 
arranged so that the quasiparticles have a high probability of diffusing into an attached 
superconductor with a smaller gap. As, before the energy esc£^es the system via phonons. 
The smaller As results in a longer bare recombination time due to the smaller phase space 
of phonons of energy a)=2As. In addition, the excess energy of quasiparticles, --Ai, 
converts into a greater number of qxiasiparticles with E'-Ag. 

In a proposed relaxation mechanism, quasiparticles produced in the high-A regions 
away from the nodes at the (jc, ji) points would diffuse to traps in momentum space at the 
lower energy states near the nodes. Several mechanisms can be envisioned, e.g., direct 
scattering of quasiparticles by phonons or spin excitations and pair breaking into near- 
nodal quasiparticle states by nonequilibrium phonons or spin excitations. The 
interpretation of nonequilibrium data in these regimes could be connected to models for 
the mechanism of HTS (see Chapter VII). It will be interesting to explore the relation of 
the specific momenta of spin excitations with relaxation processes across the d-wave 
Fermi surface. The multiplying factor upon energy degradation impHes tiiat a single 1.5 
eV photon could create up to 4000 quasiparticles trapped at the nodal points with an 
energy scale of -4 K, As pointed out above, measurable recombination times in excess 
of 10"^ sec have been reported in HTS. 

The ease of fabrication of thin-film superconductor-insulator-superconductor tunnel 
junctions was also a vital component of previous studies of LTS materials. Making 
junctions witti two HTS electrodes has proved much more difficult and most tunneling 
studies have relied on point-contact or STM tunnel junctions. However significant 
progress has been made using MBE growth of multilayers of HTS with lattice-matched 
insulators as well as the intemal junctions of BSCCO crystals offer another opportunity 
that is unique to the HTS cuprates. In the latter case, it seems necessary to intercalate 
molecules (e.g., iodine or mercury bromide) between the Bi-0 bilayers to reduce the 
current for injection near the energy gap, 2A, and avoid a significant weakening of the 
superconducting state[145]. 

VII. Theory 

h Preamble 

Since the discovery of high Tc superconducting materials, there have been many ideas 
put forth to explain their unusual and often perplexing physical properties. Here, rather 
than attempting to survey the field, we offer three individual perspectives. 



31 



2. Phenomenological Approach 



a) Status, 

The cuprates are highly correlated systems close to the Hubbard-Mott 
antiferromagnetic insulating state. In the underdoped regime, pseudogap signatures[28] 
g6 well beyond ordfnary metallic behavior Here we will limit tlie discussion to the 
optimally doped case where Hubbard-Mott modifications may not be so severe. In this 
case generalizations of techniques developed for ordinary superconductors may be 
applicable with appropriate modifications and give valuable insight. For conventional 
superconductors phonon structures in current-voltage characteristics of planar tunneling 
were exploited to derive a complete picture of the electron-phonon spectral density 
a^F(co) [146]. This function defines the kernels that enter the Eliashberg equations. The 
theory accurately predicts (at the 10% level) the many deviations from universal BCS 
laws which have been seen in a broad range of experiments [146]. Similar equations 
suitably generalized to include d-wave synmietry[23, 147, 148] can lead to an equally 
good understanding of the observed superconducting properties of optimally doped 
YBCO. In this approach the general firamework of a boson exchange mechanism is 
retained with a boson exchange spectral density (denoted by l\{(o)), to be determined 
from experimental data. In the high temperature oxides, rather than tuimeling, including 
STM, the technique of choice has so far been the infrared conductivity, from which one 
can construct a model of l\{io), [23, 147, 148] When applied to tfie conventional s-wave 
case the method reproduces the tuimeling derived model for a^F(a))[149, 150]. In the 
oxides the optical scattering is dominated by a fluctuation spectrum which is largely 
featureless and \viiich extends over a large energy scale of order several hundred meV 
(the order of J in the t-J model). Such a spectrum is expected in spin fluctuation theories 
such as the neariy antiferromagnetic Fermi liquid (NAFL)[151, 152] or in the marginal 
Fermi liquid (MFL)[153]. 

In the superconducting state a new phenomenon has been identified. One finds 
increased scattering at some definite finite value of (o associated with the growth of a new 
optical resonance in the charge carrier boson spectral density, the energy of which ((o„) 
corresponds exactly to the energy of the spin resonance measured by inelastic neutron 
scattering (when available). This correspondrace does not prove, but provides support 
for a spin fluctuation mechanism (rather than the MFL). Moreover the spectral density 
derived from the infrared data, (at Tc in optimally doped YBCO) shows a form 
characterized by a spin fluctuation energy cOsf [152]. This form is progressively modified 
by the growth of the resonance at co„ and attendant reduction of spectral weight at smaller 
energies as the temperature is lowered below Tc. The spectrum obtained depends on 
temperature (througji feedback effects due to the onset of superconductivity)[154, 155], 
and leads to good agreement with observed properties of the superconducting state. 
While the generalized (for d-wave) Eliashberg equations are not as firmly grounded in 



32 



the basic microscopic theory as in the phonon case, they do offer a phenomenology 
within which superconducting properties can be understood. These include the 
condensation energy per copper atom, the fraction of total spectral weight which 
condenses into Cooper pairs at T=0, the temperature dependence of the superfluid 
density, the peak observed in microwave data as a function of temperature and its shift in 
position with microwave frequency, the similar peak in the thermal conductivity, and the 
frequency dependence of die infrared conductivity 

b) Key Issues and Opportunities. 

An important issu^j for the future is to extend the calculations to the underdoped 
regime. There is as yet no systematic quantification of pseudogap effects and 
contradictory views exist as to their origin. In the preformed pair model[29] the 
pseudogap and superconducting gap have a common origin with the superconducting 
transition related to the onset of phase coherence. In the d-density wave model[156] 
(DDW) a new order parameter competes with superconductivity. Another problem that 
needs resolution is understanding the new ARPES data which have been interpreted as 
giving strong signatures of phonon effects[157-159]. The dressed quasiparticle energies 
must also contain important renormalization due to the spin fluctuations. Certainly a pure 
phonon model is incompatible with the infrared optical data. However, it is well known 
that transport and quasiparticle scattering rates are different In transport, backward 
collisions assume additional importance in the depletion of current, as compared widi 
quasiparticle scattering. TTie quasiparticle electron-boson spectral density may have 
important contributions from both phonons and spin fluctuations, while the transport 
spectral density may be dominated by spin fluctuations. An important aim for the future 
should be to achieve a common imderstanding of ARPES, optical and turmeling data 
simultaneously. 

3. Numerical Studies of Hubbard and t-J Models 

a) Status. 

Nimierical studies of the high Tc cuprate problem have been used to determine what 
types of correlations are significant in specific models. They have shown that the 2D 
Hubbard and t-J models exhibit antiferromagnetic[160, 161], striped domain wall[162], 
and c/^, ^2 pairing correlations[162-165]. The similarity of this behavior to the 

phenomena observed in the cuprate materials support the notion that the Hubbard and t-J 
models contain much of the essential physics of the cuprate problem. 

This is really quite remarkable when one considers that these are basically two 
parameter models involving U/t or J/t and the doping x = 1-n. Furthermore, boundary 
conditions or added next-nearest-neighbor hopping terms can shift the nature of the 
dominant correlations showing that the antiferromagnetic, stripe, and pairing correlations 
are delicately balanced in these models, reminding us of the behavior of the materials 
themselves.' 



33 



b) Key Issues and Opportunities. 

While we have seen that many of the basic cuprate phenomena appear as properties of 
these models, the interplay of the various correlations and the nature of the underlying 
pairing medianism remain open. Thus a key issue is to determine whether the underlying 
physics is to be understood in terms of spin-charge separation[166, 167], S0(5) 
symmetry[130], stripes[168], spin-fluctuation exchange[169], or whether additional 
phonon mediated interactions may play a supporting role[46, 170]. With the 
imderstanding which has been gained and with further development of computational 
techniques, we have the opportunity of addressing these issues. Here it is important to 
realize that the search for tile appropriate theoretical framework for understanding the 
cuprates also includes seeking to determine what type of models (and ultimately 
materials) are described by various scenarios. For example, we would like to understand 
what types of strongly correlated models exhibit spin-charge separation or more generally 
some type of fractionalization. Is there a sufficient temperature range for strongly 
correlated 2-leg ladders to renormalize so that an S0(5) description is appropriate? Do 
stripes suppress or enhance pairing? What role do phonons play and how is the electron- 
phonon interaction affected by strong Coulomb interactions? What is the structure of the 
phase diagram for these models? What new materials or material modifications will the 
answers to these questions suggest? 

It should also be noted that theoretical progress in first-principles band theory 
simulations of ARPES intensities in the high-Tc's has been made and the inclusion of the 
electron-phonon and strong correlation effects in these simulations can advance the 
interpretation of the data[171]. 

We are in a position to address these issues and we also have the opportunity to take 
advantage of more than a decade and a half of advances driven by the cuprate discovery. 
As part of this effort we need to continue the development of numerical techniques. We 
should also work to establish closer connections to tfie electronic structure and quantum 
chemistry communities for key information on the basic orbitals and effective parameters 
that enter model descriptions of real materials. 

4. Electronic Structure 

a) Status. 

The discovery of superconductivity in MgB2 and the subsequent response by the 
computational community demonstrated the remarkable progress that has been achieved 
in first principles calculations for the electronic properties of conventional (phonon 
mediated) superconductors. Indeed, c?F((o) can now be calculated accurately for fairly 
complex materials using density functional methods. For example, first principles 
evaluation of the electron-phonon interaction was used to calculate the superconducting 
transition temp)erature of the simple hexagonal phase of Si under high pressure[172]. Not 
only can the electron-phonon coupling be obtained, but also complete phonon dispersion 
curves for the whole Brillouin Zone (BZ) are being calculated using perturbation theory 



34 



(harmonic approximation). If anharmonic terms are important, frozen phonon 
calculations yield total energies as a fxmction of the relevant lattice distortions. Indeed, 
structural phase transitions involving soft phonon modes are frequently analyzed via such 
total energy calculations. While phonon frequencies and eigenvectors are needed to 

evaluate a^F(co), it is diflficidt to draw conclusions about superconductivity from phonon 
dispersion curves. It is interesting however, that first principles calculations of phonons 
in the cuprates have in general yielded good agreement with neutron scattering 
experiments (see for example [173]and references therein). 

When Local Dehsity Approximation (LDA) talculations were unable to produce the 
insulating antiferromagnetic state in the cuprate phase diagram[174], it became clear that 
new approaches for dealing with correlation and moving beyond standard band structure 
techniques were needed. The first of these new "band structure" approaches, the 
LDA+U method, introduces a Hubbard U term into the LDA equations, affecting the 
orbitals for which the correlations are strong[175]. The more recent LDA++, and 
Dynamical Mean Field Theory (DMFT) methods make a more direct attack at calculating 
the electron self-aiergy, 2(k,a>) [176-179]. The computational resources for evaluating 
the dynamics are demanding, and while good progress is being made, results have only 
been obtained for prototype systems. Although there is not yet a satisfactory band 
structure based technique for treating spin fluctuations when going from the Mott- 
Hubbard insulating state to optimally doped high Tc materials, straight forward band 
structure calculations of the doped cuprates yield Fermi surface geometries in remarkably 
good agreement with precise angle resolved photoemission experiments. Band structure 
calculations have also been valuable in identifying the relevant orbitals and in estimating 
values of the parameters that enter more phenomenological models. 

b) Key Issues and Opportunities, 

A key ingredient in solving the Eliashberg equation for phonon mediated 
superconductivity is the simplification made possible by Migdal's theorenx In exploring 
other boson mechanisms with higher frequency spectra the role of the retarded Coulomb 
interaction, fi*, needs to be revisited[180]. It has been suggested that for vanadium the 
effective \i* is larger than expected because of the pair-breaking influence of spin 
fluctuations[181]. In the one band Hubbard model it has also been argued that strong 
correlations suppress the electron phonon coupling in a^F and transport quantities [182]. 
The recent angle resolved photoemission measurements which show mass 
renormalization for bands passing through the Fermi energy may provide a quantitative 
measure of the electron-phonon interaction for specific states[159]. A comparison with 
first principles calculated values would be most interesting. 

There are many other questions, many identified in this document, which are now 
being approached with model Hamiltonians. While electronic structure practitioners are 
eager to participate in and learn from such studies, and to prpvide parameters and insights 
where possible, there is a strong desire to develop die apparatus required for a real first 
principles treatment of the phenomena There are many insights and ideas that need to be 



35 



developed first. Perhaps the situation today is not so different than in the early 1960s 
when tfie Fermi sxiiface was considered exotic. The dividends from the investment in 
physics of that period are the basis for what is now considered "routine" materials 
science, with applications ranging from Stockpile Stewardship to material processing to 
drug design. Solving the "high Tc problem" will likewise result in valuable tools and 
insights leading to future applications. 

VIII. Defects and Microstructure with an Eye to Applications 

Crystal lattice defects and their organization on the scale of nanometers to 
micrometers ("microstructure" for short) play a \^^^y significant role in the science and 
technology of superconducting materials: [183-188] For one thing, defects are 
unavoidable in the world of "real materials," and it is vital to characterize their nature and 
distribution so as to understand their effects on superconductivity. It is also vital to 
control the defect distribution in the polycrystalline, large-scale microstructure of 
conductors since appropriate nanoscale defects are responsible for developing high 
critical current densities, Jc, within grains. But planar defects, especially grain 
boundaries, block grain-to-grain transmission of the current, dictating the geometry of 
conductors because of the saisitivity of Jc to strain defects, etc. Defects can also provide 
insights into fundamental questions, e.g., the use of grain-boundary junctions in the 
investigation of order-parameter synmietry in cuprate superconductors. HTS conductors 
are available from several companies worldwide and have been used to dononstrate large 
components of the electric power grid such as power cables, motors, transformers and 
fault current limiters. Josephson-junction devices and other electronic devices based on 
HTS technology are in an advancing state of commercial development. However, we are 
still far from understanding or being able to optimize HTS material properties in the way 
that we have leamed to do for the workhorse conductor of LTS (Nb-Ti). The main point 
is that our ability to adequately control defects and microstructures is still rudimentary. 
Some of the remaining key issues derive from the anisotropic nature of the cuprates and 
their low carrier density. These characteristics result in inadequate magnetic flux 
pinning, percolative current flow past many interfacial barriers, inability to control the 
phase state, and a general lack of materials control 

Extensive investigation of the cuprates has developed a firm understanding of 
some of their microstructure-sensitive properties. First of all, it is painfiilly clear that 
crystallographic texture and phase purity must be tightly controlled for high Jc in 
cuprates. It also seems unavoidable that magnetic flux pinning at temperatures, above 
about 30K, is inadequate in the present conductor material, Bi-2223. It is just too 
anisotropic for magnetic field applications, tiiough adequate for self-field use in power 
cables at 77K, YBCO has much greater potential for applications in fields at 77K than 
Bi-2223, because its mass anisotropy is about 7, rather than the -100 of Bi-2223, even 
though it's Tc is 92 K rather than the 1 10 K of Bi-2223. By contrast it has been quickly 
established that MgB2 has only a small anisotropy (values vary from about 2 to 7, though 
with a greater weight on lower numbers) and that grain boundaries are not serious 
obstacles to current flow. Flux pinning also appears to be strong, leading to high critical 
current densities in prototype wires. In many respects MgB2 spears to be exactly what 



36 



its 39 K Tc suggests, intermediate in properties between LIS and HTS, benefiting in 
particular from lower anisotropy and relatively insensitive to planar defects. 

It is not surprising at all that understanding of defects in cuprate superconductors 
is such a hard-won commodity, because these are very complex materials (the most 
practically important material, Bi-2223 (Bi,Pb)2Sr2Ca2Cu30io.x) forms a 7-component 
system when embedded in Ag). The continued attrition to grain boundaries and to the 
search to understand flux-pinning defects has enhanced and will continue to increase our 
knowledge of defects in complex oxides in a much wider context, e.g., the understanding 
of defects in manganites, ferroelectric perovskites, etc. Continued investment in the 
materials physics of defects in HTS materi^s is attractive, not just because of .the 
implications for superconductivity technology 

What, then, are some of the outstanding issues in this field and how can we solve 
them? We need a new phenomenology, which combines the new physics of HTS with a 
realistic description of defects and microstructure in these complex materials. At present, 
almost all of the phenomenological discission of the effects of defects and microstructure 
on the superconducting properties of HTS materials is based on theoretical concepts 
appropriate to s wave LTS. How do defects in HTS materials really interact with 
correlated-electron phenomena, stripe-phases, and electronic phase separation? We will 
not understand the answers to such questions without a basic theory of defects in complex 
oxides that takes account of their complex electronic state and proximity to the metal 
insulator transition. 

Knowledge of lattice defects and microstructure in HTS materials is mostly 
confined to YBCO (and other 123-structure cuprates) and to the 2212 and 2223 phases of 
BSCCO. Why stick to these "old favorites?" To a very large degree, this reflects a 
"tyranny of practicality and materials complexity," which inhibits the development of a 
wider knowledge needed to understand broader aspects of the materials physics of HTS 
materials. Many HTS materials are much more complex to make and appropriate recipes 
for "good sample" manufacture are lacking. It is believed that much might be learned 
from infinite layer materials. For example, their structures are not neatly divisible into 
charge reservoir and superconducting blocks. Since grain boundaries in HTS are 
beheved to be disruptive to current precisely because charge transfer to the conducting 
cuprate planes is perturbed, their study in infinite layers might be particularly valuable. 

Many issues involving magnetic flux piiming in HTS materials remain to be 
clarified. Although much is known about the thermodynamics and phase-diagrams of 
vortex matter in HTS materials, (see Chapter IV), much remains to be learned about the 
elementary interactions between vortices and defects, e.g., die physics of the elementary 
pinning forces, fp, for various types of defects and their systematic variation among 
various cuprates. Furthermore, the knowledge of the behavior of defects, such as 
dislocations and plastic flow in vortex lattices themselves, is mostly extrapolated from 
the LTS case and almost certainly needs revision in such strongly anisotropic cases as Bi- 
2223, where line vortices in LTS materials break lUp into largely, but not completely 
disconnected pancake vortices. Experiments need to be designed specifically to 



37 



illuminate the fundamental nature of defect-vortex interactions in HTS materials. These 
would be particularly valuable when combined with parallel conductor development 
activities. The intermediate nature of MgB2 makes the nature of elementary pinning 
forces, vortex-lattice elasticity and plasticity very interesting. Are these properties 
fundamentally different or similar to those of NbaSn and other LTS intermetallic 
compounds? Does the complex electronic band structure and anisotropy of MgB2 make 
it's flux-pinning fundamentally different from that in the A15 compounds? 

What is learned about the interactions between defects and correlated-electron 
phenomena in HTS materials will pay dividends in a vnder range of materials, e.g., 
mianganites; and phenomena, e.g., magnetism and metal-insulator transitions. In fact, th« 
interactions between defects and transport properties in the normal state of cuprates are 
very poorly understood, too. A better understanding here would greatly improve the 
ability to characterize the nature and concentration of defects in cuprates in a quantitative 
manner. 

There are many needs and opportunities in the science of defects and 
microstructure of cuprates, in addition to the direct connection to superconductivity (e.g., 
flux-pinning and weak links). The latter provides the motivation for microstructural 
control, but understanding of the basic materials science of defects and microstructure is 
needed to exercise such control efficiently. Here, too, experiments and theory designed 
to gain basic understanding that can couple to the activity driven by practical 
considerations would be very valuable. For example, there is a considerable lack of 
serious theory and modeling, as well as of basic experimental studies, of the 
thermodynamics, kinetics, and mechanisms of nucleation and grow^ of epitaxial oxides 
of relevance to coated conductors (including buffer layers, etc.), despite there being a 
large amount of process development in this area. Understanding of the fundamentals of 
phase formation in cuprate systems is sparse. There is also a serious need for quantitative 
understanding of the elementary defects, such as point defects, dislocations, twin 
boundaries, stacking faults, etc., which are the "elementary particles" of microstructure in 
HTS phases. This, together with quantitative descriptions of microstructure and defect 
chemistry, is needed to develop an adequate phenomenology of current transport and flux 
pinning in HTS systems. 

Another area of fundamental materials physics that is relatively unexplored for 
HTS materials is that of mechanical properties, especially elasticity, anelasticity, and 
fracture. There is a paucity of basic experimental data, and these complex materials 
require theoretical methods more advanced than those needed for simpler materials, 
including ferroelasticity, non-linear and microcontinuum elasticity, and/ models of non- 
linear lattice statics and dynamics. Furthermore, an understanding of the coupling of 
elastic strain fields to the superconductivity of HTS materials is needed to understand 
interactions between defects and superconductivity, as well as to predict the behavior of 
conductors in devices such as high field magnets where large stresses arise during device 
operation. 



38 



The quantitative description of HTS-based conductors also requires improved 
methods of modeling the physical properties of composites, including mechanical, 
thermal and electromagnetic properties. The latter is particularly challenging, involving 
current and magnetic induction distributions in poly crystal line, defect-containing, 
multiphase composites. 

The discussion above indicates the great complexity of the defect physics and 
microstructural science of HTS superconductors, which are both of fundamental interest 
and of enormous relevance to practical applications. However, powerful instrumental 
tools are available to help meet this challenge, especiaUy modem transmission electron 
microscopy and local canning probe microscopidj and spectroscopies. These tools now 
permit the characterization of atomic and electronic structure, as well as elastic strain 
fields, over length scales ranging from atomic resolution to micrometers. This affords an 
unprecedented ability to obtain images and spectroscopy of atomic, charge, and strain 
distributions, which will revolutionize our quantitative understanding of defects and 
microstructure. The use of such instrumental tools, together with microscale 
electromagnetic characterization, coupled with the development of HTS-appropriate 
theoretical phenomenology, has the potential to yield important new insights into this 
complex problem, with wider implications for many complex new materials of the future. 



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IN THE UNITED STATES PATENT AND TRADEMARK OFRCE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479,810 
RIed: June 7, 1995 




Date: March 1, 2004 
Docket: YO987-074BZ 
Group Art Unit: 1751 
Examiner: M. Kopec 



For NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



FIFTH SUPPLEMENTAL AMENDMENT 



Sin 



In response to the Office Action dated February 4, 2000: 



YO987-074BZ 



Page 1 of 187 



08/479,810 




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BRIEF ATTACHMENT BB 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479,810 
Filed: June?, 1995 



Group Art Unit: 1751 
Examiner: M. Kopec 



Date: March 1 , 2004 
Docket: YO987-074BZ 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



FIFTH SUPPLEMENTAL AMENDMENT 



Sir: 



In response to the Office Action dated February 4, 2000: 



ATTACHMENT 49 



I . IPERATURE SUPERCONDUCTOH^ 

C N. R. Rao and A. K. Raychaudhari 



Tbe foUowing tables give pcopcrtics of a noniber of high tempcntuic supcrcoaductors. Table i lists the ciystal stnictuie (s{>ace group and lattice 
coostaots) and the critical txansttioo teinperatuic for the more important high temperature s«4>ercooductors so far slodied. TaUe 2 g^vcs energy gap, 
coDcal ntnent density, and penetration depth In the superconducting state. Table 3 gives electrical and thermal properties of some of these materials 
■ibe normal state. Hie tables were prepared in November 1992 and updated in November 1994. 

REFERENCES 

1. Ginsburg. DM^ Ed., Physical ProptrtUs of High-Tcmptraturc Superconductors^ Vols. I — IH, Worid Scientific, Singapore, 1989—1992. 

2. Rao, 04.R,, Ed,, Chemistry of High-Temperature Superconduaors, Worid Scientific; Singapore, 1991 . 

X Shackelford, J.F^ The CRC Materials Science and Engineering Handbook, CRC Press, Boca Raton, 1992, 9&— 99 and 122—123. 

A, YMif&^^BA^Maierials and Crystallographic Aspects Kluwcr Academic PubL, Dordrecht, The Netherlands. 1992. 

5. Malik, S.K. and Shah, S.S., Ed., Physical and Material Properties of High Temperature Superconductors^ Nova Science PubL, Commack, 
N.Y., 1994. 

6. Ounaissem, O. cL al., Physica, C230, 231—238. 1994. 

7. Antipov. E.V. eL al., Physica. C215, 1—10, 1993. 

Table 1 

Structural Parameters and Approximate Values of High-Temperature Superconductors 
Material Stnicturc 7*^ (maximiun vahie) 



1 La2^044j 


Bmab; a = 5 J55, = 5.401, c = 13.15 A 


39 


X La2^V^*a)'-^^4 


t.ll/--LJLL»LH « ^ O — . lO "iO 1 

14/mnun; a = 3.11% c = 13.23 A 


35 




14/iiunm, a = 3.o20, C = 15^.42 A 


60 


vij« r\ 
Y il>a2tja3U7 


rtninro, 0 = ^.ezi, p = c = 1 1.d7d A 


93 




ruuuuii, 0 — j.o*fr, I? — j.of , s. til £\ 


on 


f YiBa4Cu70,5 


Ammm; a = 3.851. = 3.869, c = 50:29 A 


93 


)tr BijSrjCuO^ 


Amaa; a = 5362, i> = 5374, c = 24.622 A 


10 


4 B BijCaSrjCQjOg 


Ajaa; a = 5.409. b = 5.420, c = 30.93 A 


92 


ft ^ BizCajSrjCa^Oio 


A^aa; fl = 539, = 5.40. c = 37 A 


no 


Bi2Sr2(Ln,^^)2CD2O|0 


P4/innun; a = 3.888, c = 17.28 A 


25 


^it "n2Ba2Co06 


A^aa; a = 5.468. ^ = 5.472, c = 23.238 A; 






l4Aiinun; a = 3.866. c = 23.239 A 


92 


4 \X TliCaBajCujOg 


14/mnim; a = 3.855, c = 29318 A 


119 


^ TljO^ajCujOio 


I4Annim; a = 3.85, c = 35.9 A 


128 


ff Tl(BaU>:u05 


P4/iiimm; a = 3.83, c = 935 A 


40 


. im(SiU)Cu05 


P4/inmni; a = 3.7, c = 9 A 


40 


(na3Pba5)Sr2Cii03 


PVmmm; a = 3.738, c = 9.01 A 


40 


1^17 HCaBajCojO? 


P4^imm; a = 3.856, c = 12.754 A 


103 


* Cna5p*\)L5)CaSr2Cu20; 


P4/mmm; a = 3.80, c = 12.05 A 


90 


llTCrjYa/^oiCuA 


P4/miiim; a = 3.80, c = 12,10 A 


90 


XX^TICajBaiCtt^CS 


TA/mnm; a = 3.853, c = 15.913 A 


110 


<tl| (na5Pba5)Sr2Ca2Cu309 


P4^imm; a = 3.81, c = 15.23 A 


120 


IX TlBa2(U,./>^Oi A 


M/mnim; 11 = 3.8, c = 293 A 


40 




Cnunm; a = 5.435, b = 5.463. c = 15.817 A 


70 


»V Pb2(SrXa)jCu206 


P22i2; a = 5.333, b = 5.421, c = 12.609 A 


32 


XST (Pb.Cu)Sr2(La,CaXi»207 


P4/nunm; a = 3.820, c = 1 1.826 A 


50 


54 CPb,CuKSr,EuXEu,Ce)CuA 


14/mmm; a = 3.837. c = 29.01 A 


25 


^ i*r Nd2.^/:u04 


Wnmm a = 3.95, c = 12.07 A 


30 


H«8f Ca,.>,Cu02 


P4/inram; a = 3.902, c = 335 A 


no 


if Sr,./Jd/:u02 


P4/mmm; a = 3.942, c = 3.393 A 


40 


Bao.6Ko.4Bi03 . 


Pin3in;a = 4Ji87A 


31 




a = 14.493 A 


31 


NdBa^CuaO; 


Pminm; a = 3.878, b = 3.913, c = 1 1.753 


58 



12-91 



liIGH TCMPERATORE SUPERCONDraORS (continued) 
c# «. .» Tabkl 



MateriaJ 
^3 SraBaScOi307 

55^GdBaSfOi,07 
PyBaSiOijO, 
tt HoBaSfOi^O, 
\b ErBaSrCttjO, (multiphase) 
TmBaSfQijO, (multiphase) 
fO YBaSiCujO, 
4^V/ HgBa/:>i04 
4- iL HgBa^CaCrup^ (amiealcd in O,) 
HgBajCijCujOg 



Structure 

I4Anmm; = 3.854, c = 11.62 
14/mmm; a = 3.845, c = I li>9 
M^innam; a = 3.849, c = 1 1 .53 

Pnunm; fl = 3.802, = 3.850, c = 1 136 
Ptamm; fl = 3.794. t = 3.849, c = 1155 
Pnanm; a = 3.787, b = 3.846, c= 1 154 
'*n>mra; a = 3.784, = 3.849, c = 1 155 
Ptomm; a = 3.803. ^ = 3.842, c = 1 1 54 
I4/romm; a = 3.878, c = 9507 
I4Anmm; a = 3.862, c = 1 2.705 
ftnmm; a = 3.85, c = 15.85 
Pinunm; « = 3.854, c = 19.008 



(maximum value) 



84 

88 

86 

90 

87 

82 

88 

84 

94 

127 

133 

126 



Table 2 
Superconducting Properties 



Je (0): Critical cunent density extrapolated to 0 K 
Kt^ Feoettatioa dq>tb in a-b plane 
k^: Boltzmaon constant 



Material 

YBaiCujO; 
BijSrjCaCuPg 
TtBajCaCujOg 
I^.jtSrj,CuO4.x = 0.15 
Nd^/>K)4 



(Obtained from peak to peak value. 
♦ Obtained from fit to BCS-typc relation. 



Form 


EneiTgy|rap(A) 


Single Qystal 
Single Qystal 
Gcrsmic 
Geiamic 
Oenunic 


5- 6 
^9 

6- 7 

7- 9 
8 


4-5 

55-65 

4-^ 

4-6 

4-5 



ia^xy,(0)^Aan- 

30 (film) 
2 

10 (film. 80 K) 
0.2 (film) 



1400 
Z700 
2000 



12-92 



BRIEF ATTACHMENT BC 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of Date: March 1 . 2004 

Applicants: Bednorz et al. Docket: YO987-074BZ 

Serial No.: 08/479.810 Group Art Unit: 1751 

Filed: June 7. 1995 Examiner: M. Kopec 

For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



FIFTH SUPPLEMENTAL AMENDMENT 



Sir: 



In response to the Office Action dated February 4, 2000: 



ATTACHMENT 50 



eRCX>NDUCTIVITY 

Terr^rature 

Temperature 

1 Temperature 

Superconducti vi ty 
• Physics 

dfoonductors 



oerconductivity 
/ma) 

kshop on Towards the 
hictors 



'ty 

spies — Ist Asia-Pacifc 

J Superconductivity 

Temperature 
Superconductivity 



PHYSICAL PROPERTIES OF 
HIGH TEMPERATURE 
SUPERCONDUCTORS I 



Editor 

Donald M. Ginsberg 

Pfofessor of Physics 

University oflttinois at Uibana-Ctiampaign 



World Scientific 

Singapore • New Jersey • London • Hong Kong 



fUbSshedby 

Wodd Scientific liibltslui^ C6. Pte. Ltd. 
P O Box 128, Fairer Road, Singapore 9128 

USA office: WorW Scientific Publidiing Co.. Ina 
687 Hartwen Street. Teanedc, W 07666, USA 

UK office: World Scientific Publishing Co. Pte. Ltd, 
73 Lyntort Mead, Tottcridge, London N20 SDH, England 



T^uf book u de 
rum to the hig 



FHYSICAL PROPERTIES OF HIGH TBMPERATURE SUPERCONDUCTORS I 

Copyright © 1989 by Worid Scientific Publishing Ca Pte. Ud. 

Att rights reserved. This book, or parts thereof, may not be reproduced 

in my form or by any means, electronic or mechmica!, biduding t^oto- 

crying, recording or any infonmti<m storage and retrievd system now 

known or to be invented, without written permission from the Fublishen 



3 



ISBN 9971-50-683-1 

9971-50-894-X (pbk) 



Printed in Singapore by Utopia Press. 



ix 



CONTENTS 



Preface 



vu 



Chapter 1: Introduction, History, and Overview of High i 
Temperature Superconductivity 
D:M. Ginsberg 

Chapter 2: Thermodynamic Properties, Fluctuations, and 39 
Anisotropy of High Temperature Superconductors 
MB. Salamon 

Chapter 3: Macroscopic Magnetic Properties of High Temperature 71 
Superconductors 
A. P. Malozcmoff 

Chapter 4: Neutron Scattering Studies of Structural and Magnetic 151 
Excitations in Lamellar Copper Oxides — A Review 
Birgcncau and G. Shirane 

Chapter 5: Normal State IVansport and Elastic Properties of 213 
High Tc Materials and Related Compounds 
P.B. Alien, Z. Fisk, and A, MiglioH 

Chapter 6: Rare Earth and Other Substitutions in High 265 
Temperature Oxide Superconductors 
J.T.Markert, Y, Dalichaouck, and M,B. Maple 

Chapter 7: Infrared Properties of High Tc Superconductors 339 
T. Timusk and D.B. Tanner 

Chapter 8: Raman Scattering in High-Tc Superconductors 409 
C. Tkomsen and M. Gardona 

Subject Index 



PHYSICAL PROPERTIES OF 
HIGH TEMPERATURE 
SUPERCONDUCTORS II 

Editor 

Donald M. Ginsberg 

Department of Physics 

University of Illinois at Urbana - Champaign 



World Scientific 

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SUreRCONDUCTORS H 

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Att righu reserved. This book, or paru thereof, tnay not be reproduced 
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ix 



CONTENTS 



Preface vii 

Chapter 1. Introduction: A Description of Some New Materials and 

An Overview of This Book 1 
D,M, Ginsberg 

Chapter 2. Specific Heat of High Temperature Supercondactors: 

A Review 13 
A. Junod 

Chapter 3. Crystal Structures of High-Temperature Superconductors 121 
RM, Hazcn 

Chapter 4. The Microstructure of High-Temperature Oxide 

Superconductors 199 
Chen 

Chapter 5. Nuclear Resonance Studies of YBa2Cu307-tf 269 

G. H. Pennington and CP, Slichter 

Chapter 6. Electronic Structure, Surface Properties, and Interface 

Chemistry of High Temperature Superconductors 369 

H. Af. Meyer III and J. H. Weaver 

Chapter 7. The Hall Effect and its Relation to other Transport 

Phenomena in the Normal State of the High-Temperature 
Superconductors 459 
N.P, Ong 

Chapter 8. Oxygen Stoichiometric Ejects and Related Atomic 

Substitutions in the High-Tc Cnprates 509 
t.ff- Greene and B.G. Bagley 

Chapter 9. The Pairing State of YBaaCusOT-^ 571 
J.f . Anneii, N. Goldenfeld and S.R. Senn 

Subject Index 687 

Appendix A 697 



Appendix B 



699 



BRIEF ATTACHMENT BD 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479,810 
Filed: June 7, 1995 



Date: March 1 , 2004 



Docket: YO987-074BZ 



Group Art Unit: 1751 
Examiner: M. Kopec 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



FIFTH SUPPLEMENTAL AMENDMENT 



Sir: 



In response to the Office Action dated February 4, 2000: 



ATTACHMENT 51 



CHEMISTRY OF 
fflGH TEMPERATURE 
SUPERCONDUCTORS 



Edited by 
C. N.R. RAO. Kits. 

(^CentnoJExcdknceinChenisbyand 
ScMStateanlStnKtiwcdChemisbylM 
Mkm Msfflufe ofSdenx. Bcmgalm. India 



World Scientific 

Singapore • New Jersey • London - Hong Kong 



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i 



CONTENTS 



Preface 

' ' " ' V 

Crystal Chemistry and Superconductivity in the Copper Oxides i 
/. B. Goodenough and A. Manthinm ' ' ' 

Defects and Microstructures in Layered Copper Ojcides cy 
M. Htrvttu, B. Domengis. C. Michel, and B. Raveau ' ' ' ' 

Important Common Features of the Cuprate Superconductors: Relation 
Between the Electronic Structure and Superconductivity «7 
C. N.R. Rao ' 

Design of New Cuprate Superconductors and Prediction of Their 
Structures 

Takahisa Arima and Yoshinori Tokura 

126 

The Modulation in Bismuth Cuprates and Related Materials irr 
/. W. Tarascon, W. R. McKinnon, and Y. LtPagt ' ' ' ' 

Electron-Doped High Tc Cuprate Superconductors .... jOS 
Carmen C. Almasan and M. Brian Maple 

Application of High-Pressure and High Oxygen Pressure to Cu-Oxides 243 
M. Takano, Z. Hxroi, M. Azuma, and Y. Takeda 

Copper-Less Oxide Superconductors . . . 
A. M. Umarji 

Synthesis, Structure and Properties of La2Ni04+i . oo, 
Douglas J. Buiiny and Jurgen M. Honig 



Structure and Superconductivity in Y-123 and Related Compounds 
G. V. Suhha Rao and U. V. Varadarajv 



viii 



Ther^dynamics of Y-Ba-a.0 System and Related Aspects ... 305 
i>. r. Pasktn and Yu. D. Trctyakov • • 406 

Investigation of the Electronic Structure of the Cuprate 

Super«>nductors Using High-Energy Spectroscopies . . ^« 

Field Modulated Microwave Absorption in High-Temperature 

Superconducting Oxides 

Micky Pun and Larry Kevan 

BijSrjCaiCujO./Ag Superconducting Tape 

Togano. H. Kumakura. H. Matda, end J. Kasc 

High rc Superconducting Thin Films - Processing Methods 

and Properties 

S. Mohan ' • • . . 411 

Abttlr^*'*'"" Superconductor Thin Films by Pulsed Laser 
S. B. Ogalt ^54 

^TSIloX: 'ral' .^"^ "^"'^ 

a SckUnkcr, J. Dumas, C. L. Liu, and S. Rcvtnaz ^ 



Published by 

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Library of Congress CaUloging-ln PublicaUoa DaU 

Chcmisliy of high^empc^«urc: superconductore/fcdiicd by CN R. 
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p. cncL 
Indudes biWiographical references. 
ISBN 98 10208057 

1- High temperature supeicofxiuctors. 2. Si4)eic«iiductiviw- 
Oicmisuy. 3. S<rfid state cbctnixtiy. LRao.CN.R. 
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" in pi 
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Since 
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is pof 
single 
the v< 
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BRIEF ATTACHMENT BE 





IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479,810 
Filed: June 7, 1995 



Group Art Unit: 1751 
Examiner: M. Kopec 



Date: March 1 , 2004 



Docket: YO987-074BZ 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



FIFTH SUPPLEMENTAL AMENDMENT 



In response to the Office Action dated February 4, 2000: 



ATTACHMENT 52 



The CRC 
Materials Science and Engineering 

Handbook 

Editor 

James R Shackelford 

Professor of Materials Science and Engineering 
Division of Materials Science and &igineefing 
and 

Associate Dean of the College of Engineering 
University of California, Davis 

Associate Editor 

William Alexander 

Research Engineer 
Division of Materials Science and Engineering 
University of California, Davis 




CRC Press 
Boca Raton Ann Arbor London 




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with pennission, <ukI soun*s are indicated A wide variety of^i^^^Sv^J^' ^^'^ " '^'"^ 

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Direct all inquiries to CRC Press. Inc.. 2000 Cc^mc Blvd. N. W.. Boca Ratoo. Horida. 3343 1 . 

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CRC Materials Science and Engineering Handbook iii 

TABLE OF CONTENTS 



The Elements 1 

Elements for Engineering Materials 2 

Elements in the Earth's Crust 4 

The Periodic Table of The Elements 6 

The Metallic Elements 7 

The Elements in Ceramic Materials 8 

TTie Elements in Polymeric Materials 9 

The Elements in Semiconducting Materials 10 

Available Stable Isotopes of the Elements 12 

Properties of Selected Elements , 20 

Melting Points of Selected Elements 26 

Densities of Selected Elements 28 

Crystal Structure of the Elements 30 

Atomic and Ionic Radii of the Elements 34 

Atomic Radii of the Elements ! 39 

Ionic Radii of the Elements 41 

Selected Properties of Superconductive Elements 43 

T^ for Hiin Films of Superconductive Elements 44 

Engineering Compounds 47 

Engineering Ceramics 48 

Refractories, Ceramics, and Salts 53 

Type n Superconducting Compounds: 

Critical Temperature and Crystal Structure Data 65 

High Temperature Superconducting Compounds: 

Critical Temperature and Crystal Structure Data 98 

Crystal Structure Types 101 

Critical Temperature Data for 

Type n Superconducting Compounds 104 

Selected Superconductive Compounds And Alloys: 

Critical Field Data 121 

Tc Data for High Temperature Superconducting Compounds 122 

Bonding, Thermodynamic, and Kinetic Data : 125 

Bond Strengths in Diatomic Molecules 

(Listed by Molecule) 126 

(Listed by Bond Strength) 135 

Bond Strengths of Polyatomic Molecules 

(Listed by Molecule) 144 

(Listed by Bond Strength) 147 



CRC Materials Science and Engineering Handbook 

Table of Contents (Continued) 



Carbon Bond Lengths (Periodic Table Presentation) 150 

Carbon Bond Lengths j ^ j 

Bond Length Values Between Elements 

(Listed by Bond) 

(Listed by Bond Length) 156 

Bond Angle Values Between Elements 

(Listed by Bond) j^g 

(Listed by Bond Angle) ZZ.l.... 159 

Heat of Formation of Selected Inorganic Oxides 150 

Heats of Sublimation (at 25"C) of Selected Metals 

and their Oxides 

Melting Points of Selected Elements and Inorganic Compounds 

(Listed by Element or Compound) j 74 

(Listed by Melting Point) /.Z.Z... 186 

Melting Points of Ceramics 

(Listed by Compound) j 

(Listed by Melting Point) 

Heat of Fusion For Selected Elements and 

Inorganic Compounds 206 

Surface Tension of Liquid Elements 21 8 

Vapor Pressure of the Elements 

(V eiy Low Pressures) 235 

(Moderate Pressures) ; 237 

(High Pressures) 240 

Specific Heat of Selected Elements at 25 X 

(Listed by Element) 243 

(Listed by Specific Heat) 11.1.11Z..248 

Heat Capacity of Selected Ceramics !.. '.1.1".. 253 

Specific Heat of Selected Polymers 255 

Phase Change Thermodynamic Properties 

for Selected Elements ; ^ 26O 

for Selected Oxides 269 

Thenmodynamic Coefficients 

Description 281 

for Selected Elements 283 

for Selected Oxides 292 

TTiermal Conductivity of Metals 

at Cryogenic Temperatures 395 

at 100 to 3000 K ZZZ'Z 321 



CRC Materials Science and Engineering Handbook v 

Table of Contents (Continued) 

TTiennal Conductivity of Selected Ceramics 334 

Hiennai Conductivity of Special Concretes 345 

Thennal Conductivity of Cryogenic 

Insulation and Supports 346 

Hiermal Conductivity of 

Selected Polymers 348 

Thermal Expansion of Selected Tool Steels 355 

TTiermal Expansion and Thennal Conductivity 

of Selected Alloy Cast Irons 356 

Thermal Expansion of Selected Ceramics 357 

Thermal Expansion Coefficients for Materials 

used in Integrated Circuits 374 

Thermal Expansion of Selected Polymers 376 

Values of The Error Function 384 

Diffusion in Selected Metallic Systems 385 

Diffusivity Values of Metals into Metals : 406 

Diffusion in some Non-Metallic Systems 416 

Diffusion in Semiconductors 417 

Temper Designation System for Aluminum Alloys 424 

Structure, Compositions, and Phase Diagram Sources 425 

The Seven Crystal Systems 426 

The Fourteen Bravais Lattices 427 

Structure of Selected Ceramics 428 

Density of Selected Tool Steels 434 

Density of Selected Alloy Cast Irons : 435 

Density of Selected Ceramics 436 

Specific Gravity of Selected Polymers 439 

Composition Limits of Selected Tool Steels 450 

Composition Limits of Selected Gray Cast Irons 459 

Composition Limits of Selected Ductile Irons 464 

Composition Ranges for Selected Malleable Irons 468 

Composition Ranges for Selected Carbon Steels 470 

Composition Ranges for Selected Resulfurized Carbon Steels 475 

Composition Ranges for Selected Alloy Steels 478 

Composition Ranges for Selected Cast Aluminum Alloys 498 

Composition Ranges for Selected Wrought Aiiminum Alloys 502 

Typical Composition of Selected Glass-Ceramics 506 

Phase Diagram Sources t 



vi 



cue Materials Science and Engineering Handbook 

Table of Contents (Continued) 



Mechanical Properties 

Tool Steel Softening After 100 Hours , 
for Various Temperatures 

Mechanical Properties of Selectii Gray Ca^'t tons 

Mechanical Properties of Selected Ducdle Iron' 

Average Mechanical Properties of Treated Ductile froi^s ^\ 

Mechanical Properties of Selected Malleable Iron CasSgs' " 

Young's Modulus of Selected Ceramics ^ 

Modulus of Elasticity in Tension for Sele;;t;i poty^;i; ■"'12 

Poisson's Ratio for Selected Ceramics 

Yield Strength of Selected Cast Aluminum Allocs ' "^^^ 

(Listed by Alloy) 

(Listed by Yield Strength ) 

Yield Strength of Selected Wrou^t Aj;r;;i;.um'Xu;;;s '"^ 
(Listed by Alloy) ^ 

(Listed by Yield Stren^ ) .... ^^'^ 
Yield Strength of Selected Polymers 
Tensile Str^gft of Selected Aluminum (itiiig iioys 

(Listed by AUoy) ^ ^ 

(Listed by Tensile Strength ) 

(Listed by Tensile Strength ) 
Tensile Strength of Selected Cerariiics 
Tensile Strength of Selected Polymers 
Total Elongation of Selected Cast Alum'iii;m"ilj;>i; 

(Listed by Alloy) ^ 

(Listed by Total Elongation ) 
Total Elongation of Selected Polymers 

Elongation at Yield of Selected Polymers fl 

Shear Slrength of Selected Wrought Aluminum Albys 

(Listed by Alloy) ' 

(Listed by Shear Sti-ength) 

Hardness of Selected Wrought ■Aluminui;;'i^li:s 

(Listed by Alloy) ^ 

(Listed by Hardness) ' 

Hardness of Selected Ceramics : 

Hardness of Selected Polymers 

647 



CRCMateriaUScUnceandEn,ineerint Harulbook 

Table of Contents (Continued) 
Compressive Yield Stt«j^ o 

^S^^^^^^!^. 

(Listed by AUoy)-.^ 

(Listed by Fatigue StrengA^^^^.^— 

Jfficient of Static Fnction for Selectea ro y 

Electrical Resisnvity of Selecieo j 

R„istivi.yofSelcc.cdC«3m.cs 



Volume^isttvityofSdeCcdPolym^. 

Dielectr 

S:S^^StorforSelectedPolymers 



Dielectric Strength of Selected Polymei.^ 



; Constant of Selected Polymers. 



Resistance of Selected Polymers ■ • - 

nSoeision of Optical Matenals at 298 K 

Uispeabiuu « r -r^raimcs 

Transmission Range of Glass v^^r 

T^sparency of Selected Polyiners 

SctivelndexofSelectedPolymers 

Chemical Properties 

Composition of Sea Water 

ArionsinSeaWat^._p— 

Water Absorption of beieciea ru j 



BRIEF ATTACHMENT BF 





IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479,810 
Filed: June 7, 1995 



Group Art Unit: 1751 
Examiner: M. Kopec 



Date: March 1,2004 
Docket: YO987-074BZ 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



FIFTH SUPPLEMENTAL AMENDMENT 



In response to the Office Action dated February 4, 2000: 



ATTACHMENT 53 



AMTO Science Committee, 

duwlo^caitcnowtedge, 

'ties. 

s in conjunction with the 



ng Coqporation 
vYoric 

ic Putitishers 
Dn and London 



Materials and 
Crystallographic Aspects 
of HTQ-Superconductivity 



edited by 

E.Kaldis 

Laboratorium fur Festkdrpeiphysik, 

Eidgendsstsche Technische Hochschule HdnggeitTerg, 

Zurich, Switzerland 



rg. New Yoric, London, 



(iographioal references 
tk>ns from international 

fs: 

ESRIN, 

retrieval software k\ 
E Technologies Inc. 

ird of Publishers or 

■ . Kluwer Academic Publishers 

Dordrecht / Boston / London 

Published in cooperalion with NATO Scientific Affairs Division 



PfX)ceedings of the NATO Advanced Study Institute on 
Materials and CiystallogfapWc Aspects of HT^.-Superconductivity 
Erice, Sicily, Italy 
May 17-^, 1993 

A CJ.P. Catalogue record ftx thfe book Is avaHaWe from 1^ 



TABLE 01 
Preface 
Part I: Stru 



ISBN (>-7923-2773-X 



Pul)nshed by Kluwer Academic Publishers. 

P.O. Box 17. 3300 AA Dordrecht, The Netheriands. 

Kluwer Academic Pufcrfisheis incorporates the publishing programmes of 
D. Reidel, Martiruis Nqhoff . Dr W. Junk and MTP Press. 

Sow and distrftnited ki the U.S A and Canada 

by Kluwer Acadeiroc Put>6shers, 

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In all other countries, sold and cBstrftRited 

by Kluwer Acadenrvc Publishers Group, 

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Panted on add-free paper 



All Rights Reserved 

© 1994 Kluwer Academk: PubTishers and copyright holders as spedfied on appro- 
^ 4>riate pages within 

No part of the material protected by this copyright notk^e may be reproduced or 
utilized in any fomi or tiy any means, electronfc or mechancal, including photo- 
^ copying, recording or by any information storage and retrieval system, without written 
permissk>n from the copyright owner. 

Printed in the Netheriands 



Af. Marezio . 
A dassificati 
between the 

Hewat 
Neutron pow 
superconduct 

r, Egami 
Local structu 
temperatuie s 

D. Hohlwein 
Superstructun 

VJ, Simonov 
Accurate X-^n 
materials 

C. ChaiUom c 
Structural and 

John B. Good 
Electron en^ 

John B, Goodi 
The system La 

John B. Goodi 
The n-type cof 



TABLE OF CONIENIS 
Preface 

Part I: Strurture and Structure-Properties Relationship 

M. Marezio and C. ChaiUout 

AW. Hewat 
r. Egam 

^ sfructund distortion: im^ication to the mechanism of high 
tempCTaturc superconductivity ^ 

D. Hohhvein 

Supeistn.ct«r«. in 123 compou«b X-ray and neutnm diffiaction 

VJ. Simonov 

A^te x-ray stnictural investigations Of Single ci^ 
C. ChaiUout and M. Marezio 

Structural and physical properties of superconducting La,CuO^ 



IX 



John B. Goodenough 

The n-type copper oxide superconductors 



17 



45 



65 



83 



129 

John B. Goodenough 
1 appro- Electron energies in oxides 

uced or r l d ^ 

I photo- ^' Goodenough 

t written system La2^Sr,Cu04 



145 



161 



175 



vi 



Shin-ichi Uchida 

Chaige dynamics in higli T, copper oxides 
Y. Maeno 

Lattice instabflities and supeiconductiviQr in U-214 compounds 
Part H: Ph jsics of HTSC 
D. Brinhmnn 

Probing oystanographic and materials properties of Y-Ba-Cu-O 
superconductors by NMR and NQR 

U. Welp. G.W. Crabtree, J2. Uu and Y. Fang 
Infrared properties of selected high T. superconductois 

H. Keller 

Probing high-temperature superconductivity with positive muons 
T. Schneider 

Extreme type n siqjcrconductors: Univeisal properties and trends 
G. Ruani 

m-exdted Raman spectroscopy on HT. superconductois 

I.Morgenstern. JM. Singer, Th. Hu Jldn andH.^. Matuttis 
Numerical smiulation of high temperature supercond»<^ 

/. Rdhler 

AM. Hermann. M. Paranthaman ami HM. Duan 

Smglc crystal growtfi and characterization of thallium cuprate 

supercwiductors - A review 

Part m: Flux Pinning, Pinning Centers, Applications 

PJi'Kes 

Hux pinning in high-iemperaturc SBpeiconductois 
M, Murakami 

Hux pimiing of high temperature superconductors and tfieir applications 



187 
203 



225 

249 
.265 
289 
311 
331 

353 

373 



/. Mannhart, J. 
High-T, thin fil 

/. Alarco, Tu. £ 
Z. fvanov. VJC. 
J. Ramos. E. Sh 
Engineered grail 
api^cations 

Part IV: Organ 

/- Fink. P. Adeln 
M. Kniqjfer, Af. A 
afidE.Sohmen 
High-energy spec 
superconductors 

G. van Tendeloo < 
Electron microsco, 
materials and luDe 

JackM. Waiiams, 
UrsGeiser,John/ 
Eugene L. Ventwii 
Structure-property : 
and annion-based ( 
use m die design o 

Part V: Phase Di» 

/. KarpinsU. K. Cc 
and E. Kaldis 
Phase diagram, syn 
oxygen pressure Pc 

GJF. Voronin 
Thermodynamic sU 



401 



433 



/. Mannhart. J.G. Bednorz, A, Catam, CK Gerber and D.G. Schlom 

Hi£|i-Te thin fflms. Growth modes - stmctore - qjfdications 453 



/. Alarco. Til Boikov, G. Brorsson, T. Claeson, G. Daabncms, J. Edstam, 
Z. Ivcam, VX Kaplunaiko, P.-A. NUsson. E. Olsson, HJC. Olsson. 
J. Ramos, E. StqxMtsav. A. Tzalenchuk, D. WinkUr and Y.-M. Zhang 
Engineered grain boondaiy junctions - diaracterisdcs, stnicture. 
applications 

Part IV: Organic Superconductors 



/. Fink. P. Adelmann. M. Alexander, K.-P. Bohnen. MS. Golden, 

M. Knupfer, M. Mertel, N. NOcker, E. Pellegrin, H. Romberg. M. Roth 

and E, Stamen 

Higji-eneigy spectroscq>ic studies of fiillerene and oiprate 

supercxMiductors 493 

G. van Tendeloo and S. Amelinckx 

Electron microscopy and the stnictural studies of superconducting 

materials and fiillerites 52 1 

Jack M. Waiiams, K. Douglas Carlson. Aravinda M. KM, H. Hau Wang, 
Urs Geiser, John A, Schlueter. Arthur J. Schultz. James E. Schirber. 
Eugene L Venturini, Donald L. Overmyer and Myung-Hwan Whangbo 
Structure-propetty rdationships in radical-cadon (dectron-donor molecule) 
and annionrbased Onduding fiillerides) oiganic siq)erconductois and their 
use in Ae design of new materials 539 

Part V: Phase Diagrams of HTSC 

/. Katpinski, K. Conder, Ch. KrUger, H. Sckwerl. Mangelschots. E. Jilek 
and E. Kaldis 

Phase diagram, synthesis and crystal growth of YBaCuO phases at high 
oxygen pressure Po2<3000 bar. 555 



GJ". Voronin 

Thennodynamic stabiliQr of superconductors in the Y-Ba-Cu-0 system 585 



BRIEF ATTACHMENT BG 





IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479,810 
Filed: June?, 1995 



Group Art Unit: 1751 
Examiner: M. Kopec 



Date: March 1, 2004 
Docket: YO987-074BZ 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



FIFTH SUPPLEMENTAL AMENDMENT 



Sir: 



In response to the Office Action dated February 4, 2000: 



ATTACHMENT 54 



Physical and Material 
Properties of 
High Temperature 
Superconductors 



Edited by 
S.K. Malik and S.S. Shah 



NOVA SCIENCE PUBLISHERS, INC. 



Art DirectOK Christopher Concaimon 

Grap^HoKwRdiberg and Maria Ester Hawivs 
Book Production: Michael Lyons, RoseaimW^ 
Casey pfalzer, June Martino, 

r,-«^i« T J"^ySauter,andMicheneLalo 
Circulation: IreneKwartiroff, Annette Hellinger, 
and Ber^amin Fung 

Physical andmaterialproperties of high temperature 
superconductors / edited by S.K. MaIikaiidS5. Shah, 
p. on. 

Jjdudes bibliographical ref erenteS and index. 

ISBN l-56072-ll«: $145.00 

1. High tenqjetature siq>erconductons. Z Hidi 

537.6'23-dc20 ^ 



© 139* Nova Sderwe Publishers, Inc. 
6080Jaidw TunqOx, Sidk 207 
CommticNemYork 11725 
Tele. 51^499-3103 Fax 516499-3146 
E MaU NovasdlQttoLcom 

part of this book nuy be reproduced. 

Printed in the United States cf America 



LIBRARY 

University Of Miami 



Contents 



Af. GnatWaU and M.-H. Pan 

C^^^ and Snpercoaducfing Ropertics of I^BaSiCuaOy 
V. Badri, U.V. Varaiar^u. and G.V. Subba Eao 

hudnre andProperties of Hedron Supereondactms 
G. BaUunshnan 

L Soderholm and CW. Williams 
J.S. Xite, M. Reedyk and /,£. Greedan 

Y.V. Yakkmi and RM. Iyer 

T 1?*^****" Superconducting FuUeienes 
W. mmtpson a Spam, K. Hdkza, O. Odn, G. Gruncr 
R^. Kaner, F. Diedmdi. and ILL maten 

P- GanguJy 

CheDoical Doping and Charge Balance in High 
Temperature Superconductors 
£.£. Alp and SM. Mini 



C-i:. Loong and L Soderhohn ^ 

Srinivasan 

^i^a«^ Ak, /i-Onw^ How amf /osepft Brill 
Diffraction from the Flux-Line Uttice in Hi..!. 
. Ten^^atureSuperconductors ^ 
^- McKenzie Paul and T.Fotgan 



ides 



nfs cm Inhoniogeneoas Magnetk St^^ 
>Iiiieiniype^andiype-nSiipeix»t^ 421 
It JQmwr, S. Eamakrishmn, and A,ti Groaer 

lantized Lorentz Rmx<v Micrawavc Absoipfion and Magnetic 
Kcsonance in Hig^i Tcmpenttare SapeicmdacfQzs 445 
JC-N. Shrivasiava 



^04 and 



ui 



I Growth and Characterization of Oxide Sapercondoctots 
S.C Gadkitri, MJL Gupta, and S.C Sebharmd 

tietic Fropcrties in BiaSirzCaCu^Qx Single Oystals 

tecent Theories of Hig^i Tc Saperconductivify 
Sinha 



477 



529 



ndYb) 
icral. 



sin file 

Vinokur, 



actors 
t Brill 



itical Oment in High Temperatore Supercondnctois 
P. Bhattacharyya 

ical State Model for Samples with Non*Zero 
Demagnetization Factor 
P. Ckaddah and Bhagwat 

33 Eligh-XcJosephsonJimctions— A Review 
Gupta 

3J|Stntctiiial, Morphological and Snperconduding Ptoperties of flie Thin 
Hhns of Hig;h*Tc Oxide Sapercondadots Dq>osited by Pulsed 
Laser Ablation 

$£. Ogdc, SM. Kanetkdr, RJ), VisputCr 
5 Jf. Viswanathanr and ST. Bendrc 



3S 



4Q 



In-Sita Growfii of Supercondacting YBa2Ca307^ Thin Hlms 

Pinto 

Preparation and Characterization of YBa^CnsOr-^ Thick Films 

DX Aswal MX, Gupta, A,K. DebnatK 
S.K. Gupta, and S.C Sabharwal 



541 



557 



571 



591 



629 



649 



N.C K. AMbay, .ni S.K Atrfa 

^'G. Kulkarni 

Subjectlndex 




lie idea ofl 
me Siq 
Febmazj 

Ocpaxtzne 
itute of Faad 



the 



It was decide 
tlie form of a I 
rorkshop ntaiiy 
f therefore, fdl 
Id invite artid 
very happy to j 

Weareindebt^ 
id made it sdf^ra 
ience mi Tedm* 
Reseaxch, Mara 
[aadLidixs 



si^SatuteofF 
ay 400 005, 1 



BRIEF ATTACHMENT BH 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



in re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479,810 
Filed: June 7, 1995 



Group Art Unit: 1751 
Examiner: M. Kopec 



Date: March 1, 2004 
Docket: YO987-074BZ 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



FIFTH SUPPLEMENTAL AMENDMENT 



Sir: 



In response to the Office Action dated February 4, 2000: 



ATTACHMENT 55 



ELSEVIER 



PhywcaC230 (1994) 23J-238 



Synthesis and characterization ofHgBa,Ca„_,Cu,0,„,,,, 

(« = I,2,and3) 

O. dmaissem, L. Wessels, ZX Shene • 



Abstract 



Ba.a^..Q.,O,„,.,„amdyHg-120l.Hg-,2I2andS^"SjJlSL"^^ superconducting compounds Hg- 

jj^hesis parameter is snnJicd in dcuiL Using the scaS o^II^kT ^'^ ^' of ,hc 

100% rcprodudbility of ncariy 100% puxe ^201 T^i^SlyT^^""^."^ P«>«duns a« found ,o ensure a 
.20, a.300.Cfor ,8h «s«hsin«.enhan^. ofTu 



1. Inlrodaction 

Following the discoveiy of superconductivity with 
7;=94 K m the ondaycr HgEa^CuO^^, compound 
11], a yanety of new mercury cuprates have been 
qmthesizei' (2-lOJ. HgBa,QiO,^, (Hg-1201 ) is the 
rust memSer of the homologous series Hg- 
Ba,a._ ,Cta,02„+ The of the fim, second 
and third members are 94 K, 127 K and 134 K, re- 
spectively. HgBa,Ca,_ , Q.,0^,,,, are isostructural 
to the Tl based superconducton Tl- 
Ba,a„_,Cu„0^.,, { 11. 12] but unlike the thallium 
compounds the mercury layers are heavily oxygen 
defiaent. The structure of the Hg based supercon- 
ductors HgBa,Ca„_ ,Cu,0^,,,, can be described as 
a sequence of layers: 

..[(BaO),(HgO,)„(BaO).(Cu02)„- 



' Contsponding author. 



0921-4534/94/$07.00 ©i994BsevicrSdniof RV aii 
SSD/0921-4534 (94)00460-9 ' "ghts reserved 



{(«-l)(aMCu02).)](BaO),.„ 

in whid. blocks (BaO),(HgO,)„(BaO), having the 
rock-salt structure and a thickness of about 5 5 A al- 

tcmatewithblocks(CuO,)„{(„-i)(Q,),(Q,o,)o} 
havmg a perovskite-like structure and an apprcxi' 
nwtc thickness I4.00+(„_i)x3.16J ^ n,e sub- 
scnpuoandcindicateifthecationisattheoriginor 

r rf.?°Jf """^^ »° '^y"- All Hg-1201 
n3.14J Hg-1212 {3J and Hg-1223 [15] are found 
to aystaliize with symmetry of space group P4/ 
mmm. An orthorhombic symmetry was also pro- 
posed by Meng et al. [ 1 6 J for Hg- 1 223. 

The research conduaed on the thallium-based 
compounds showed that these materials offer a wide 
vancty of possible substitutions on the different sites 
of their structures. Many compounds were prepared 
having their 7;above 100 K. As we mentioned above 
many new mercury-related compounds were already 
successfully synthesized with 7; around 100 K Fur- 



232 



no practical v;,„clSa^'Jf^'^»^^ 
rcouirivi ^^"^ cnonnous pressure 

ducting compounds Qf hijh puS'^L'^ r*™"* 
ous chaUcngc until this daVc ^coTS^^ " T 

h!o . *'«»™P«ition of the mercuiy o^^ 
at lowtcmpcrature (between 500 aJS^t 
and by coasequence. the formation of tJe su^i' 
ducting phases is due to the reaction 

U j the high-pressure methods in which ii,. ^ 
position of HgO is slow, and 
(2) the sealed quartz tube methods 
Several groups reported their success in nr^, • 

method. Usmg diis method, manydassicaJ ^il ■ 
routes were employed. Mcnk etTJn^ 
synthesis Of the m^c^y^^J^ot^^ 
using an original method in ^ch thl Z^T 

cont^Uedbytheinsertionofp^^S^^S'i.e 
scaled quam tube togetiier ^th^^f^f 

composition HgBa,5 .CuT 

thesis Of ^'c^:^^j'z';;^±z 

tcrent preparation procedures such «« 
rials.heatingtempJLture.^Z'i^/^'^"^^^^^ 
of our wor. was to study' U.e^ «^Tf 
parameters and to find a mor,. ^„ ail these 
wHchsuaranteestoufu.:^™-^^^^^ 

d^n^dsupereonductingphasesM^thhiCS^^^^^^ 
report herem the optimization of the3th«^; „f 

samplesofgoodquahtyaad 100%repr«tv ° 
ing the sealed quartz tube method """""^ 



O. Chnumscm^al. .PHynca CiS0fJ994J231-23S 



2. Experimental 



•00% repr^ucibl^rAr^S 1^^?^'^ 

and heating ^^n^O^^ZT^;'^"^^ 
preparations were all based . ^ '"^^ 

in which we fim^e ° 
Ba,a, .Cu O ThrL.*^ precursors ol 

taiiedVmS^m^r^^^^^^ 
Priate amounts c^«I^;:H-^^?*'^0"«PPn>- 

^onnula U9T^^^'SXZ ITT^ 
crucible and introduced i„7« » u ^° 
650-C for 1-2 h Preheated furnace at 

to ISo'cVJ ''^*^»«»P«^t"re is then incr^ 
'o /50 Cand mamtamed for 1-2 h befon- thTT^ 
Perature is increased to 80O-93O->r^ 
heated a, this temperature for ,1,^- J^! « 

. f-''-"«"2ji+i+* (non-reacted HRrwi^ 
(total weight about 1.8 g) were cTirT OCO) 

vacuum ,^ cj^^'^rro"^: 

3.5»C/nun) to 80a-95O«r n.- . "<^ica ^i- 
n«intained for 3 to^O K 

1 s-r/™- J *° h before cooling slowly (1- 
tu^S'oT^^^^'^'^^e furnace was'tii 

Td 1. l^r^ " P^'^'^^t*^ f»™ace at 300-C 
2Ln , 1 ' '^"•^ «f '8 »>■ ^« samples we„ 
*a d;"'S "' ^"^"^"^ " 
iThc samples were characterized using the X-iay 
Aff«ct.on,echmque.,heACmagneticslceptibility 
^trfo™ T ™-^--««^- X-ray experimZ 
^S^aTn °" " diffntctometer 
wto Cu Ka radiation and showed that the supercon- 
ducting phases were the majority phases in^TTe 



a Oimaissem eld. /Physica C230 (1994) 19^238 



233 



inally suc- 
>urity and 
•t made to 
sin^c-step 
1 together) 
The other 
sp method 
arsors of 
; those ob- 
]) in appro- 
chiometric 
in alumina 
furnace at 
1 increased 
rc the tem- 
: sample is 
;forc being 
ingthefur- 
ideraflow- 
. are inmie- 
me of the 
ing powder 
1 and then 
P) and of 
HBCCX)) 
>gcther in a 
iter, 1.0 cm 
was in turn 
precaution 
heated (1- 
eraturc was 
. slowly (1- 
X was then 

^ to a heat- 
the samples 
zt at 30O'C 
imples were 
temperature 

g the X-ray 
usccptibility 
experiments 
ffractometer 
he supcrcon- 
es in all the 



samples prepared under the conditions described 
above together with some impurity phases which may 
be estimated to be in the order of 5-20%, These im- 
purity phases arc mainly CaHg02 and CaO. The AC 
magnetic susceptibility measurements showed that 
the samples prepared at temperatures above 900'C 
and the samples heated for more than 10 h were not 
superconducting. These experiments also showed 
sharp transitions from the normal stale to the super- 
conducting state with AT;, in the order or 5 K. 



3. Results 
II Hg' 1201 

As the first member of the homologous series 
HgBa2Ca„.iCu„02«+2+* Hg-1 201 docs not contain 
calcium; its synthesis can be done very easily using 
our procedures with very good quality and a sharp 
superconducting transition. The precursor was first 
heated at 750*C (1-2 h) and after the total decom- 
position of the barium nitrate the temperature was 
raised to 900*C for 20 h before being pulled out and 
quendied to room temperature in the dry box. Slow 
cooling in the furnace gave the same good quality of 
precursors. The resulting precursor was partially 
melted and very well crystallized. An appropriate 
amount of HgO was added to the precursor and pel- 
tetized. Pellets of both precursor (P) and non-re- 
acted mixture of HgO+prccursor (HBCOO) were 
scaled together at a weight ratio (P/HBCOO) of 0.48 
and slowly heated (3*C/min) to SIO'^C maintained 
for 6 h. and then slowly cooled (3.5**C/min) to 
575*C. The power was then shut off and the furnace 
was naturally cooled to room temperature. 

X-ray diffraction pattern of aHg-1201 sample pre- 
pared under these conditions is presented in Fig. 1 
and shows that Hg-1201 is the majority phase 
(>95%) and that the compound is nearty single 
phased. The structure is tetragonal with the space 
group P4/mmm, and there is no evidence of any kind 
of special extinction. The refined cell parameters of 
the as-synthesized sample arc: a=3.8831(l)A and 
c=9.5357(2) A. 

AC magnetic susceptibility and resistivity mea- 
surements (Fig. 2) performed on Hg-1201 samples 
show a sharp superconducting transition and a zero 



5000- 



g 4000- 

J 3000-! 
% 

^ 2000-1 



I Hs -1201 I 



d 



iooo- 



10 



ii 



i 



20 



50 



60 



30 40 
2-Theta (deg.) 

Fig. 1. X-ray diffraction pattern of an as-prepared He-I20l sam- 
ple. The Hncs are hidcxed in a tctragooal cell with lattice con- 
sttnu a=3.8831(l ) Aand r=9.5357(2) A. 



5.00 

E 

^ 3.00 
u 
c 

B 2.00 



if • 


— t— 

J 


CO 10 too 130 

<^ Tenpefature CK) 



DO 



1.00 



0.00 



120] 



As-prepared 




0 



300 



50 100 150 200 250 

TempCTature (K) 

Fig. 2, Resistivity measurements carried out on a Hg-1201 sam- 
ple. A sharp drop of the resistivity is observed at 94 K in the as- 
syntfaesized sample, it increases up to 97 K in the oxygen-an- 
nealed sanq>!e (300 *Q 18 h).ACmagnctic measurements (real 
and imaginary pans) are shown in the inset. 

resistance at 94 K. Annealing the sample in O2 at 
300*0 for 18 h results in an increase of iu critical 
temperature up to 97 K, The curves presented in Fig. 
2 show the resistivity measurements of the as-pre- 
pared and the oxygen-annealed sample. The oxygen- 
annealed samples were checked by X-ray diffraction 
and found to be remaining intact with no sign of any 
apparent change in the structure. 



5.2. Hz-ni2 

With the introduction of the calcium into the 
structure, the synthesis procedures become more del- 



234 



Chmaissemeial, /PhysicaC 230(1994) 2SI-2S8 



icatc and special care should be taken in the different 
stages of the preparation. 

Some groups have reported the successful synthe- 
sis of Hg.l2I2 and Hg-1223 using the single-step 
method (20-24 J, However, their procedures in- 
cluded the preparation of fresh oxides of BaO and 
CaO and the isolation of the sample from the quartz 
walls by wrapping the materials with a gold or silver 
foil [21-23] or even by using alumina lubes to be 
inserted in the quartz tubes (24). Our experiments 
using this method were not successful probably be- 
cause the samples were introduced in the quartz tubes 
without wrapping. Unlike the prcparaUons based on 
the iwo-siep method, the samples are rudely reacted 
with the quartz even at temperature as tow as 750°C 
and the resulting materials were multicolored pow- 
ders with no sign of any homogeneity and particu- 
larly no supcrconduaiviiy. 

Our Hg-1212 samples were prepared by repealing 
the same procedures employed for the synthesis of 
Hg- 1201. The purity of the samples was estimated by 
both the X-ray diffraction patterns and the AC mag- 
netic-susceplibility measurements. We found that 
samples prepared at temperatures between 825 *C and 
860**C contain not more than 65% of the supercon- 
ducting phase Hg.l212. Table 1 shows the depen- 
dence of the Hg-1212 volume percentage on the 
preparation conditions. The best samples were ob- 
tained by heating at relatively low temperature 790*C 
for 10 h. X-ray diffraction pattern and the supercon- 
ducting properties are shown in Figs. 3 and 4. respec- 
tively. Hg-1212 is also tetragonal with lattice param- 



TaWc 
Selected 



clCR ^=3.8624(1) A and c= 12.7045(2) A. The 
Tionsc of the as-prepared samples is between 1 10 K 
and 120 K. Samples annealed in at 300X for 18 
h have their T^^^ increased up to 1 27 K. 

3.3.Hg-1223 

BajCaaCuaO, precursors were prepared by heating 
the starting materials at 935»C for 7 h. Details are in 
the experimental section. The first preparations based 
on these precursors were partially successful as we 
were able lo obtain a superconducting volume in the 
order of 60%. However, the superconducting phase 
was Hg-1212 rather than Hg-1223 (according lo the 
X-ray diffraction patterns). Table 2 shows two sets 
of experiments with detailed synthesis conditions of 
Hg.I212 from nominal 1223 composition. The up- 
per part of the table concerns the preparations in 
which the weight ratio P/HBCCO=0. The intro- 
duced pellets were only those with the nominal com- 
position HgJBaaCaiCujO, assuming that the pre- 
pared precursors had their initial composition. The 
mercury oxide was added in excess to the stoichio- 
metric formula in order to compensate the loss re- 
sulting from its reaction with the quartz tube. In the 
lower part of the table are presented the experiments 
of the Hg controlled vapor by using the method de- 
scribed in the experimental section with the weight 
ratio P/HBCCO>0. In these preparations the esti- 
mated superconducting volume (Hg-1212) is rang- 
ing between 0 and 60%, These estimations are based 
on the X-ray diffraction patterns which also showed 



Name 


Weight 


Heating rate 




ratio 


CC/min) 


ch26 


0.386 




ch27 


0.412 




ch28 


0.388 


2.5 . 


ch30 


0.257 




ch3I 


0.184 




ch32 


0.314 




ch33 


0.398 




ch34 


0.325 




ch35 


0.4 ]0 




ch36 


0.210 





Cooling rate 
CC/min) 


Temp. 
(*C) 


Time 
(h) 


Hg-1212 
vol. (%) 


2^565«C 


825 


. 6 


65 


2-^565"'C 


845 


8 


65 


I-5I5*C 


860 


5 


25 


2-515'C 


835 


6 


65 


2-»5I5X 


835 


6 


65 


2-515X 


835 


6 


65 




835 


6 


55 


1-^565*C 


835 


6 


50 


2-H»565«C 


790 


10 


85 


2--565'C 


790 


10 


25 



O. Chmaissem et ai. fPhysica C 230 (1994) 



235 



2) A. Tlic 
v^ecn llOK 
)0*Cforl8 



i by heating 
etails are in 
itions based 
:ssful as we 
lumc in the 
cling phase 
rding to the 
ws two sets 
>nditions of 
^n. The up- 
>arations in 
The intro- 
rminal com- 
lat the pre- 
>sition. The 
he stoichio- 
the loss re- 
tubc. In the 
^xperimenu 
method de- 
1 the weight 
>ns the csti- 
12) is rang- 
ns are based 
also showed 



sc experunents 



1212 



6000 -r 
5000- 
4000^ 
3000-- 
2000- 
1000- 
0- 



J 



I Hg-1212 I 



JLju,'. 




15 



45 



55 



25 35 
2-Theta (deg.) 

Fig. 3. X-ray diffraction paticm of an as-prcparcd Hg-I2l2 sam- 
ple. The diffraction lines arc indexed in a tetragonal cell with the 
Utticc parameters fl=:3.8624( 1 ) A and c= 12.7045(2 ) A. 



2.50 



2.00 



a 
a 

o 

1 1.00 



1.50 



0.50 




0 50 100 150 200 250 300 

Temperature (K) 

Fig. 4, Resistivity measurements of a sample Hg-1212. The fig- 
ure shows clearly the increase of the 7coo«t from 1 1 7 K (as-syn- 
thesized sample) to 127 K (oxygcn-anncalcd sample). The inset 
shows the AC magnetic mcasurcmenU (real and imaginaiy paru) 
pciformed on an oxygcn-anncalcd sample. 

that the impurity phases arc CaHg02 and CaO, with 
traces of a weak unknown phase. It is clear from the 
table that the formation of the superconducting phase 
is favored by the presence of the precursor pellets, Tlic 
highest superconducting volume is obtained when 
healing to temperatures close to 850'*C. At 870*Cthe 
sample (chl 1 ) is still superconducting but with a de- 
creased volume down to 40% and the sample is par- 
tially melted, indicating that preparations above this 
temperature could not be carried out successfully. 

This work was carried out simultaneously with at- 
tempts to synthesize the fourth member of the mer- 
cury-based series, namely Hg-1234. The first results 
showed that the superconducting phase obtained with 
precursors assumed to be Ba2Ca3Cu409 (234) was 



Hg-1223. By consequence, we started a new series of 
experiments based on the 234 precursors for the syn- 
thesis of Hg-1223. 

Nominal Hg;^a2Ca3Cu40^ pellets and 
Ba2Ca3Qi409 pellets were sealed together and treated 
as described in Table 3. Very good Hg-1223 samples 
with a volume st:90% were obtained with tempera- 
tures between 870X and 885 "C The samples pre- 
pared at PWC were partially melted and presented 
only 30 to 40% superconduaing volume (samples ch2 
and ch5), a longer reaction time at this temperature 
results in the destruction of the superconducting phase 
(sample chl 9). The reproducibility of the Hg-1223 
phase using these procedures is 100%. Using precur- 
sors obtained from different batches and following the 
same conditions given in Table 3 gave 90% Hg-1223 
at each time. Together with the superconducting pel- 
lets were found drops of mercury inside the closed 
quartz tube. 

X-ray diffraction pattern is given in Fig. 5 which 
shows the good quality of our Hg- 1 223 sample. Based 
on the tetragonal symmetry ( 4, 1 5 ] of space group P4 / 
mmm, the refined lattice parameters were found to 
be a= 3.8564 ( 1 ) A and c= 1 5.8564 (9 ) A. During in- 
dexing the diffraction pattern we found that many 
peaks were doubled and caimot all be indexed in the 
tetragonal symmetry, indicating that the symmetry 
might be orthorhombic. Refinements in an ortho- 
rhombic cdl were equally successful and the doubled 
suong lines were all indexed in a unit cell of lattice 
parameters ^=5.4537(1) A, 6=5.4247(1) A and 
c= 15.8505(7) A. 

The AC magnetic susceptibUity an the resistivity 
measurements for a Hg-1 223 phasic sample are given 
in Fig. 6. The Tcoosct is around 105 K for the as-pre- 
pared samples. A Tconsct of 135 K can be easily ob- 
tained by following the same annealing treatment 
performed on Hg-1201 and Hg-1212 (O2. 300*^C, 18 
h). The resistivity measurement shows a sharp tran- 
sition at 135 K and a zero resistance is achieved 
around 1 34 K. 



4. Discussion 

As we stated above, the preparation of Hg-1201, 
Hg-1212, and Hg-1223 was carried out using the 
sealed quartz tube method. The insertion of 



236 



Tabic 2 



a Chmaissemetal. /PhysicaC 230(1994) 2SJ-2S$ 



Cooling rate Toud. t.». 

CC/min) 



Name 


Weight 


Heating rate 




ratio 


CC/min) 


Hgl* 


0 


4 


Hg2 


0 


30 


Hg3 


0 


preheated furnace 


hgI2 


0 


1.5 


hg]6 


0 


3.5 


hgll 


0.33 


4.5 


hgl3 


0.35 


4.5 


hgU 


0.50 


3.5 


hgl5 


0.40 


2.5 


hgl7 


0.26 


2.5 




0.40 


3.5 



1. 5-^ room temp, 
power shut off 
power shut off 
power shut off 
power shut off 
power shut off 
power shut off 
power shut off 
power shut off 
power shut off 
power shut off 



800 

850 

750 

860 

850 

850 

850 

830 

850 

850 

870 



8 
7 
7 
8 
5 
5 

5 

5 

5 

8 

5 



0 
7 
2 
6 
10 
55 
55 
50 
55 
65 
40 



Table 3 

Selected experiments carried out for the preparation of Ifc-l 223 Tlic nom.*„^i ^ 
«Ba,Ca3Cu,O.C6lumn2givestheweiitLoPm^/l^^ 

and=1.0for«llthe other preparations "^^/"8^iCa,Cu,0^whcrc j:= 1.5 for the preparations maAcd with an asterisk 



Name 


Weight 


Heating rate 




ratio 


CC/min) 


chl4 


0 


1.5 


chlO 


0.40 


3.5 


chl5 


0.40 


3.5 


chl6 


0.40 


3.5 


cht3 


0.40 


3.5 


cfal7 


0.40 


3.5 


chl8 


0.38 


3.5 


cfa]9 


0,49 


1.0 


ch4* 


0.41 


2.5 


hgl» 


0.39 


2.5 


hg3* 


0.35 


2,5 


ch2* 


0.40 


2.5 


ch3* 


0.42 


2.5 


ch5* 


0.40 


1.0 



Cooling rale 
CC/min) 



Temp. 
CC) 



Time 



l.O-^room temp. 

2.5-^600'C 

2.5^600''C 

2.5^600'C 

1.5-H»550'C 

2.5^600 ^'C 

2.5 room temp. 

1.0-»n>om temp, 
power shut off 
power shut off 
power shut off 
2,5^140*C 
power shut off 
power shut off 



Hg-I223 
vol. (%) 



870 

870 

870 

870 

870 

880 

885 

900 

880 

870 

900 

900 

950 

900 



5 
5 
5 
5 
5 
8 
5 

10 
10 

8 

5 
10 

3 

3 



50 
90 
90 
90 
90 
90 
90 
0 
0 

65 

40 

40 
0 

30 



Ba^Ca^^.Cu^O, pellets (P) together vath Hg- 
^ •Ba.a^.jCu.O^. pellets (HBCCO) in the scaled 
quartz tubes suggeste that the total amount of the ma- 
lenal inside the tube is mercury deficient. Surpris- 
ingly, drops of mercury were observed in almost all 
the experiments. The formaUon of Hg.l212 instead 
of Hg-I223 from nominal 1223 composition and the 
formation of Hg.l223 instead of Hg-1234 from nom- 
inal 1 234 composition mean that there are some cal- 
cium and copper left CaHgO^ was observed as the 
major impurity phase and there are negligible traces 



of CuO and its related compounds. One may specu- 
late that the copper and the meixniry cations are 
mixed. The substitution of Cu for 8% Hg was ob- 
served by Wagner ct al. [13] in their Hg-1201 sam- 
pie. As a consequence, they found additional extra 
oxygen atoms on the edges of the mercury layer (J, 
0. z) together with the already existing extra oxygen 
atoms at ( i, i , 0). In the first, second, third and fifth 
member of the mercury-based series the mercury at- 
oms are found to have an unusually high temperature 
factor [ 14 J 5,25-27] . This can be reduced to a more 



h<$ebHg*1212,i[nd 
Oifi, where jr= 1 for 



0 
7 
2 
6 
10 
55 
55 
50 
55 
65 
40 



in these experiments 
uted with an asterisk 



Hg-1223 
voL(%) 

50 
90 
90 
90 
90 
90 
90 

0 

0 
65 
40 
40 

0 
30 



One may specu* 
cury cations are 

8% Hg was ob- 
;irHg-1201 sam- 
additional extra 
acrcury layer (J, 
ing extra oxygen 
d, third and fifth 
s the mercury at- 
bigh temperature 
educed to a more 



O. ChmaissemetaL /Physka €230(1994) 232-238 



237 



5500 



c 

S3 



4125 - 




« 2 « 



2750 

to 



o 
U 



1375 Hi % 

LjLi 



— cj - IT- 





IS 



-T — I — r 

25 

2-Theta (dcg.) 



35 



45 



Fig. 5. X-ray diffraction pattern of an as-prcparcd Hg-1223 sam- 
ple. The diffraction lines arc indexed in both tetragonal cell with 
lattice constanu fl=3,8564( 1 ) A and c= 1 5.8565(9) A and or- 
thorhombic ceU (in parentheses) with lattice constants 
fl= 5.4537 ( 1 ) A, 6= 5.4247( 1 ) A and c= 1 5.8505(7) A. The in- 
set shows the splitting of the line ( 1 1 0) (tetragonal symmetry) 
into two lines, 2 0 0 and 0 2 0 (orthorhombic symmetry). 




0.50 



300 



Tenq)erature (K) 



Fig. 6. Resistivity measurements carried out on both as-syn&c- 
sized and oxygen-annealed Hg-1223 samples. The Tco-ct (orip- 
nally 105 K) is increased up to 1 35 K. The curve shows a sharp 
transition around 135 K with a zero resistance at about 134 K. 
The real and imaginary paru of the AC magnetic-susceptibility 
mcasurtmenu carried out on an oxygen-aimcaled sample are 
shown in the inset 

reasonable value by mixing the mercury cations with 
atoms like copper for example. This possibility was 
investigated but not proved. The successful prepara- 
tion of nearly "100%" pure Hg-1201 samples using 
our method where the mercury cations enclosed in 
the quaru lube present only 0.57 mole to I mole of 
the precursor Ba2Cu03+xConfirms that the mixing of 
Cu and Hg is very possible. The increase of Tc onset 
(97 K) might be due to this mixing. However, this 
conclusion must be interpreted with some caution. A 



molar ratio Hg/Cu of 0.57 seems to be rather small 
compared to 0.85 found by Wagner et al.. Even though 
our sample looks pure using the X-ray diffraction 
tedinique, it might not really be the case. An unde- 
tectable (by X-rays) amorphous Ba-Cu-O sub- 
stance could exist in the powder as well. Such obser- 
vation was reported by Dolhcrt et al. [28] who 
studied the low dctcaability of excess yttrium and 
barium in YBajCu^OT by X-ray diffraction. Thus the 
X-ray "pure" sample may not be actually very pure. 
However, the formation of (Hg, 
Cu)Ba2Ca„_,Cu„02„+2+tf is possible and seems to be 
dependent on the preparation conditions. More de- 
tails need to be studied. As the X-rays arc not too sen- 
sitive to the oxygen anions, neutron experiments arc 
needed to deterinine the value of the extra oxygen at- 
oms and their location and to confinn the occupancy 
of the mercury sites and also to investigate the possi- 
bility of any change in the structure. 

Our Hg-1223 phase is very likely to be orthorhom- 
bic. The orthoitombicily of our samples is observed 
by the splitting of some of the X-ray diffraction lines. 
The possibility of the coexistence of two phases with 
very high rate of overlapped lines would suggest that 
these two phases arc both members of the mercury- 
based series and by consequence we must be able to 
observe at least two well-defined superconducting 
transitions in our measurements. As this was not the 
case and as the lines (00/) are singles and not split 
we may conclude that our Hg-1223 phase is ortho- 
rhombic. The refined cell parameters are in good 
agreement with those reported by Meng et al. [16] 
and Huang etal [29] for their orthorhombic samples. 



Acknowledgements 

We thank John Shullz for his assistance in powder 
X-ray diffraction. This work was supported by the 
Advanced Research Projects Agency and the Arkan- 
sas Energy Office, USA. 



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> ^hy any 



T^t Oflhc 



«1 is given 
dilion that 
nnitted by 
tide lo the 
$ aoi given 
81 may be 
per page.) 



t$ liability, 
J herein. 



ctherlands 



PbysicaC2l5(l993) l-IO 
Nonh-Holland 



PHYSICA S 



The synthesis and characterization of the HgBa2Ca2Cu308+ ^ and 
HgBa2Ca3Cu40,o+ J phases 

E.V, Antipov S.M. Lourciro ^ C ChaiUout ^ J J. Capponi ^ P. Bordct ^ J.L, Tholence \ 
S.N. Putilin • and M. Marczio " 

• Department of Chemistry, Moscow State University, 119899 Moscow, Russian Federation 
Uboratoirede CristallographieCNRS-VJF, BP 166, 38042 Grenoble Cedex 09, France 

^ CRTBT, CNRS-VJF, BF 166, 38042 GrenoNe Cedex 09. France 

* ATdTBeli Laboratories, Murray HilL NJ 07974, USA 

Received 2S June 1 993 

Revised manuscript received 9 July 1 993 



The third (Hg-I223) and the fourth (Hg-1234) members of the rcccnUy-discovcred homologous scries Hg- 
BajCa^-iCu^Oj^+a+rf have been synthesized by solid state reaction, carried out at 950 *C under 50 kbar at different annealing 
times. These phases have a tetragonal ccU with lattice parameters: a=3.8532(6} A, c= 15.818(2) A and fl=3.8540(3) A, 
c= 1 9.006 ( 3 ) A, respectively. The c parameters are in agreement with the formula cs 9.5 + 3.2(rt- 1 ). Electron microscopy study 
showed similar lattice parameters as well as the occurrence of diifcrent tntergrowths and sucking faults. A periodicity of 22 A has 
also been detected, which may be attributed to the existence of the Hg-1245 phase. EDS analysis data of several grains of Hg-1223 
and Hg-1234 are in agreement with the proposed chemical formulae. AC susceptibility measurements show that an increase of 
the superconducting transition temperature with n in the HgBajCa,. iCu.02,+2+, series occurs tiU the third member, after which 
a saturation seems to be achieved. 



1. Introduction 

Superconductivity at about 94 K and well above 
120 K has been recently reported for HgBa2Cu04+^ 
(Hg-1201) (II and HgBa2CaCu206+, (Hg-1212) 
(2), respectively. These phases are the first and the 
second members of the Hg-based homologous series 
of layered Cu mixed oxides. Their structures contain 
rock-salt-Iikc slabs, such as (BaO) (HgO^) (BaO) al- 
icmaiing with either one (CuOi) layer in the former 
or an anion^eficient perovskilc-like slab, such as 
(CuOjXCaDXCuOj), in the latter. A supercon- 
ducting transition temperature as high as 133 K has 
been reported for a multiphasic sample in the Hg- 
Ba-Ga-Cu-O system by Schilling ct al. [4]. These 
authors could not identify by X-ray diffraction the 
phases responsible for the superconductivity at this 
lemperature, but proved by high resolution electron 
microscopy that the sample contained the Hg-1212 
and Hg-1223 phases as well as different inter- 
growihs. Putilin et al, [2] showed that in the sample 



conuining Hg-1212 as the majority phase, a small 
drop on the AC susceptibility curve versus T oc- 
curred at about 1 32 K which could be attributed to 
the third member of the Hg-bcaring series. 

Putilin et al. also showed [2] that it was possible 
to synthesize the Hg-1212 phase, practically in pure 
form, under high pressure (40-60 kbar) and at 
800*C for about I h. The high pressure synthesis al- 
lows one to lower the mercury oxide decomposition. 
This decomposition occurs at ambient pressure at a 
temperature at which the reactivity of the other com- 
ponents is very low. It was suggested that the same 
technique could be used for obtaining the higher 
members of the series. We found that the reactions 
have to be carried out at higher temperatures 
(950**C) and for longer annealing times. The same 
occurs for the higher members of the Bi- or Tl-based 
Cu oxide series, which are formed by the formation, 
at the initial stages of the reaction, of the lower mem- 
bers of the corresponding families. We report herein 
the synthesis and characterization of the Hg- 



092M534/93/$06.00© 1993 Elsevier Science Publishers B.V. All rights reserved. 



a ^ei. ,,^?"'- carried out ,•„' 



Powder samples containing the H.r 

Obtained by high-pressure and high-temperature re- 
actions usmg the beJt-type apparatus of the Ub^' 
atcre de Cnstallographie. A precur^^ with Ae 
nominal composition Ba,Ca,Cu30, was preZdt 

>99%), Ca(N03), 4H,0 (Nomiapur Prolabo an- 
alytical reagent) and Cu(NO.), 3HO 

Chemical Inc 99 5% ^ tk ^ 

11^1 inc., The mixture thus obtain<>H 

was mitially heated at 600-C in air for 2 h thef 
ygen flow with three mtennediate regrindings. Then 

J . ^"'^ ^'^^ was thorouEhlv 

grounded ui an agate mortar and sealed in aTSp"^ 
sule specific for high pressure synthesis >Lw 
emperatures and annealing times « a pTisu^ of 50 
were tned m order to obuiu the Hg-1223 and 
Hg-1234 phases. In these experiments the pressure 
was fir^t increased to 50 kbar. subsequently th^em- 
^™.ure was raised to the desin^d^lue during Jh 
then the temperature and the pressure were kem 
o^nstant for I -4 h. After this, the fumac^ ^Zr X 

Snslto!^™^------^^^^ 

fn.U'l'^^i" x-ray powder dif- 

f^ction performed with a Guinier focusing came,; 
and Fe Ka radiation (1.93730 A). Finely ^wdTred 
silicon (a=5.43088 A at 25-C) was u Jd as an i„ 

and SCANPI programs were used for processing the 

The phase HgBa,Ca,Cu,0,^, was present in the 
sample synthesized at 950-C for 3 h (sample i) tl 
gather vWth a smaller amount of Hg-1212 ao and 

phase whose intensities were less than 4%. The X-ray 



diffraction pattern of samole I aH^r k,^i, 
straction is shown in firi j^e 20^^^°""'^'"'" 
responding to Hg-1223 were i«d«^ 

^i^o^i^i^JiL^^^^ «"-'ont 
served, I-ding^^prcr^?;^^^^ 
formula per unit cell. Tl.e'^.ea' u^^^^^e of 

=^X^fhe=^^^^^ 
with/i=3(ij. «^-3';>f J.^(/j-i) 

A scanning electron microscope JEOL 84nA 

(ED^r^ttaTi' " So'l^ 
(EDS) attachment was used for the analysis of Z 
ration composition of the two prepared sampled Ka 
lines were used for the analysis of the Ca^d S 
.ons. and Dx-li„es for the Ba and Hg ones ED^an^ " 

mat besides Hg. Ba. Ca, Cu and O no other elemem 
rnr"'r^--::,^--gemet:'S 

Hg:Ba:a:Cu=,3(2):24(,).26(n.38rn 
«andard deviations ^twe^n^ti'tie^^'Aer 
^n stoichiometry is in good agreement with theTx- 
pected formula of the Hg-1223 phase 

teninil'"* of Hg-1212 refined from 

ten reflections (a=3.859{4) A. c= 12.68(2) A) ar^ 

should be noted that there is severe overiappi^i be 

mine a?,t o-erlapPings did not allow us to dete' ^ 

!S ^ ^i^"** '^^^ ''"^ (103and 104) . 

shows clearly that the Hg-1223 is the predomin7n ' 
Phase in sample I (fig. l ). cuominani 

let^eJ ThT ""T'' ' ^'"'"^ ""^-"be^ »^ * 
vSto H ' CaO. Ob- . 

nTcomnf of Hg-1223 was * 

for 2 h led to the for- ' 

mation of Hg-1212 which was found to be the main . 

Pha^ m Uie sample together with the starting con,- * 

pounds. TTiese data show that the formation of , 

S *y»<hesis of the lower * 

members of the series. The increase of the annealing 



and sub- 
ons cor- 
tragonal 
(6) A, 
ection is 
wcrcob- 
aind one 
of ihc c 
expected 

L 840A 
troscopy 
is of the 
oIcs.Ka- 
I Cu cat- 
DSanal- 
> showed 
clement 
;Ul ratio 
was 
), with 
rhe cat- 
1 the cx- 

cd from 
) A)are 
- I2J. It 
ping he- 
ld those 
Hections 
sof Hg- 
X) deter- 
bwcvcr, 
fines for 
nd 104) 
>minant 

nbcr to- 
aO, ob- 
223 was 
lie syn- 
Ihe for- 
ie main 
ig com- 
tion of 
e lower 
mealing 



5000 



4000 



3000 



2000 



1000 



£ K Antipav e(a!./ HgBa/:afiu/>»^s and HgBa^fljCMX>/o+# 
SAMPLE! 

3 

o* 

290 
210 
190 
170 
150 




il 



-M 



«J 6.7 6.9 7.1 7J 7J 



30 



40 



50 



60 



70 



80 



2Tbcta 



Fig. I . X-ray powder pattern for sample 1. Indexed XRD intensities correspond to Hg- 1 223 and Hg- 1 2 1 2 ( undcriinc ) . Impurities of CaO, 
CuO. CaHgOa and an unknown phase are marked by ( ). The inset displays the characteristic intensity of 001 for Hg-1 223. 



time up to 3.5 and 4 h at 950 and the same pres- 
sure led to the expected disappearence of Hg- 1 2 1 2 as 
well as of CaO. In these samples the formation of a 
new phase was detected Its amount was relatively 
high (more than 50%) in samples annealed for 3.5 
h (sample II), A total of 17 reflections of this phase 
were indexed on a tetragonal cell with lattice param- 
eters a=3.8540(3) A, c= 19.006(3) A. As for Hg- 
1223 no systematic absences were observed, leading 
to space group P4/mmm. Similar parameters were 
found by electron diffraction (see below). The c pa- 
rameters of jthis phase corresponded to the value cal- 
culated from the formula c^9.5 + 3.2(/j- 1 ) for 
/i=4. This strongly suggested that the new phase was 
the fourth member of the Hg-based series: Hg- 
Ba2Ca3Cu4O|0+^ The approximate cations ratio de- 
termined by EDS analysis of five well-crystallized and 
flat grains was Hg:Ba:Ca:Cu = 
9(1):18(1):29(2):44(2). These data are in good 
agreement with the proposed formula for the new 
compound. 



Besides Hg-1 234 as the main phase, a smaller 
amount of Hg-1 223 was present in sample II to- 
gether with small amounts of CuO and of an un- 
known phase. This unknown phase was predomi- 
nant in a sample treated for 5 h in the same 
conditions which did not contain any member of the 
Hg-based series and did not exhibit any supercon- 
ductivity. The presence of the latter oxides can be 
explained as a result of the decomposition of Hg-1223 
and the formation of Hg-1 234. Hg-1212 was absent 
in this sample as well as in that annealed for 4 h. The 
X-ray diffraction pattern of sample li after back- 
ground subtraction is shown in fig. 2. The ratio of 
the main intensities for both Hg-based layered cu- 
prates, 104 for Hg-1 223 and 105 for Hg-1 234, shows 
that the latter was the main phase in this sample. As 
for sample I the overlapping of hkd reflections for 
both phases occurs because of the similarity of the 
two a parameters. Moreover, the hk6 reflections of 
Hg-1 234 are overlapped with the hkS ones of Hg- 
1223. 




SAMPLE 2 



5000 



4000 



3000 



2000 



iOOO 



MM 



30 



I 



■• -I 




50 



60 



70 



80 



2Theta 



Fig. 2. X-ray powder pattern for sample U, Indexed XRD intensities correspond to Hg-1234 (bold) and Hg-1223. Impurities of CuO 
and an unknown phase are marked by ( • ). 



3. Electron microscopy 

The I and II samples were studied by electron mi- 
croscopy. A suspension of crystals in acetone was 
grounded in an agate mortar. The crystallites were 
recovered from the suspension on a porous carbon 
film. A Philips EM 4(X)T operating at 120 kV was 
used. 

Figure 3 (a) and (b) shows two diffraction pat- 
terns obtained for sample I corresponding to the 
[001] and the <riO> zone axes of the Hg- 
Ba2Ca2Cu308+^ (Hg-1223) phase, respectively. In 
both cases, the diffraction spots are sharp, which in- 
dicates that the crystal is well ordered. In fig. 3(b). 
one can notice a modulation of the intensity of the 
diffraction spots along the c*-axis, with maxima for 
/rW reflections with /=5/i (w=6, 1.2, ...).On the mi- 
crograph (fig. 3(c)) corresponding to the diflTrac- 
lion pattern shown in fig. 3(b), one can see the very 



regular periodicity of the fringes separated by 15.8 
A. During the observation under the electron beam, 
dark spots appeared near the edge of the crystal, 
probably due to the decomposition of the crystal 

Some diffraction patterns obtained for other crys- 
tals present difluse lines parallel to the c*-axis and 
passing through the Bragg spoU (fig. 4 (a)). They 
are due to the presence of intergrowths as given evi- 
dence for by fig. 4(b). On this micrograph, two dif- 
ferent spacings of 1 5.8 A and 12.7 A can be mea- 
sured, attributed to Hg-1223 and Hg-1212. 
respectively. 

In the case of sample II, almost all the observed 
crystallites have diffraction patterns corresponding 
to the Hg-1234 phase (HgBa2Ca3Cu40io+^) with cdl 
parameters a=6=3-85 A and c= 19 A. Figure 5(a) 
and (b) give examples of the [001 ] and < 100 > zone 
axes, respectively. As for Hg-1223, also for Hg-1234 
the intensity of the Bragg spots varies according to 



5 






Rg. 3. Electron diffraction patterns of Hg-1 223 ukcn along (001 ] 
(a) and < 1 10) (b) zone axes, (c) Micrograph corresponding to 
the diffraction pattern (b). The interfringc spacing is 15.8 A. 



ihe vaKie of-the / index, the maxima of intensity being 
obtained for /=6n (rt = 0, 1, 2, ...). This intensity 
pattern might be explained by the fact that c/6 is 
equal to 3.17 A, which corresponds to the distance 
between two neighboring (CUO2) layers. The in- 
crease of the layer number n in the structure leads to 
ihe increase of the intensity of the hkl reflections with 



Fig. 4. Electron diffraction pattern of sample I along < 100> and 
corresponding micrograph showing the intergrowths of Hg-1 223 
andHg-1212. 

/=n+2. These periodicities of the (CuO^) layers ex- 
plain the overlapping of such reflections on the X- 
ray powder pattern (see above). Most of the images 
taken along the < 100) zone axis show very regular 
fringes separated by 1 9 A (fig. 5(c) ). However, some 
crystals present intergrowths between the Hg-1 223 
and Hg-I234, as revealed in fig. 6. In this case, the 
following sequence is observed over about 500 A: 
-19 A-19 A-19 A-19 A-19 A-22 A-. On the corrc- 
sjx>nding diffraction pattern, besides the diffraction 
spou of the Hg-1 234 phase, additional spots related 
to the 22 A periodicity are present. Such a period- 
icity may be attributed to a 1245 phase (Hg- 
Ba2C:a4Cu50,2+a). The fact that the extra diffraction 
spou are sharp indicates that this phase is well or- 
dered at least over a certain number of cells in these 
crystals. 



4. AC susceptibiiit)' measurements 
The critical temperature Tc» ar^d the apparent su- 



6 





perconduding volume of samples I and II have 
de^ed from AC suscepUbiUty measulem«S; 
fine powder samples. This avoids overestimal« 
the superconducting volume due to the larger scrl^^ 
•ngs m sintered samples. Tie AC suscepS,il,>^ 
measure, mth an alternating maximum field of 0^ 
Oe and a frequency of 119 Hz. The temperature was 

tSete^^ ^ "''^-^^ " 

The as-synthesized sample I undergoes a tiansi- 
tion from the paramagnetic to the diamagnetic state 
with an onset above 133 K (fig. 7). Several mea- 
surcmenu were made with the same sample and die 
reprdducibility of is + /- 1 K (mainly due to the 
thermal contact between the sample and the ther- 
mometer). The estimated magnetic susceptibility at 
4 K corresponds to a large volume of ideal dia- 
magnetism indicating the bulk nature of supercon- 
ductivity. We can suggest that the sharp and large 
drop on the AC suscepUbility curve above 133 K 
should correspond to the Hg-1223 phase because Hg- 
1212, which IS present in this sample as the minority 
phase, has a not higher than 126 K f 3J. 

The as-synthesized sample U undergoes a transi- 
Uon from the paramagncUc to the diamagnetic state 
with an onset as high as 1 32 K. Actually, two onseu 
at two different temperatures are visible, the smaDer 
one at 1 32 K and the larger one at about 1 26 K. There 
are two Hg-based layered cupratcs in this sample: Hg- 
1234 as the main phase and Hg-1223 as the minority 
one. Taking into consideraUon the results of sample 
I. we might suggest that the first onset ( 1 32 K) cor- 
responds to Hg-1223 and the larger one at the tower 
temperature (126 K) to Hg-1234. In any case, it is 
obvious that 7; for Hg-1234 is not higher than that 
for Hg-1223. 



Fig. 5. Electron diffraction patterns of Hg- 12 J4 taken along [001 1 
(a).nd <IO0> (b) zone axes. (c)Miu»graph corresponding to 
the diffraction pattern of (b). The inteifringe spacing is 19 A 



5. Discussion 

The synthesized HgBa^CajCujOg.^, (Hg-1223) 
and HgBaiCajCu40,o+, (Hg-1234) phases are the 
third and the fourth members of the Hg- 
Ba2Ca„_,Cu,02„+,+, series, in analogy with those 
of Hg-1201 [1.7.8] and Hg-12l2 [2] their struc- 
tures can be schematized as containing rock-salt-like 
slabs. (BaO)(HgO,)(BaO). alternating with per- 
ovskite-Iike slabs, consisting in three (Hg-1223) or 



o 



I 

-1 

-3 
-5 
-7 
-9 
-II 
-13 
-15 



SAMPLE 1^ as syotbesizcd 




25 



50 



75 



100 



150 

TfK) 



Fig. 7. AC susceptibility vs. r for a^^th*. ^ ^ ^'^^ 

phase. y vs. / for as^thcsucd sample 1, where HtA22^ is nres^n. « .k * 

H presem as the ma.n phase and Hg-,212 as the nunoriiy 



SAMPLE 2 -as synthesized 



^ -3 
E 



^ -7 



-13 



-15 



25 



50 



75 



100 



125 - 150 
8 i^J-* as the mam phase and of Hg-1223 as ihe 

1212 The appropriate treatment for He-1234 ran 

possibly change 7; for this phase. Therefore we **^""/°' TlBa,Ca„_ ,Cu„0,„.3., homologous 




£1 K Antipov ei al. / HzBa^a^ufi^^^ and HgBa/:fl/:«/>,, 



ninoniy 



} as the 



ogous 
;mber 

;s, the 





Fig. 9. The CTyslal stniclures of Hg-I223 (a) and Hg-1234 (b). The Uigesi and medium lai^c circles refer lo Ba and Ca atoms respec- 
nvcl) . The Cu atoms art the smaUest circles. Those at the base of the shaded pyramids arc not shown. The circles forming the squares 
around ihc Cu arc oxygen atoms. The dumbbells around the Hg atoms are formed by apical oxygen atoms. Partially filled circles refer to 
mc partially occupied oxygen sites on the Hg layer. 



parameter and just al it remains practically con- 
stant between Hg-1223 and Hg-1234. 
The electron microscopy study of Hg- 1201 [10] 



revealed the absence of intergrowths and this was at- 
tributed to the absence of the Ca^'*^ cations in the 
system. On the contrary, the addition of Ca layers in 



IT 



10 



Tablet 



U«tep.,,„.e.en.ndtni,rition,empcni,„,^fo,H e.ba5cdQ.oxid« 
Formula 



HgBa,Qi04« 
HgBaXii,Cu,0,», 



Short form 

He-1201 
Hs-1212 

Hg-I223 
Hg-I234 



(A) 

3.8797(5) 
3.8SS6(8) 

3.8S32(6) 
3.8540(3) 



the ^icm leads to inteipowths due to different 

f Such intergro>vth$ were already reported 

L i'J- °f 1i"'-'-ent in- 

tergrowths may explain why the variation venus 
temperature of the AC susceptibUity does not pres- 
ent distmct and abrupt transitions which could be 
attributed to pure Hg-12l2. 1223 and 1234 phases 
The synthesis of the higher membere of the Hg- 
bascd homologous series as bulk samples has been 
performed at higher temperature than that used for 
Hg-1212 and with longer treatment times. We sug- 
gest that the synthesis of such phases occurs through 
the formation at an iniUal sute and subsequent de- 
composition of the lower members of the series. This 
feature « similar to that existing for the Tl- 

'^^-^J-ta-* homologous series [91 The 
use of high pressure, possibly, lowers the mercury 
oxide decomposiUon. It also leads to a decrease of 
mbUity of CaHgO,. whose synthesis at the first stage 
of the reaction inhibiu the foimaUon of Hg-based 
compounds. 



Acknowledgements 

Tbe-authors would like to thank M.F. Gorius. M. 



c(A) 


T,^ (K) 


9.509(2) 


94 


12.652(4) 


121 




126 


15.818(2) 


133 


19.006(3) 


<I32 



Ref. 

12] 
P] 

f4), this work 
this work 



^"So7eva'1''°:l'''^^ 

the French Ministry of Foreign Affaiis. EVA and SNP 
would hke to thank the suppon of the Russian sl^ 
""pS")''sm? °" ^"•--"<^"ctivi,y (p„^ 
derEx^changt^^rnT"'*^^'^^^-- 

References 

" N«u^?'^fV«r''°°''^""<'M.Ma«zio. 
Nature (London) 362 (1993) 226 

(i?937S6°: ".2 

m^i*L!:!ir'!f ^^-^^ ^""^ communication. 

(London) 363 (1993) 56. 
15] K.E Johansson. T. Palm and P.-E. Weraer. J Phys. E: Sci 
Inaroa. 13 (1980) 1289 ^- f nys. t- Sa. 

OnRwri^) (IWl) 1645 

' ^-^^ M. Ma«xio and A. 

Santoro, Piiystca C212 (1993) 259 

^993^tr"'°-^'^"''^^-^''^'' 
19] J NaMiima. M. Kikuchi. Y. Syono. T. Oku. D. Shindo. K. 

1 10] I. Biynise and S.N. Putilin, Physica C 2 1 2 ( 1 993) 223. 



i 

I 
I 
I 



5 



BRIEF ATTACHMENT Bl 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479,810 
Filed: June 7, 1995 



Group Art Unit: 1751 
Examiner: M. Kopec 



Date: March 1, 2004 
Docket: YO987-074BZ 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 



FIFTH SUPPLEMENTAL AMENDMENT 



Sir: 



In response to the Office Action dated February 4, 2000: 



ATTACHMENT 56 



PhyjicaC2l5 (1^93)1-10 
Nonh-Holland 



PHYSICA S 



<w by any 
r, Elsevier 



i«ht of the 



is given 
litioti thai 
-mitied by 
ide lo the 
noCfivcn 
Jl maybe 
^crpage.) 

TXKCS, Of 



The synthesis and characterization of the HgBa2Ca2Cu308+^ and 
HgBa2Ca3Cu40,o+^ phases 

EV. Antipov • ^ S.M. Lourciro ^ C. Chaillout ^ J J. Capponi ^ P. Bordct \ J.L, Tholcncc ^ 
S.N. Putilin * and M. Marezio ** ** 

• Department of Chemistry, Moscow State University. 1 19899 Moscow, Russian Federation 

* Laboratoire de Cristallographie CNRS-UJF. BP 166, S8042 Grenobie Cedex 09, France 
' CRTBT, CNRS-VJF, BP 166, S8042 Grenoble Cedex 09, France 

' ATdcT Bell Laboratories, Murray Hilt, 07974. USA 

Received 28 June 1993 

Revised manuscript received 9 July 1993 



The third (Hg-1223) and the fourth (Hg-1234) members of the recently-discovered homologous series Hg- 
BajCa,_iCu.02«+3^4 have been synthesi2ed by solid state reaaion, carried out at 950*C under SO kbar at different annealing 
times. These phases have a tetragonal cell with lattice parameters: a=3.8532(6) A, r=lS.8l8(2) A and a-3.8540(3) A, 
c= 1 9.006 ( 3 ) A, respectively. The c parameters are in agreement with the formula f s 9.5 + 3.2 ( w - 1 ). Electron microscopy study 
showed similar lattice parameters as well as the occurrence of diifcrcnt inleigrowths and sucking faults. A periodicity of 22 A has 
also been detected, which may be attributed to the existence of the Hg-1 245 phase. EDS analysis dau of several grains of Hg- 1 223 
and Hg-1234 are in agreement with the proposed chemical formulae. AC susceptibility measurements show that an increase of 
the superconducting transition temperature with n in the HgBa2Ca,-|Cu,02«+2+< series occurs till the third member, after which 
a saturation seems to be achieved. 



I. Introduction 

Superconducliviiy at about 94 K and well above 
120 K has been recently reported for HgBa2Cu04.>rf 
(Hg.I20I) [I J and HgBa2CaCuj06+^ (Hg-12I2) 
1 2 J, respeclively. These phases are the first and the 
second members of the Hg-bascd homologous scries 
of layered Cu mixed oxides. Their structures contain 
rock-salt-like slabs, such as (BaO)(HgOrf)(BaO) al- 
ternating with either one (CuO^) layer in the former 
or an anion-deficient perovskitc-like slab, such as 
(Cu02)(CaD)(Cu02), in the latter. A supercon- 
ducting transition temperature as high as 133 K has 
been reported for a multiphasic sample in the Hg- 
Ba-Ca-Cu-d system by Schilling et al. {4 J. These 
authors could not identify by X-ray diffraction the 
phases responsible for the superconductivity at this 
temperature, but proved by high resolution electron 
microscopy that the sample contained the Hg-1212 
and Hg-1223 phases as well as different inter- 
growths. Putilin et al. [2 J showed that in the sample 



containing Hg-1212 as the majority phase, a small 
drop on the AC susceptibility curve versus T oc- 
curred at about 132 K which could be attributed to 
the third member of the Hg-bcaring scries. 

Putilin et al. also showed [2] that it was possible 
to synthesize the Hg-1212 phase, practically in pure 
form, under high pressure (40-60 kbar) and at 
800*C for about 1 h. The high pressure synthesis al- 
lows one lo lower the mercury oxide decomposition. 
This decomposition occurs at ambient pressure at a 
temperature at which the reactivity of the other com- 
ponents is very low. It was suggested that the same 
technique could be used for obtaining the higher 
members of the series. We found that the reactions 
have to be carried out at higher temperatures 
(950*C) and for longer annealing times. The same 
occurs for the higher members of the Bi- or Tl-bascd 
Cu oxide series, which are formed by the formation, 
at the initial stages of the reaction, of the lower mem- 
bers of the corresponding families. We report herein 
the synthesis and characterization of the Hg- 



092 1-4534/93/$06.00 © 1 993 Elsevier Science Publishers B.V. All rights reserved. 



(HgJ234) phases. The reactions we,e carried oJun 
a> S50 C for 3 and 3.5 h. respeclivcly. 



2. Synthesis and characlerlration by X-ray and 
tub analysis 

Powder samples containing the H^. 

obtained by high-pressure and high-tempeniture re- 
acnons using , he bel.-type apparatus ofVhe Ub^' 
nZn^" Cnstallographie. A precui^r with the 
nominal composifon Ba.Ca^Cu^O, was prepared by 

>99%\ cttn7 ^^<^^^>' (Aldrich! 

> 99%). Ca(NO,), 4H,0 (Normapur Prolabo. an- 
alytical reagent) and CuCNO,), 3H,0 (S rem 
Chemical nc. 99.5%). The mixture thus obtained 
H^s .mtially heated at 60b»C in air for 12 h tJen 
regnnded and annealed at 925-C for 72 h in an ox- 
ygen flow with three intermediate rcgrindings. TTien 
>59%riL?/r7'"r.' ^^^^^''^-HeO (Aldrich! 
or^ Jr '""^ ""^ thoroughly 

grounded .n an agate mortar and sealed in a Pt S^^^ 
sule specific for high pressure synthesis. Variou^ 
temperatures and annealing times at a pressure of 50 
kbar were tried in order to obtain the Hg-1223 and 
Hg-1234 phases. In these experiments the pressure 
was first mcreased to 50 kbar. subsequently the tern! 
perature was raised to the desired value during I h 
then the temperature and the pressure were kept' 

srt^Ta^dl;;''^^""*^'^'''''^'"™^"'---" 

fr J?l "^"^ ' ^-"y ponder dif. 

andFeKarad.at.on (I.93730A). Finely powdered 
s Iicon («=5.43088 A a. 25-C) was u Jd « an n 

Ztl^T"- ^^^'"^ ^^rc 
data f^t processing the 

The phase HgBa,Ca,Cu,0,,, was present in the 
sample synthesized at 950-C for 3 h (sample I) to- 
gether with a smaller amount of Hg-1212. CaO and 
CuO and traces of CaHgO, f6] and of an unknown 
Phase whose intensities were less than 4%. The X-ray 



shown .„ theinsen. No systematic absen^^'^ 

formula per unit cell. The measured value of the^ 
parameter of Hg-1 223 corresponded to t^^ exniSted 
value calculated by the formula r^9 5+3 2frn 
with/is3(|). j-rj.ztn-i; 

A scanning electron microscope JEOL 840A 

EDSratta^h' " ^P^ctro^Py 
(tDS) attachment was used for the analysis of thJ 

l^t-on composition of the twoprepa«d saS« 

l.nes were used for the analysis of the Ca and Cu 

.ons. and U-li„es for the Ba and Hgones EDSan^ 

y^.s of several well crystallized and L grains sho^* 

was p^:em in^h'^' '"^ ^ "° 

Znr-^-r-'-tr'^Tr"''-'" 

Hg:Ba:Ca:Cu=,3(2):24(l):26(n(l) Z 
standard deviations between parentLe.^ "^ke 
^n «o.ch.ometry is in good agreement with the cx- 
Peaed formula of the Hg-1223 phase 

The lattice parameters of Hg-1212 refined from 
cn reflections («=3.859(4) A. c= 12.68(2) A) Z 

t!^ IT ""^^^ overiapp „g bc- 

Si/.^f/K "'T^ '''''' "^-'212 and t'hose 

n^J -i^ reflections of Hg- 

I-J23. These overlappings did not allow us lo dcter- 
mme all the intensities of the two phases. However. 

n OMA, ^'■•hc strongest lines for 

^£11 , ^ ? '03) and Hg-1223 (103and IM) 
shov« clearly that the Hg-1223 is the predominant 
phase m sample 1 (fig. i ). 
The presence in sample I of the lower member to- 

viously mdicates that the formation of Hg-1223 was 
not co„,p,e,e aAer a 3 h annealing period. The syn- 
U^esis earned out at 900-C for 2 h led to the for- 
mation of Hg-1212 which was found to be the main 
Phase m the sample together with the starting com- 
pounds These data: show that the formation of 
Hg-1223 occurs through the synthesis of the lower 
members of the series. The increase of the annealing 



1 

I 

I 

i 

i 



P 



nd sub* 
uiS4:jDr- 
ragonal 
6) A. 
ction is 
/crcob- 
nd one 
)f the c 
tpcclcd 

. 840A 
roscopy 
i of the 
Ics. Ka- 
Cucal- 
>S anal- 
showed 
dement 
al ratio 
was 
, with 
"he cat- 
the ex- 

d from 
A) are 
{2J. It 
ling be- 
d those 
ections 
ofHg. 
) deter- 
)wcver, 
ncs for 
id 104) 
minant 

ibcr to- 
lO. ob- 
23 was 
he syn- 
hc for- 
c main 
g corn- 
lion of 
! lower 
Dealing 



E. v. Andpov ei al. / /ftBd7Ca/CiijO,+ j and HeBa^j jCM/>«+i 

r 

SAMPUl 



5000 



4000 



3000 



2000 



1000 




3 



30 



40 



50 



130 - 

210 - 
190 ~ 
170 - 
IJO - 
I JO - 
110 - 



I M I I 



6. J 4.1 4f ri 7J 7J 



60 



70 



80 



2'nieu 



Fig. I . X-ray powder pattern for sample K Indexed XRD intensities correspond lo Hg- 1 223 and Hg- 1 2 1 2 (underline ). Impurities of CaO. 
CuO. CaHgOj and an unknown phase arc marked by ( * ). The inset displays the characteristic intensity of 001 for Hg-1 223. 



time up to 3.5 and 4 h at 950'*C and the same pres- 
sure led to the expected disappearence of Hg-1212 as 
well as of CaO. In these samples the formation of a 
new phase was detected. Its amount was relatively 
high (more than 50%) in samples annealed for 3.5 
h (sample II ). A total of 17 reflections of this phase 
were indexed on a tetragonal cell with lattice param- 
eters a=3.8540(3) A, 0=19.006(3) A. As for Hg- 
1223 no systematic absences were observed, leading 
to space group P4/mmm. Similar parameters were 
found by electron diffraction (see below). The c pa- 
rameters of this phase corresponded to the value cal- 
culated from the formula r^9.5 + 3.2(n- 1 ) for 
/I =4. This strongly suggested that the new phase was 
the fourth member of the Hg-based series: Hg- 
BajCajCu^Ojo+rf. The approximate cations ratio de- 
termined by EDS analysis of five well-crystallized and 
flat grains was Hg:Ba:Ca:Cu = 
9(1): 18(1 ):29(2):44(2). These data are in good 
agreement with the proposed formula for the new 
compound. 



Besides Hg-1234 as the main phase, a smaller 
amount of Hg-1 223 was present in sample II to- 
gether with small amounts of CuO and of an un- 
known phase. This unknown phase was predomi- 
nant in a sample treated for 5 h in the same 
conditions which did not contain any member of the 
Hg-based series and did not exhibit any supercon- 
ductivity. The presence of the latter oxides can be 
explained as a result of the decomposition of Hg-1 223 
and the formation of Hg-1234. Hg-1 212 was absent 
in this sample as well as in that annealed for 4 h. The 
X-ray diffraction pattern of sample li after back- 
ground subtraction is shown in fig. 2. The ratio of 
the main intensities for both Hg-based layered cu- 
prates, 1 04 for Hg- 1 223 and 1 05 for Hg- 1 234, shows 
that the latter was the main phase in this sample. As 
for sample 1 the overlapping of hkQ rcflectioiis for 
both phases occurs because of the similarity of the 
two a parameters. Moreover, the hkd reflections of 
Hg-1234 are overlapped with the hk5 ones of Hg- 
1223. 



i 




30 40 50 60 70 80 2Thcu 

Fig, 2. X ray powder pattern for sample II. Indexed XRD intensities correspond to Hg-I234 (bold) and Hg-1223. Impurities of CuO 
and an unknown phase arc marked by ( * ). 



3. Electron microscopy 

The I and II samples were studied by electron mi- 
croscopy. A suspension of crystals in acetone was 
grounded in an agate mortan The crystallites were 
recovered from the suspension on a porous carbon 
film. A Philips EM 4(K)T operating at 120 kV was 
used. 

Figure 3 (a) and (b) shows two diffraction pat- 
terns obtained for sample I corresponding to the 
[001] and the (HO) zone axes of the Hg- 
BaiCaiCuaOs+j (Hg-1223) phase, Tespectively. In 
both cases, the diffraction spots are sharp, which in- 
dicates that the crystaf is well ordered. In fig. 3(b), 
one can notice a modulation of the intensity of the 
diffraction spots along the c*-axis, with maxima for 
U7 reflections with /=5n (n=0, 1, 2. ...). On the mi- 
crograph (fig. 3(c)) corresponding to the diffrac- 
tion pattern shown in fig. 3(b). one can see the very 



regular periodicity of the fringes separated by 15.8 
A. During the observation under the electron beam, 
dark spots appeared near the edge of the crystal, 
probably due to the decomposition of the crystal 

Some diffraction patterns obtained for other crys- 
tals present diffuse lines parallel to the c*-axis and 
passing through the Bragg spots (fig. 4 (a)). They 
are due to the presence of inteigrowths as given evi- 
dence for by fig. 4(b). On this micrograph, two dif- 
ferent spacings of 15.8 A and 12.7 A can be mea- 
sured, attributed to Hg-1223 and Hg-1212, 
respectively. 

In the case of sample II. almost all the observed 
crystallites have diffraction patterns corresponding 
to the Hg-1 234 phase (HgBa2a3Cu40io+rf) with cell 
parameters fl=A=3.85 A and c= 19 A. Figure 5(a) 
and (b) give examples of the (001 ] and <I00> zone 
axes, respectively. As for Hg-1223, also for Hg-1234 
the intensity of the Bragg spots varies according to 



t, . . AntipoY €t at. / HgBoiCajCujOs^s HgBa jCojCm/: 





Tit 3. Electron diffraction pailcms of Hg-1 223 taken along lOOl 1 
(a) and < 1 10> (b) zone axes, (c) Micrograph corresponding to 
the diffraction pattern (b). The inlcrfringe spacing is 1 5.8 A. 

the vahic oRhe / index, ihe maxima of intensity being 
obtained for /=6/j (/i = 0. 1, 2, ...). This intensity 
pattern might be explained by the fact that c/ 6 is 
equal to 3.17 A, which corresponds to the distance 
between two neighboring (CuOj) layers. The in- 
crease of the layer number n in the structure leads to 
the increase of the intensity of the hkl reflections with 




Fig. 4. Dcctron diffraction pattern of sample I along < 100) and 
corresponding micrograph showing the intergrowths of Hg-1 223 
and Hg^l212. 

/^„+2. These periodicities of the (CuOj) layers ex- 
plain the overlapping of such reflections on the X- 
ray powder pattern (see above). Most of the images 
taken along the < 100 > zone axis show very regular 
fringes separated by 19 A (fig. 5(c) ). However, some 
crystals present intergrowths between the Hg-1 223 
and Hg-1 234, as revealed in fig. 6. In this case, the 
following sequence is observed over about 500 A: 
-19 A.19 A-I9 A-19 A-19 A-22 A-. On the corre- 
sponding diffraction pattern, besides the diffraction 
spots of the Hg-1234 phase, additional spots related 
to the 22 A periodicity are present. Such a period- 
icity may be attributed to a 1245 phase (Hg- 
BajC:a4CujO,2+i). The fact that the extra diffraction 
spots are sharp indicates that this phase is well or- 
dered at least over a certain number of cells in these 
crystals. 



4. AC susceptibilitj' measurements 
The critical temperature and the apparent su- 



6 



E, K Antipov aL /ffefla/Tfl^w/),^, and HgBajCajCu/}^ 





Fig. 5. EOcctron diffraction patterns of Hg-1234 taken along (001 ] 
(a) and < I00> (b) zone axes, (c) Micrograph corresponding to 
the diffraction pattern of (b). The interfringe spacing is 1 9 A. 



pcrconducting volume of samples I and II have been 
determined from AC susceptibility measurements on 
fine powder samples. This avoids overestimates of 
the superconducting volume due to the laigcr screen- 
ings in sintered samples. The AC susceptibility was 
measured with an alternating maximum field of 0,01 
Oc and a frequency of 119 Hz, The temperature was 
measured by a calibrated 100 Q platinum 
thermometer. 

The as-synthesized sample I undergoes a transi- 
tion from the paramagnetic to the diamagneiic state 
with an onset above 133 K (fig. 7). Several mca- 
surements were made with the same sample and the 
reproducibility of Tc is + / - 1 K (mainly due to the 
thermal contact between the sample and the ther- 
mometer). The estimated magnetic susceptibiUty at 
4 K corresponds to a large volume of ideal dia- 
magnclism indicating the bulk nature of supercon- 
ductivity. We can suggest that the sharp and large 
drop on the AC susceptibility curve above 133 K 
should correspond to the Hg-1223 phase because Hg- 
1212, which is present in this sample as the minority 
phase, has a not higher than 126 K [3], 

The as-synthesized sample II undergoes a transi- 
tion from the paramagnetic to the diamagnetic stale 
with an onset as high as 132 K. Actually, two onsets 
at two different temperatures are visible, the smaller 
one at 132 K and the larger one at about 126 K. There 
are two Hg-based layered cuprates in this sample: Hg- 
1234 as the main phase and Hg-1223 as the minority 
one. Taking into consideration the results of sample 
1, wc might suggest that the first onset ( 1 32 K) cor- 
responds to Hg-1 223 and the lai:gcr one at the lower 
temperature (126 K) to Hg-1234. In any case, it is 
obvious that 7; for Hg-1234 is not higher than that 
for Hg-1223, 



5. Discussion 

The synthesized HgBa2Ca2Cu,OB+^ (Hg-1223) 
and HgBa2CajCu40,o+, (Hg-1234) phases arc the 
third and the fourth members of the Hg- 
Ba2Ca„_|Cu„Oj«+2+a scries, in analogy with those 
of Hg-1201 (1,7,8) and Hg-1212 [2) their stnic- 
turcs can be schematized as containing rock-salt-Iike 
slabs, (BaO)(HgOj)(BaO). alternating with pcr- 
ovskite-like slabs, consisting in three (Hg-1223) or 



£. K Andpov ft ai. / HgBajCajCujOs^^ andHgBa/ki/:u/>,, 
SAMPLE 1- as synthesized 



IT 

E 
o 

o 



I 

-1 
-3 
-5 
-7 
-9 
-II 
-13 
15 



/ 



100 



125 150 



0 25 50 75 

Fig.J. AC .usceptibilhy vs. Tfor ^-synthesized sample I, where Hg-1223 is present as .he main phase and Hg.I2.2 as the minority 

SAMPLE 2 • as synthesized 



E 




Fig. 8. AC susceptibility vs. Tfor as-synthcsized sample II showing the 
minority phase. 



125 150 
T(K) 

presence of Hg-1234 as the main phase and orHg-1223 as the 



1212. The appropriate ireatmeni for Hg-1234 can 
possibly change for this phase, therefore, wc can 
only conclude that for the as-prepared samples a sat- 
uration of 7; seems to occur in the Hg-Ba-Ca-Cu- 
O system at the third member. A similar behavior 



occurs for the TlBaiCa.^.Cu.Oi,^,^^ homologous 
series, for which increases up to the third member 
(120 K) also (91. 

One can see in table 1 that for the Hg series, the 
increase of is accompanied by a decrease of the a 



unority 



as the 



>gous 
mbcr 

5. the 
the a 





Fig. 9. The crystal siniciurcs of Hg l223 (a) and Hg-1234 (b). The largest and medium large circles refer to Ba and Ca atoms, rcspcc- 
lively. The Cu atoms arc ihc smallest circles. Those at ihc base of ihe shaded pyramids are not shown. The circles forming the squares 
around the Cu arc oxygen atoms. The dumbbr ^5 around the Hg atoms arc formed by apical oxygen atoms. Partially filled circles refer to 
the panially occupied oxygen sites on the Hg layer. 



parameter and just at Tc it remains practically con- 
stant between Hg-1223 and Hg-1234. 
The electron microscopy study of Hg-1201 {10] 



revealed the absence of intergrowihs and this was at- 
tributed to the absence of the Ca^^ cations in the 
system. On the contrary, the addition of Ca layers in 



to 



Table 



E, K Antipov €t al. / HiBa/:Q^u/)t^,andHgBa^a/:u40 



Utticc parameters and transition temperature for Hg-based Cu oxides 



Formula 


Short form 


«(A) 


c{k) 


7;^(K) 


Ref. 


HgBa,CuO^+> 
HgBa2CaCua04+^ 


Hg-I20i 
Hg-I212 


3.8797(5) 
3.8556(8) 


9.509(2) 
12.652(4) 


94 
121 


[1) 
f2J 


llgBa^Ca^CuiO,^^ 
HgBa,Ca,Cu,0,o*i 


Hg-I223 
Hg-I234 


3.8532(6) 
3.8540(3) 


15.818(2) 
19,006(3) 


126 
133 
<I32 


131 

|4), ihis work 
this work 



the system leads to intergrowths due to diflfcrcnt 
numbers of (CuO^) and Ca layers in the perovskite- 
likc slabs. Such intergrowths were already reported 
in ref. [4]. Possibly, ihe occurrence of different in- 
tergrowths may explain why the variation versus 
temperature of the AC susceptibility docs not pres- 
ent distinct and abrupt transitions which could be 
attributed to pure Hg-J212. 1223 and 1234 phases. 

The synthesis of the higher members of the Hg- 
based homologous series as bulk samples has been 
performed at higher temperatures than that used for 
Hg-1212 and with longer treatment times. We sug- 
gest that the synthesis of such phases occure through 
the formation at an initial state and subsequent de- 
composition of the lower members of the series. This 
feature is similar to that existing for the Tl- 
Ba2Ca„„,Cu„02«+3_^ homologous series [9]. The 
use of high pressure, possibly, lowers the mercury 
oxide decomposition. It also leads to a decrease of 
stability of ClaHgO^, whose synthesis at the first stage 
of the reaction inhibits the formation of Hg-based 
compounds. 



Acknowledgements 

Tbe- authors would like lo thank M.F. Gorius, M. 



Pcrroux and R. Argoud for their technical assistance 
The visit of EVA has been supported by the fund from 
the French Ministry of Foreign Affairs. EVA and SNP 
would like to thank the support of the Russian Sci- 
cntific Council on Superconductivity (Project 
"Poisk"). SML was supported by the Erasmus Stu- 
dents Exchange Program. 

References 

( } S.N. Puliltn. E.V. Antipov. O. Chmaisscm and M. Marczio 

Nature (London) 362 (1993) 226. 
|2 JS.N. Putilin. E.V. Antipov and M. Marczio. Physica C2I2 

(1993)266. 

[3 J S.M. Lourciro and JJ. Capponi. private communication. 
14 J A. Schilling. M. Onioni, J.D. Guo and H.R. Otl. Naiurc 

(Undon)363(l993)56. 
(5 J K.E. Johansson. T. Palm and P.-E. Werner. J. Phys. E: Sci 

Instrum. 13 (1980) 1289. 
f 6 1 S.N. PutiUn, M,G. Rozova. D. Kashpocov, EV. Antipov and 

LM. Kovba. Zh. Ncof^ganichcskoi Khimiii 36 ( 1 99 1 ) 1 645 

(in Russian). 

[7 J O. Chmaisscm, Q. Huang. S.N. Putilin, M. Marczio and A. 

Santoro. Physica C 212 (1993) 259. 
1 8 1 J.L Wagner, P.G. Radaelli, D.G. Hints. JI>. Joigcnscn. J.F. 

MitcbeU. B. Dabrowski, G.S. Knapp and MA. Bcno. Physica 

C2I0( 1993) 447. 
|9J S. Nalcajima. M. Kikuchi. V. Syono. T. Oku. D. Shindo. K. 

Hiraga. N. Kobayashi. H. Iwasaki and Y. Muio. Physica C 

158 (1989) 471. 
1 1 0 J 1. Brynisc and S.N. Putilin. Physica C 2 1 2 ( 1 993 ) 223. 



BRIEF ATTACHMENT BJ 





IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re application of: 



Date: November 6, 2006 



Applicants: Bednorz, et al. 



Docket: YO987-074BZ 



Serial No.: 08/479,810 



Group Art Unit: 1751 



Filed: June 7, 1995 



Examiner: M. Kopec 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 22313-1450 
(571)273-8300 



I hereby certify that this Ninth Response After Final Rejection (_4_ pages) 
is being facsimile transmitted to the U.S. Patent and Trademark Office to (571) 



In response to Office Action dated October 20, 2005, please consider the 
following: 



CERTIFICATE OF FACSIIilLE TRANSMISSION 




Dr. Daniel P. Morris, Esq. 
Reg. No. 32,053 



NINTH SUPPLEMENTAL RESPONSE 



Serial No. 08/479,810 



1 Docket No. YOR919870074US5 



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ATTACHMENT BK 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 
Applicants: Bednorz et al. 
Serial No.: 08/479,810 
Filed: June 7, 1995 



Group Art Unit: 1751 
Examiner M. Kopec 



Docket: YO987-074BZ 



Date: November 25, 2006 



For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH TRANSITION 
TEMPERATURE, METHODS FOR THEIR USE AND PREPARATION 



Commissioner for Patents 
Box AF 
P.O. Box 1450 
Alexandria, VA 22313-1450 



CERTIHCATE OF RRST CLASS TRANSMISSION 

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following: 



1 



ATTACHMENT A 



4 




Edited by 

B.A.HANDS 



< 

■ORE H3fl«J2T 



HANDS 




Cryogenic Engineering 



Edited by 



B. A. Hands 

Department of Engineering Science, University ofOrf^ a 
and St. Hilda's CoUege, Oxford. England 



1986 




Academic Press 

Harcourt Brace Jovanovich, Publishers 
London Orlando New York San Diego Austin 
Boston Tokyo Sydney Toronto 



ACADEMIC PRESS INC. (LONDON) LTD. 
24/28 Oval Road, London NWl 7DX 

United States Edition published by 
ACADEMIC PRESS, INC. 
Orlando, Florida 32887 



Copyright © 1986 by 
Academic Press Inc. (London) Ltd. 

All rights reserved. No part of this book may be reproduced 
or transmitted in any form or by any means, electronic or 
mechamcal, including photocopy, recording, or any 
information storage and retrieval system without permission 
in writing from the publishers 



British Library Cataloguing in Publication Data 

Cryogenic engineering. 
1. Low temperature engineering 
I. Hands, B.A. 
621 .5'9 TP482 

ISBN 0-12-322990-1 
ISBN 0-12-322991-X (Pbk) 



Computer typeset and printed by 
Page Bros (Norwich) Ltd 



C. A, Bail! 
eering S 
and Fell 

R. A. Byrn 
Formerh 
Califom: 
Dew-Hi 
versity o 
versity C 

D. Evans 
OQX, Er 

E. J. Grego 
Fordhou 

B. A. Hand 
eering S< 
and G.E 

G. Kram 
Karlsruht 

J. T. Morj 
OXll oc 

N. Nambud 
Bombay 
Engineer 

B. W. Ric* 
inghamsh 

J. M. Robei 
Establish; 

H. Sixsmit] 
Hampshi] 

W. L. Swi] 

Hampshii 
W.J.Tallis 

Science, 1 
R. M. Tho] 

Chemical; 
T. J. Webst 

England. 



Contributors 



C. A. Bailey University Lecturer, Cryogenics Laboratory, Department of Engin- 
eering Science, University of Oxford, Parks Road, Oxford OXl 3PJ, England 
and Fellow of Keble College, Oxford 

R. A. Byrns Consultant, 2457 Marin Avenue, Berkeley, California 94708, U.S.A. 
Formerly Staff Senior Scientist, Lawrence Berkeley Laboratory, University of 
California, Berkeley, California 94720, U.S.A. 

D. Dew-Hughes University Lecturer, Department of Engineering Science, Uni- 
versity of Oxford, Parks Road, Oxford OXl 3PJ, England and Fellow of Uni- 
versity College, Oxford 

D. Evans Rutherford Appleton Laboratory, Chilton, Didcot, Oxfordshire OXll 
OQX, England 

E. J. Gregory Chief Process Engineer, Marston-Palmer Limited, Wobaston Road, 
Fordhouses, Wolverhampton WVIO 6QJ, England 

B. A. Hands Research Associate, Cryogenics Laboratory, Department of Engin- 
eering Science, University of Oxford, Parks Road, Oxford OXl 3PJ, England 
and G.E.C. Lecturer in Engineering, St. Hilda's College, Oxford 

G. Krafft Koordinationstelle Technologietransfer, Kemforschungszentrum 
Karisruhe GmbH, Postfach 3640, D-7500 Karlsruhe 1, West Germany 

J. T. Morgan Rutherford Appleton Laboratory, Chilton, Didcot, Oxfordshire 
OXll OQX, England 

N. Nambudripad Tata Institute of Fundamental Research, Homi Bhabha Road, 
Bombay 400 005, India. Formerly of the Cryogenics Laboratory, Department of 
Engineering Science, University of Oxford 

B. W. Ricketson Cryogenic Calibrations Limited, Pitchcott, Aylesbury, Buck- 
inghamshire HP22 4HT, England 

J. M. Robertson Heat Transfer and Huid Flow Service, Atomic Energy Research 
Establishment, Harwell, Oxfordshire 0X11 ORA, England 

H. Sixsmith Creare Inc., PO Box 71, Great Hollow Road, Hanover New 
Hampshire 03755, U.S.A. 

W. L. Swift Creare Inc., PO Box 71, Great Hollow Road, Hanover, New 

Hampshire 03755, U.S.A. 
W. J. Tallis Design Engineer, Cryogenics Laboratory, Department of Engineering 

Science, University of Oxford, Parks Road, Oxford 0X1 3PJ, England 
R. M. Thorogood Director, Cryogenic Research Programs, Air Products and 

Chemicals Inc., PO Box 538, Allentown, Pennsylvania 18105, U.S.A. 
T. J. Webster Consultant, 38 Parkland Grove, Ashford, Middlesex TW15 2JR, 

England, Formerly Safety Manager, British Oxygen Company Ltd., England 



Preface 



The 1960s saw great activity in the field of cryogenic engineering, stimulated 
particularly by the American space effort and by developments in superconductivity. 
As a result, a number of books on cryogenic engineering in general were published. 
Since then, most volumes have concentrated on a particular aspect of the subject, 
rather than attempting a comprehensive review. In view of the steady, if unspec- 
tacular, advances made since that time, it seems opportune to attempt a new 
account of the basic science and of the engineering methods employed. 

Cryogenic engineering covers a wide spectrum of disciplines, in traditional terms 
embracing much of electrical, mechanical and chemical engineering, its dis- 
tinguishing feature being the use of temperatures well below ambient. In order to 
produce a volume of reasonable length, it was decided to assume that the reader 
should have knowledge appropriate to that of a final-year or graduate engineer or 
physicist. Further, since much of the body of knowledge of engineering at room- 
temperature can be applied directly to cryogenic problems, reference in such 
cases is made to standard textbooks, although since this book is biased towards 
engineering, the physicist may need to consult rather more of them than the 
engineer. 

It was also decided, again on the grounds of overall length, to restrict the account 
of superconductivity. The design of superconducting magnets is very largely an 
electrical engineering problem, the cryogenic design, apart from training problems 
and stabilisation, being relatively straightforward. Further, the monograph 
"Superconducting Magnets" by M. N. Wilson (Oxford University Press, 1985) 
treats the subject comprehensively, and is required reading for anyone with other 
than a superficial interest in magnet design. Thus, the coverage of this topic is 
deliberately brief. 

There are some other deliberate omissions, also. In particular, an account of 
refrigeration using hydrogen and neon is omitted, on the grounds that the techniques 
involved are broadly the same as those used for helium. Similariy, the particular 
problems involved with cryogenics in space are given only passing mention, since 
most of the design principles involved are also applicable to earth-based equipment. 
There is no attempt to provide complete property data; general trends are indicated, 
and, it is hoped, enough references for the reader to locate detailed data as 
necessary. However, since the book is intended for potential (and practising) 
cryogenic engineers, details of practical methods and current practices have been 
included. 



PREFACE 

The production of this book has been a co-operative effort, and I thank the 
authors for their tolerance of the editor's quirks. I should Uke to acknowldge those 
who have read parts of my own contributions and assisted with the provision of 
information, photographs and diagrams, particularly Dr A. Acton Dr V D Arp 
Mr R. J. Allam, Dr C. A. Bailey, Dr M. L, Christie, Dr. G. Davey, Prof G B 
Donaldson, Mr R. Harper, Dr D. B. R. Kenning, Dr R. D. McCarty Dr W 
Obert, Dr. C. Ruiz, Dr L. Solymar and Dr. R. M. Thorogood. Acknowledgements 
and sources for diagrams and photographs are given as appropriate in the text- I 
am most grateful to the organisations which supplied these and gave permission for 
their use. I am mdebted to Johanne Beaulieu for preparing much of the text to 
Mrs Judith Takacs for drawing the diagrams with her usual patience and skill and 
to Mrs Stella Seddon for preparing the index. Finally, gratitude is due to my family 
for their tolerance, and for foregoing the use of the dining table for many months. 

^ord,^9S5 B. A. Hands 

In the tables of data, a dash indicates that information was not available. 



1.1 Introd 

1.2 TheC 

1.3 Featuj 

1.4 Lique) 

1.5 Air S€ 

1.6 Liquic 

1.7 Liquic 

1.8 Supen 

1.9 Cryog. 

1.10 Cryog. 

1.11 Medic 

1.12 Cryop 

1.13 Instrui 
Refert 
Journ£ 
Gener 
BibliO] 
Non-s| 



2.1 Introdu 

2.2 Propert 



PREFACE 



id I thank the 
Jiowldge those 
le provision of 
Dr V. D. Arp, 
ly. Prof G. B. 
Carty, Dr W. 
owledgements 
; in the text; I 
permission for 
of the text, to 
and skill, and 
e to my family 
many months. 

A. Hands 

2hle. 



Contents 



Contributors 
Preface 



1. A Survey of Cryogenic Engineering 
B. A. Hands 

1.1 Introduction 

1.2 The Cryogenic Temperature Range 

1.3 Features of Cryogenic Engineering 

1.4 Liquefied Natural Gas (LNG) 
/ 1.5 Air Separation 

1.6 Liquid Hydrogen 

1.7 Liquid Helium 

1.8 Superconducting Magnets and Machinery 

1.9 Cryogenic Electronics 

1.10 Cryogenics in Space 

1.11 Medical and Biological Applications 
I 1.12 Cryopumping 

1.13 Instrumentation 
References 
Journals 

General Bibliography 
Bibliography of Specific Topics 
Non-specialist Reading 

j 2. Properties of the Cryogenic Fluids 

B. A. Hands 

i 2.1 Introduction 

; 2.2 Property Data 

I 2.3 Hydrogen 

2.4 Helium 

2.5 Equations of State 



X 



CONTENTS 



COI 



2.6 The Two-phase Region 

2.7 Computer Packages 

2.8 Approximate Equations 

2.9 Properties of Mixtures 
References 

Sources of Data 



54 5.9 

56 5.10 

58 5.11 

59 5.12 
63 5.13 
63 5.14 



3. Cryogenic Safety 
T. J. Webster 

3.1 Introduction 

3.2 Organisation for Safety 

3.3 Relationship between Fluid Properties and Safety 

3.4 First Aid 

3.5 Combustion 

3.6 Oxygen Hazards 

3.7 Unexpected Hazards 

3.8 Fluorine Safety 
Bibliography 



67 
68 
68 
76 
77 
79 
83 
87 
87 



4. Thermal Design 
C. A. Bailey and B. A. Hands 



4.1 Conservation of Energy Considerations 

4.2 General Energy Requirements 

4.3 Specific Heat 

4.4 Thermal Contraction 

4.5 Thermal Conductivity of Solids 

4.6 Conduction through Gases 

4.7 Radiative Heat Transfer 

4.8 Thermal Insulations 

4.9 Applications to Design 
References 
Bibliography 



5. Fluid Dynamics 
B. A. Hands 



5.1 Introduction 

5.2 Pressure Drop Calculations 

5.3 Single-phase Pressure Drop 

5.4 Characteristics of Two-phase Row 

5.5 Two-phase Pressure Drop 

5.6 Critical (Choked) Flow 

5.7 Cooldown Behaviour 

5.8 Introduction to Instabihties 



89 
90 
93 
97 
100 
106 
107 
112 
116 
121 
121 



123 
124 
125 
128 
130 
131 
131 
132 



CO^JTENTS 



CONTENTS 



54 
56 
58 
59 
63 
63 



5.9 Density Wave Oscillations 

5.10 The Ledinegg Instability and Pressure-drop Oscillations 

5.11 Geysering 

5.12 Thermoacoustic Oscillations 

5.13 Stratification. Thermal Overfill and Rollover 

5.14 Sloshing 
References 



134 
136 
138 
141 
143 
146 
148 



67 
68 
68 
76 
77 
79 
83 
87 
87 



89 
90 
93 
97 
100 
106 
107 
112 
116 
121 
121 



123 
124 
125 
128 
130 
131 
131 
132 



6. Heat Transfer to Fluids 
J. M. Robertson 



6.1 Introduction 

6.2 Heat Transfer to Single-phase Fluids 

6.3 Heat Transfer Rates 

6.4 Pool Boiling 

6.5 Boiling in Channels 

6.6 In-tube Condensing 
References 



7, Heat Transfer Below 10 K 
G. Krafft 



7.1 Introduction 

7.2 Basic Considerations 

7.3 Heat Transfer to Supercritical Helium 

7.4 Heat Transfer to Two-phase Helium 
References 



8. Heat Exchangers 
E. J. Gregory 



8.1 Introduction 

8.2 Regenerators 

8.3 Coiled Tube Heat Exchangers 

8.4 Plate and Fin Heat Exchangers 
References 



9. Electrical Conductors at Low Temperatures 
D. Dew-Hughes 



9.1 Introduction 

9.2 Simple Theory of Electrical Resistivity 

9.3 Real Conductors at Low Temperatures 



151 
153 
156 
157 
160 
166 
168 



171 
172 
174 
181 
191 



193 
195 
197 
199 
216 



217 
219 
221 



CONTENTS 

9.4 Magnetoresistance 223 

9.5 Superconductivity 225 

9.6 Theories of Superconductivity 229 

9.7 Flux-pinning and Critical Current Density 232 

9.8 Conductor Stability 235 ^^'^ 

9.9 Stress Effects 236 ^^'^ 
9.10 Conunercial Superconductors 238 ^^'^ 

Bibliography 240 ^^'^ 

13.5 : 
13.6 
13.7 ■ 

10. Mechanical Design with Metals j^*^ '. 

B. A. Hands 13.10 ' 

10.1 Introduction 24 1 13.11 

10.2 Elastic Moduli 242 = 

10.3 Plastic Behaviour 243 ^ 

10.4 Fracture Behaviour 246 

10.5 Fatigue Behaviour 252 

10.6 Aluminium Alloys 254 

10.7 Stainless Steels 257 

10.8 Nickel-Iron Alloys 262 

10.9 Titanium Alloys 265 

10.10 Copper Alloys 266 

10.11 General Discussion 267 
References 269 
Bibhography 270 



11. Design with Non-metallic Materials 
D. Evans and J, T. Morgan 

11.1 Introduction 

11.2 Mechanical Properties of Polymers and their Relation to Structure 

11.3 Thermal Contraction 

11.4 Thermal Conductivity 
Bibliography 



12. Construction and Assembly Methods 
W. J. Tallis 

12.1 General Design Considerations 

12.2 Permanent Joints 

12.3 Demountable Joints 

12.4 General Comments 



271 i 




276 : 




285 i 


15.1 5 


289 i 


15.2 I 


292 1 


15,3 : 


i 


15.4 I 




15.5 ( 




15.6 1 




15.7 1 




15.8 < 




15.9 1 




15.10 I 


293 


15.11 ] 


295 


15.12 : 


302 


15.13 1 


309 i 


15.14 1 



CONTENTS 



CONTENTS 



xiii 



223 
225 
229 
232 
235 
236 
238 
240 



241 
242 
243 
246 
252 
254 
257 
262 
265 
266 
267 
269 
270 



13. Principles of Refrigeration, Liquefaction and Gas Separation 
C. A. Bailey and B. A. Hands 

13.1 Refrigeration 

13.2 Liquefaction 

13.3 Cooling Methods 

13.4 Simple Cycles 

13.5 Irreversibility 

13.6 Second Law Violations 

13.7 Compound Cycles 

13.8 The Separation of Gases 

13.9 Principles of Distillation 

13.10 The Single Column Linde System 

13.11 The Double Column 
References 



14. Cryogenic Turbines and Pumps 
H. Sixsmith and W. L. Swift 



14.1 Introduction 

14.2 Turboexpander Design 

14.3 Gas Bearings 

14.4 Protective Devices 

14.5 Turbine Performance 

14.6 Pumps 

14.7 Conclusions 
References 



313 
314 
316 
320 
324 
324 
325 
328 
329 
336 
339 
340 



341 
342 
344 
348 
349 
352 
355 
355 



271 
276 
285 
289 
292 



293 
295 
302 
309 



15. Large Helium Refrigeration and Liquefaction Systems 
R. A. Byms 



15.1 Specification of Heat Load and Capacity 


357 


15.2 Design of J-T Stage 


360 


15.3 The Claude Cycle 


362 


15.4 Design and Optimisation 


364 


15.5 Compressors 


366 


15.6 Heat Exchangers 


368 


15.7 Expanders 


369 


15.8 Control, Instrumentation, Purity and Gas Management 


371 


15.9 Distribution and Cooling Methods 


372 


15.10 Large Helium Plants 


375 


15.11 Large Purification Liquefiers 


375 


15.12 The 1500 W Refrigerator 


376 


15.13 Lawrence Livermore National Laboratory (3000 W) System 


379 


15.14 Fermi National Accelerator Laboratory (23 kW) System 


381 



xiv CONTENTS 

15.15 Brookhaven 24.8 kW Refrigerator 388 

15.16 Refrigeration Equipment Cost 389 
References 389 



16. Large Gas Separation and Liquefaction Plants 
R. M. Thorogood 



16.1 Introduction 39I 

16.2 Cryogenic Air Separation Processes 392 

16.3 Natural Gas Processes 409 

16.4 Natural Gas Liquefaction Processes 411 

16.5 Equipment for Large Air Separation Plants 418 

16.6 Equipment for Natural Gas Plants 424 

16.7 Operation and Safety 427 
Acknowledgements 428 
References 42g 



17. Small Refrigerators 
N. Nambudripad 

17.1 Introduction 43 1 

17.2 The Stirling Refrigerator 433 

17.3 The Gifford-McMahon Refrigerator 438 

17.4 The Pulse-tube Refrigerator 441 

17.5 The Vuilleumier Refrigerator 443 

17.6 Losses in Regenerative Mechanical Coolers 445 

17.7 Regenerators 447 

17.8 Magnetic Refrigeration 452 
References 453 



18. Thermometry 
B. W. Ricketson 

18.1 Introduction 457 

18.2 Temperature and Accuracy 458 

18.3 Criteria for Choosing a Sensor 459 

18.4 Sensors 460 

18.5 Thermal Anchorage for Electrical Leads 467 

18.6 Measurement 468 

18.7 Temperature from the Measurement 473 

18.8 Conclusion 476 
References 476 



Appendix 
Index 



477 
485 



>rrENTs 



388 
389 
389 



Symbols Used 



391 
392 
409 
411 
418 
424 
427 
428 
428 



431 
433 
438 
441 
443 
445 
447 
452 
453 



457 
458 
459 
460 
467 
468 
473 
476 
476 



Centrifugal 
Compressor 



Aftercoder 



Turbine Turbine 
Expander Compressor 



Reciprocating 
Compressor or 
Expander 



Chiller 



Q-{ 



yd. 




Turbine Expander 
with Electric 
Broke 



Pump 



Inlet Air 
Filter 



Heater 




Heat Exchangers 
Counter flow Crossf low 

-tXl- -K}- 

Valve Check Valve 



Reboiler- 
Condenser 



Reversing 
Valve 



Distillation 
Column 



I 



Absorber Vessel 

Containing 
Liquid 



477 
485 



1 

A Survey of Cryogenic Engineering 



B, A. HANDS 



1.1 Introduction ^ 

1.2 The Cryogenic Temperature Range 2 

1.3 Features of Cryogenic Engineering 3 

1.4 Liquefied Natural Gas (LNG) ^ 

1.5 Air Separation 
1-6 Liquid Hydrogen 

1.7 Liquid Helium 

1.8 Superconducting Magnets and Machinery 

1.9 Cryogenic Electronics 

1.10 Cryogenics in Space 

1.11 Medical and Biological Applications 

1.12 Cryopumping 

1.13 Instrumentation 
References 
Journals 
General Bibliography 

Bibliography of Specific Topics 3^ 
Non-specialist Reading 3^ 



26 
29 
29 
30 
33 
34 



1.1 Introduction 

Most of this book is concerned with an outline of the theory and practice 
of cryogenic engineering. It has not been possible within a volume of 
reasonable size to explore every aspect in detail, nor has it been possible 
to give a detailed account of all the applications of cryogenics. This chapter 
is intended to give an impression of the wide range of cryogenic engineering. 
After a discussion of the meaning of cryogenics, the chapter covers the 
uses of the commoner cryogenic liquids (natural gaS, oxygen, nitrogen 
hydrogen and helium), and then deals with superconductivity and cryo- 



CRYOGENIC ENGINEERING 
ISBN 0-12-322990-1 y 



Copyright © im Academic Pros Inc. (London) Umited 
Ail rights of reproduction in any form reserved 




^ B. A. HANDS 

pumping. The chapter concludes with a brief outline of cryogenic 
instrumentation. 



1.2 The Cryogenic Temperature Range 

The 1960s were a decade which saw a rapid expansion both in low- 
temperature physics and in the commercial exploitation of low-temperature 
techniques. Towards the end of this period, a need was felt for the stand- 
ardisation of low-temperature terminology, and, on the initiative of Pro- 
fessor Nicholas Kurti, the Comite d 'etude des termes techniques frangais 
organised a meeting in 1969, at which was formed a small international 
committee to consider the terminology of low temperatures, remembering 
the necessity of unambiguous translation between EngUsh and French, and 
paying due regard to current practice in the United States. As an example 
of the confusion which then existed, temperature levels in Britain were, by 
some people, referred to as 'low' (below 0**C), Very low' (around 100 K), 
'deep low' (around 4K) and 'ultra low' (less than 0.3 K), although the 
French had only two terms 'basse' and 'tr^s basse'. It was never clear how 
the British users of this terminology would refer to temperatures in the 
microkelvin region! 

The working group, with members from six countries, made its re- 
commendations in 1971 [1.1], and these have largely been accepted by the 
scientific community. 'Cryogenics' and the corresponding prefix 'cryo' were 
to refer to 'all phenomena, processes, techniques or apparatus occurring 
or used at temperatures below 120 K' approximately, that is, around or 
below the normal boiUng point of Hquefied natural gas. It was recognised, 
however, that some inconsistencies were unavoidable, in particular the use, 
on historical grounds, of the terms cryohydrate, cryoscopy, cryochemistry 
and the French cryodessication, all of which refer to temperatures well 
above 120 K; and, because they use cryogenic fluids and techniques, cryo- 
surgery, cryomedicine and cryobiology. Otherwise, the temperature range 
between 120 K and 0*C is covered by 'refrigeration' technology. 

The scientific community has, on the whole, adhered to these proposals, 
but they have not been rigidly adopted by industry, where the technology 
of handhng liquid ethylene (at around 150 K) is, with some justification on 
the grounds of the equipment used, included in the cryogenic domain, and 
'cryogenic' is also used, with less justification, to describe equipment 
designed for use at still higher temperatures. However, since all fluids 
and materials used in cryogenics must at some time be brought to room 
temperature, properties and processes in the temperature range up to room 
temperature cannot be ignored. 



1, A SURVEY OFCR^ 

In this book, we 
engineering' to refe 
most widely used liq 
liquefied natural gas 
liquid hydrogen (LI 
importance of hydro 
range, the producti 
regarded as 'physics' 
at present to experii 
demagnetisation anc 
be covered in this v( 



1.3 Features of Cryo 

It is worth considerii 
'ordinary' (or room 1 
that the properties o 
a particular mystiqu 
accepted that, in fac 
behave similarly to c 
ability to recognise an 
the use of low temp 
different from that re 
ment of design criter 
with identification c 
methods to achieve 
should, therefore, be 
in its own right. 

There are, howeve 
eering temperature n 
fluidity — ^the ability o 
The superfluid state b 
etical physicists for m 
has been achieved. 1 
because of the very h 

The other phenomt 
of electrical resistant 
different for each metj 



* According to [1.1], the 
wide acceptance. 



\. HANDS 
cryogenic 



1 in low- 
nperature 
the stand- 
ee of Pro- 
:s fran^ais 
jrnational 
lembering 
ench, and 
1 example 
1 were, by 
id 100 K), 
lOugh the 
clear how 
res in the 

de its re- 
ted by the 
:ryo' were 
occurring 
around or 
^cognised, 
ar the use, 
(Chemistry 
tures well 
ues, cryo- 
ture range 

proposals, 
echnology 
ication on 
main, and 
equipment 
all fluids 
t to room 
ip to room 



1. A SURVEY OF CRYOGENIC ENGINEERING 3 

In this book, we follow the 1971 recommendation and take ^cryogenic 
engineering' to refer to the temperature range below about 120 K. The 
most widely used liquids, in order of descending normal boiling point, are 
liquefied natural gas (LNG), hquid oxygen (LOX), liquid nitrogen (LIN), 
liquid hydrogen (LH2) and liquid helium (LHe), although at present the 
importance of hydrogen has declined. At the lower end of the temperature 
range, the production of temperatures less than about 1.5 K may be 
regarded as 'physics' rather than 'engineering', since their use is restricted 
at present to experimental work. Therefore, techniques such as adiabatic 
demagnetisation and the use of the light isotope of hehum (He^) will not 
be covered in this volume. 



1.3 Features of Cryogenic Engineering 

It is worth considering at this stage the differences between cryogenic and 
'ordinary' (or room temperature) engineering. For a long time, it was felt 
that the properties of cryogenic fluids were in some way peculiar, so that 
a particular mystique arose around this area of engineering. It is now 
accepted that, in fact, cryogens (with the exception of superfluid helium) 
behave similarly to other fluids, and that the art of cryogenics lies in the 
ability to recognise and cater for the particular problems which arise through 
the use of low temperatures per se. This requirement is, of course, no 
different from that required in any other branch of engineering: an assess- 
ment of design criteria and possible causes of equipment failure, together 
with identification of the best techniques, materials and construction 
methods to achieve safe, efficient and reliable operation. Cryogenics 
should, therefore, be regarded more as a special art rather than as a subject 
in its own right. 

There are, however, two phenomena peculiar to the cryogenic engin- 
eering temperature range which merit special consideration. One is super- 
fluidity — the ability of liquid helium to behave as if it has zero viscosity. 
The superfluid state has been investigated by both experimental and theor- 
etical physicists for many years, and a deep understanding of its behaviour 
has been achieved. From the engineer's point of view, it is of interest 
because of the very high rates of heat transfer which can be attained. 

The other phenomenon is that of superconductivity,* the complete loss 
of electrical resistance below some well-defined temperature which is 
different for each metal. Superconductivity is of increasing technical import- 

* According to [1.1], the proper term is superconduction, but this word has never achieved 
wide acceptance. 




. B- A. HANDS 

a^^icSi^;^^^^^^^^^^ -ab,e magnetic fields, and its 

1962, the discovery^ re Joip^^^^^^^^^^ ^'J r'"^'"^'^ ^'"^^ed. In 

of superconducting electroSe4es '^"'^ *° ' 

mu^rSt^'srxs^^^^^^^^^ 

the second law of therrnodyn^Tut ^^rT^T"'' 

roughly in inverse proportioLo the mln f ? ?f '""^^se 

For instance, to extras ^jTh 't 

of work, while to extract 1 J at 4 2 K rl. • 5 ^-^^ 
practice, of course, revers biWy In^ofhe!?^^^^^ f ^ «f work. In 
required is somewhat larger ZaTewtJ^^^^^^^ '"^ ^^^'^ ^<^t"«"y 

temperatures, to a fac^^r of ^tenTn t^^, '^'^^^^ 

e«,nomic grounds thereTset^in";^^^^^^^^^^^ ^^"^^ - 

wherever possible "^e of cryogenics 

in Geneva, Switzel^fn^Z Jluk f ^^^^^ ^i^^t 

France.* Each used a differlt ' ChatiUon-sur-Seine in 

470 bars to ZTuO KuZll 'T' oxygen a" 

carbon dioxid^ a wWcHem "^^^^^ ^"^^^^"^ 
through a valve, and saw a Snr^^nf . 'f''''' ^^^S^" »° ««^^Pe 
jet. Cailletet, o^ the Xer hTd ^,^7 ^^^"'4 
liquid sulphu; dioxide and then ne^ . ' '° °°'y -29°C using 

a mist of Lplets in hi;'^as t^Mt^^^^^ ^'f ^^P^"^-" ^° 
Kctet's method of 'cascade' c^ ni fni ^'^fP'''^ »°t-rest to observe that 
is still used in many des^Lr SriS Joule-Thomson expansion 

in association with'exteSlf S^^^^^^ ^^^^-^^ "^lly 

De^a^^lii&dlS^^^ 

paved the way for the liquefaction S hvH ^ ""'^ 
invention, the liquids wS^edTntL^ ^"^'" ""'^ ^"^^ J^^^^^'^ 

vessels, each coLiniL rtuml r^^^^ 

vacuum insulated, gTsf ia ^Ts no^ S I'"'' ^'^'^'^ temperature. TT,e 
'Thermos'; in the sLnti^c co™i7v he"°"" P"^"^ «^ ^ 

is also used for small stora^ vreTo? ' ' Jr"' ' " P'^'^"^'' 

Developments during the Lxt two hI ? °' PoIym^ric construction, 
in France and Linde in Ger^^Tdev^^^^^^^^^^^ Claude 
and fractional distillation of airrpTdr^Tn^r^^^^^^^^^^^ 



1- A SURVE 

forming coi 
today to m 
the 'permar 
afterwards j 
above the li* 
plentiful su] 
Leiden fror 
especially fo 
Between t 
production c 
process of 'a: 
100 (100 1 
was still a co 
duction bein^ 
basis, and the 
the world. 

Immediatel 
Massachusset 
hquefier usin 
making liquid 
the same timi 
during the 19: 
comparatively 
As a result, 
produced in q 
conducting 
was readily ava 
those research 
since the savir 
water-cooled s 
As confidence 
constructed, so 
tens of superc( 
refrigerators in 
engines were d( 
several kilowatt 
As to the futi 
argon by the frac 
process for mar 
present forms a > 
in importance as 
are developed. I 



B. A. HANDS 



1. A SURVEY OF CRYOGENIC ENGINEERING 



5 



ilds, and its 
y studied. In 
a new range 

is that work 
juired; from 
will increase 
emperature. 
; about 3.7 J 
of work. In 
^ork actually 
er cryogenic 
t. Thus, on 
f cryogenics 

the end of 
Raoui Pictet 
sur-Seine in 
)1 oxygen at 
de and solid 
n to escape 
he resulting 
-29°C using 
sion to form 
observe that 
n expansion 
)ugh usually 

sk by James 
periods and 
itil Dewar's 
<f concentric 
;rature. The 
1 public as a 
eferred and 
instruction . 
with Claude 
liquefaction 
xogen, and 

roversy, which 



forming companies which are still in the forefront of cryogenic engineering 
today to market their inventions. Finally, in 1908, helium, the last of 
the 'permanent' gases, was liquefied by Kamerlingh Onnes, who shortly 
afterwards produced superfluid helium by reducing the vapour pressure 
above the liquid using a vacuum pump. It is worth noting, in these days of 
plentiful supplies, that Onnes's helium was painstakingly extracted at 
Leiden from large quantities of monazite sand imported from India 
especially for the purpose. 

Between the two World Wars, there was a steady development in the 
production of oxygen and nitrogen by the distillation of liquid air (the 
process of 'air separation'), and during the 1930s plants producing around 
100 m^ (100 1) of hquid oxygen per day were in operation. Liquid helium 
was still a comparatively rare and expensive commodity, the rate of pro- 
duction being Umited to a Utre or two per hour, often only on an intermittent 
basis, and the Hquid being available in only very few laboratories throughout 
the world. 

Immediately after the Second World War, Professor Sam Collins, at the 
Massachussetts Institute of Technology, developed a new design of helium 
hquefier using reciprocating expansion engines, which was capable of 
making liquid on a continuous basis at a rate of several litres per hour. At 
the same time, the extraction of helium from natural gas wells, begun 
during the 1920s, had greatly increased, so that helium gas, although still 
comparatively expensive, was no longer a rare commodity. 

As a result, when, during the 1960s, Type II superconducting wire was 
produced in quantity on a commercial basis, enabling high-field super- 
conducting magnets to be constructed for the first time, liquid helium 
was readily available for cooling. This development was quickly exploited by 
those research estabUshments concerned with high-energy nuclear physics, 
since the saving in energy costs compared with those of an equivalent 
water-cooled system quickly outweighed the much higher capital cost. 
As confidence was gained, magnets of increasingly complex design were 
constructed, so that each of the major laboratories now contain several 
tens of superconducting magnets. In parallel with these developments, 
refrigerators incorporating expansion turbines rather than reciprocating 
engines were developed; a number of refrigerators capable of extracting 
several kilowatts at 4 K have now been built. 

As to the future, it is clear that the production of oxygen, nitrogen and 
argon by the fractional distillation of liquid air will remain a major industrial 
process for many years. The transport of liquefied natural gas by sea at 
present forms a vital Hnk in the world's fuel supply system, but will decrease 
in importance as supplies of natural gas diminish and other energy sources 
are developed. Hydrogen may well be one of these fuels, but at present in 



^ B. A. HANDS 

energy tenns it is expensive to produce, requiring large amounts of primary 
energy, and the liquefaction process also consumes much energy. Liquid 
hydrogen, therefore, may never be economically viable as a fuel other than 
for a few specialised applications. 

Superconducting magnet technology has assumed great importance, and 
since it is economically attractive compared with the use of conventional 
magnets and can also produce more uniform and time-invariant fields, 
applications are expanding. For a number of years, superconducting mag- 
nets have been routinely manufactured for experimental work in physics 
and chemistry, notably for nuclear magnetic resonance (NMR) and electron 
spin resonance (ESR). These methods have recently been extended to 
biological applications and now to medical diagnosis. This latter provides 
the first truly large-scale, commercial apphcation of superconductivity. 

Although superconducting motors, generators, transmission lines, and 
so on have been under active development in a number of countries, the 
scenario so far has been that each advance in superconducting electrical 
engineering has been matched by an advance in the corresponding room- 
temperature technology. Since the latter is usually less complex, it has been 
more attractive on the grounds of both cost and reliability. 

In electronic engineering, the Josephson effect opened new prospects in 
the precise determination of voltage, in the measurement of very small 
magnetic fields and in rf apphcations. Devices based on the Josephson 
effect are now used on a routine basis. 

Thus, although cryogenics is a field of relative antiquity, there has been 
an unusually long time between the discovery of some phenomena and 
their commercial exploitation. This was particularly so in the case of 
superconductivity, which was discovered in 1911 but only ceased to be a 
laboratory curiosity some 50 years later. On the other hand, devices using 
the Josephson effect were marketed within a few years of its prediction and 
discovery. 



1.4 Liquefied Natural Gas (LNG) 

Natural gas is typically composed of 85-95% methane, the remainder 
being mainly nitrogen, ethane, propane and butane, although quantities of 
heavier hydrocarbons, carbon dioxide, water, sulphur compounds and, 
occasionally, mercury, may also be present, the precise composition 
depending upon the reservoir from which it is extracted. Certain sources, 
notably in Kansas, are comparatively rich (about 0.4%) in hehum and are 
the major sources of this element. Natural gas is extracted by drilhng in a 
way similar to that used for oil production and is somewhat refined before 



1. A SUK 

use: the 
or as liq 
reduced. 

Natun 
century J 
pipeline 
of Amei 
rehed en 
of Japan 
Europe i 



y 

1! 



1980 
1990 



-F: 



Sources 
with the r 
of large di 
southwarc 
is liquefie 
decrease ] 
pressurisa 

The firs 
from Lake 
and as a re 
to Canve> 
Twenty ye 
Europe, fi 



B. A. HANDS 



1. A SURVEY OF CRYOGENIC ENGINEERING 



7 



imounts of primary 
uch energy. Liquid 
as a fuel other than 

at importance, and 
ise of conventional 
ne-invariant fields, 
)erconducting mag- 
tal work in physics 
NMR) and electron 
been extended to 
rhis latter provides 
iperconductivity. 
smission lines, and 
£r of countries, the 
inducting electrical 
)rresponding room- 
omplex, it has been 
dlity. 

td new prospects in 
ment of very small 
I on the Josephson 

lity, there has been 
ae phenomena and 
so in the case of 
Dnly ceased to be a 
hand, devices using 
Df its prediction and 



ine, the remainder 
though quantities of 
ir compounds and, 
necise composition 
id. Certain sources, 
>) in helium and are 
cted by drilling in a 
what refined before 



use: the heavier hydrocarbons are separated as natural gas liquid (NGL) 
or as liquefied petroleum gas (LPG), and the nitrogen content may be 
reduced. 

Natural gas was used on a local basis in the United States during the 19th 
century for both fuel and heating; by the 1940s it was being distributed by 
pipeline throughout much of the country and now provides about a quarter 
of America's energy requirements. Since about 1975, Great Britain has 
relied entirely on natural gas for its gas supphes; it forms a significant part 
of Japan's energy consumption; and its use is widespread throughout 
Europe and the USSR (Table 1.1). 



Table 1.1 





Past and Projected Consumption 


of LNG (lO^t/year)" 


Year 


Japan 


United States Western Europe Total 


1975 


5,0 


0,25 


8 13.3 


1980 


19 


11 


11 41 


1985 


44 


39 


22-36 105-119 


1990 


47-55 


50-105 


33-39 130-199 


Sources of natural gas (lO^t/year)" 




Americas 


USSR Middle East 


Far East Africa Total 


1980 


1 


— 3 


15 22 41 


1990 


6-30 


9-35 15-17 


35-39 67-78 130-199 



" From Thorogood [1.3]. 



Sources of natural gas are scattered relatively evenly around the globe, 
with the result that a trade has developed in transferring the gas to areas 
of large demand. Thus there are, for instance, major pipehnes from Alaska 
southwards, and from the USSR to Western Europe. However, much gas 
is Uquefied for both transport and storage to take advantage of the large 
decrease in specific volume which is achieved without the necessity for 
pressurisation. 

The first shipments of LNG by sea were made on an experimental basis 
from Lake Charles, United States, to Canvey Island, England, during 1959, 
and as a result of the success of these voyages a regular service from Algeria 
to Canvey Island was instituted in 1961, carrying about 700,000 t/year. 
Twenty years later, routes had been established from Algeria and Libya to 
Europe, from Algeria to the United States, and from Alaska, Abu Dhabi, 



B. A. HANDS 




Fig. 1.1 The LNG tanker *LNG Aquarius*, launched in 1977, L.O.A. 285 m. The LNG 
is carried in 5 spherical aluminium tanks, each of 25,260 m^ capacity. (Courtesy of British 
Gas Corporation.) 



Indonesia and Brunei to Japan, and another ten or so routes were under 
active development [1.4]. The shipping terminals are supphed by large 
liquefiers with up to 5000t/day capacity in a single train (Fig. 16.22). 

Apart from storage at hquefaction plants and trading terminals, natural 
gas is stored as liquid for *peak shaving' operations, that is, to provide an 
additional source of gas during periods of peak demand when the normal 
supply system is inadequate (usually in winter). Liquefaction, using small 
(200 t/day) plants takes place during periods of low demand in the summer. 
Storage tanks may be as big as 100 m in diameter and 30 m in height, 
containing teng of thousands of tonnes of hquid (Fig. 1.2). In the past, they 
were usually constructed of either aluminium or 9% nickel steel; now, 
prestressed concrete (with a suitable thin metal liner to eliminate porosity 
problems) is being increasingly used. During the 1960s, a number of tanks 
were formed by excavating a hole in the ground and installing a thin 
steel liner, but this design has proved to be unsatisfactory due to large 
evaporation rates and to an ever-increasing area of frozen ground around 
the tank, although new designs are now being developed in Japan. 



\. HANDS 



. The LNG 
y of British 



;re under 
by large 
i.22). 
i, natural 
ovide an 
e normal 
ing small 
summer. 
1 height, 
)ast, they 
■el; now, 
porosity 
of tanks 
ig a thin 
to large 
i around 
n. 




H H ^ 



10 

B. A. HANDS 

H^f^'J^fxrl^T''^^'^ it has proved economic 

o distnbute LNG by truck and to keep it in small storage vessels close to 
the point of use. The technology adopted is similar to the well-established 
methods used for oxygen and nitrogen. 
Purification ('upgrading') of natural gas is achieved by cryogenic 

methods. Many natural gas sources contain significant quantitiesof nitrogen 
and carbon dioxide, which reduce the calorific value and render the gas 
incompatible with other supplies to the pipeUne distribution network 
Upgrading plants are based on successive Uquefaction and separation of 
nT*TT""?P°°^°*' Sas and are frequently installed at the 

well-head. In these plants, solid impurities (sand, etc.) are filtered, and 
then water, sulphur compounds and carbon dioxide are removed using 
either molecular sieves or chemical absorption, for example, using glycol 
to absorb water or monoethanol amine to absorb carbon dioxide Liquefac- 
tion can then take place without blocking the low-temperature heat 
exchangers with frozen components of the gas. Currently, natural gas 
conipames are projecting a significant increase in the number and size of 
such plants. This mcrease is associated with the use of nitrogen injection 
mto the gas wells to enhance gas recovery, thus creating a double use of 
cryogenics for both injection and rejection, since the nitrogen will be 
produced on-site by the fractional distillation of liquid air 



1. A SURV 



Fig. 1.3 W 



A consic 
compressec 
hospitals. C 
oxidation o 
methanol p 
and in the t 



1.5 Air Separation 

The production of oxygen, nitrogen and argon by the fractional distillation 
of air, or 'air separation' as it is known, forms a vital part of the infra- 
structure of the industrialised world. The major developments have 
occurred since the Second World War: in 1948, a system to produce 140 
t/day of liquid oxygen was built in the United States; in the 1970s plants 
with ten times that capacity were under construction in various parts of the 
world. The daily world production of oxygen is now about 5 x lO^t (Fig 
1.3), a purity of around 99.5% being easily achievable even on this scale 
By far the greatest amount of oxygen is consumed by the chemical and 
steel industries (Table 1.2). Since the daily consumption of a chemical or 
steel works may amount to several hundred tonnes per day, it has become 
common practice to build an air separation plant on an adjacent site and 
deliver the oxygen by pipeline. Because a continuous supply is essential 
stringent conditions may be imposed by the user, and emergency electrical 
generators and back-up storage vessels may have to be provided to guaran- 
tee a supply until faults can be rectified or oxygen brought in by road 



St< 



Nc 
Fa 
Ch. 
I 
I 

^ 

^ 
c 

Pol. 
Mis 



iANDS 

'nomic 
lose to 
)lished 

ogenic 
trogen 
he gas 
twork. 
tion of 

at the 
d, and 
I using 

glycol 
luefac- 
e heat 
ral gas 
size of 
jection 

use of 
will be 



illation 
; infra- 
5 have 
ice 140 

plants 
> of the 

t (Fig. 
5 scale, 
cal and 
lical or 
)ecome 
ite and 
sential, 
ectrical 
>uaran- 
oad- 



1. A SURVEY OF CRYOGENIC ENGINEERING 
200r 



11 




I960 



1965 



1970 



1975 



1980 



1985 



Fig. 1.3 Worldwide annual production rate of oxygen. (Courtesy of R. M. Thorogood.) 



A considerable quantity of oxygen is produced in gaseous form and 
compressed into cylinders to be used, for instance, for welding, in diving and 
hospitals. Other important and growing uses for oxygen are in the partial 
oxidation of coal and heavy hydrocarbons to synthesise gas mixtures for 
methanol production and to produce hydrogen for ammonia production, 
and in the treatment of waste water by activated sludge processes. The use 



Table 1.2 

Industrial Consumption of Oxygen in the United States in 1979* 



Percent of total consumption 



Steel making 

Basic oxygen process 39.6 

Open hearth process 9.3 

Electric furnace 1.7 

Cutting, welding, blast 

furnace air enrichment 14.8 

Total 65.4 

Non-ferrous metals 3.0 

Fabricated metal products 7.0 
Chemicals 

Ethylene oxide 8.2 

Acetylene 3.8 

Titanium dioxide 2.8 

Propylene oxide 2.3 

Vinyl acetate 2.3 

Other 0.6 

Total 20.0 

Pollution control 3.0 

Miscellaneous 1.6 



" From Thorogood [1.3]. 



12 



B. A. HANDS 



1. A SURVEY C 



of oxygen in the production of fuels from coal is expected to increase as 
oD reserves diminish, an important aspect of this being the very large 
consumption which will be required at an individual site, perhaps 20,00G-. 
30,000 t/day: the SASOL II complex which is operational in South Africa 
uses 15,(KK)t of oxygen per day. 

Liquid oxygen is also produced in quantity for use in aerospace activities, 
both as a fuel oxidiser and for life support systems. The amounts required 
can be large: for instance, each Apollo flight to the moon consumed about 
2000 1 (Fig. 1.4), and the annual consumption of the American space 
programme at its peak was about 400,000 1 [1.5]: 

At the same time as oxygen is separated from air, nitrogen is also, of 



Cable duct 




J-2 Engines 



Liquid Hydrogen 
tank 



Insutation 



Insulated 

common bulkhead 



Liquid Oxygen 
tank 



Liquid Hydrogen 
suction tine 



Thrust structure 



Ullage rocket 



Fig. 1.4 Second stage of the Saturn V rocket launcher used for the Apollo flights to the 
moon. This stage was about 25 m high and 10 m diameter. 



course, produc 
oxygen. In th 
by-product an 
developed anc 
production. 

Liquid nitro 
cations, such b 

(1) for coc 
tamination mu 

(2) for free 
uses up to 700 

(3) in the i 
either side of I 
whole system; 

(4) in recla 
of many metal 
cold motor ve 
constituents se 
can be shattere 
which does no 
treated. In Bel; 
being fragment 
consumption o 
from the non-f 

(5) in defla 
deflashing can 
each item indi\ 

(6) in the h 
resistance of ce 

(7) for the 
the cattle induj 

(8) inastroi 

(9) in groui 
to be performe 

(10) in bon 
porarily harmle 

However, th 
for various che 
dependent upor 
for such applici 
and chemical t 



HANDS 

rease as 
ry large 
20,000-. 
a Africa 

:tivities, 
required 
;d about 
m space 

also, of 



ead 



flights to the 



1. A SURVEY OF CRYOGENIC ENGINEERING 

course produced, the current world-wide consumption being about that of 
oxygen In the early years of the industry, nitrogen was considered a 
by-product and sold relatively cheaply. However, new uses have been 
developed and some plants are now biassed more towards nitrogen 

^Tlquid nitrogen is a useful source of cold and finds a diversity of appli- 
cations, such as: 

(1) for cooling cold traps in vacuum systems, especially where con- 
tamination must be avoided, as in semi-conductor device manufacture; 

(2) for freezing food: one major fast-food franchise in the Umted States 
uses up to 700 t/day for freezing hamburgers; 

(3) in the repair of pipeUnes: by freezing the liquid in the pipehne on 
either side of the fracture, a repair can be effected without emptymg the 

whole system; j , u -^i^^^^* 

(4) in reclamation processes, where use is made of the embnttlement 
of many metals and polymers, at low temperatures, when, for instance, 
cold motor vehicle tyres can be pulverised, and the steel and polymer 
constituents separated and re-used; the polymer coating of electric cables, 
can be shattered into small pieces whUe the copper or alumimum conductor, 
which does not become brittle, remains intact. Large items can also be 
treated. In Belgium, for example, complete automobUes are cooled before 
being fragmented; it is claimed that the process reduces the overall energy 
consumption of the process and makes it easier to separate the fenous 
from the non-ferrous (non-embrittled) scrap; , » 

(5) in deflashing of moulded polymer products: in the embnttled state, 
deflashing can be achieved by a tumbling process rather than by treating 
each item individually; 

(6) in the heat treatment of metals: for instance, to improve the wear 

resistance of certain tool steels; .,.,_„ r 

(7) for the storage of biological specimens, especially bull semen tor 

the cattle industry; 

(8) in astronautics, forpre-cooling fuel tankspnorto filhngwith oxygen, 

(9) in ground freezing, to enable tunnelling and excavation operations 
to be performed in wet and unstable soils; 

(10) in bomb disposal, for freezing explosives to render them tem- 
porarily harmless. 

However the widest use for nitrogen is as an inert blanketing gas. 
for various 'chemical and metallurgical processes. The purity required is 
dependent upon use, with medium purities (1-3% oxygen) being acceptable 
for such applications as blast furnace feed systems, coal handling systems 
and chemical tank purging. High purity (less than lOppm oxygen) is 



B. A. HANDS 

essential for many purposes, of which steel anneahng, float glass manu- 
facture and fabrication of semi-conducting devices are important examples. 
Gaseous nitrogen is also used as a feedstock for the production of some 
chemicals, particularly ammonia. For large-scale uses, the nitrogen is sup- 
plied by an on-site plant or by pipehne. In other cases, it is often convenient 
to store the nitrogen as Uquid rather than as gas in cyhnders and vaporise 
it as required. 

As already mentioned, a relatively recent and growing use of nitrogen is 
as a displacing medium in the recovery of oil and gas. By forcing oU or 
natural gas out of the well under pressure, a significant increase in the 
percentage extracted can be achieved. Such applications are of large volume 
and require delivery pressures between 130 and 700 bars. 

The other major constituent of air is argon, which is in great demand for 
inert blanketing when nitrogen is too reactive, and for inert gas-shielded 
welding (TIG, MIG, etc.), although helium tends to be preferred in the 
United States. Because a very high purity (>99.9%) is required for most 
purposes, the impure product from several air-separation plants may be 
sent to a central point for purification. The air-separation industry is, in 
fact, so competitive that the recovery of argon may be necessary to prevent 
a plant running at a loss. The demand for argon is increasing rapidly, and 
it is possible that in the future some air-separation plants will be operated 
for the production of argon only, the nitrogen and oxygen being discarded. 
Although much argon is suppUed as compressed gas, it is more economical 
for even moderate users to receive and store argon as liquid. 

Of the minor constituents of air (Table 1.3), neon, krypton and xenon are 
extracted mainly for use in the lamp industry and laboratory instruments. It 
is not at present economic to recover hehum due to its availabiUtv from 
LNG weUs. 



Table 1.3 

Potential Yield of Atmospheric Rare Gases from a 1000 t/day Oxygen Plant« 



Total in air passing 

through plant Typical yield 

(mVhr at NTP) (%) CyUnders per day 



Argon 


1395 


55 


2800 


Neon 


2.7 


60 


6 


Helium 


0.75 


60 


. 2 


Krypton 


0.17 


30 


0.2 


Xenon 


0.014 


30 


0.015 



From Thorogood [1.3]. 



1. A SURV 

1.6 Liquid 

Hydrogen 
explosive ( 
(0.02 mJai 
no unusua 
1970s, whe 
Its imports 
for exampl 
Hydroge 
hydrocarbc 
gas or fuel 
scale, elecl 
due maini) 
hydrocarbc 
burning hy 
Electrolytic 
hydrogen. ^. 
since it cle2 
the resultin 
tigation of 
thermochen 
Hydrogei 
(Chapters 1 
higher. A cc 
and para (C 
conversion i 
being usual 
Care must a 
oxygen whi< 
believed, ca 
perature pai 
Liquid hy 
nuclear phys 
a target for i 
from the en^ 
to measure 
interactions ; 
volume of lie 
of a charged 
a piston in oi 



B. A. HANDS 

lat glass manu- 
rtant examples, 
action of some 
litrogen is sup- 
?ten convenient 
:^ and vaporise 

e of nitrogen is 
' forcing oil or 
ncrease in the 
)f large volume 

;at demand for 
rt gas-shielded 
referred in the 
uired for most 
plants may be 
industry is, in 
;ary to prevent 
.g rapidly, and 
Jl be operated 
ang discarded, 
re economical 
d. 

and xenon are 
nstruments. It 
lilability from 



nPlanf 



)er day 



1. A'SURVEY OF CRYOGENIC ENGINEERING ^ 
1.6 Liquid Hydrogen 

Hydrogen gas is a somewhat hazardous substance to handle due to its wide 
explosive concentration range with air (4-72%) and its low ignition energy 
(0.02 mJ at 30% concentration), although the liquid itself appears to present 
no unusual problems and was in wide use for cooUng purposes until the 
1970s, when liquid helium became more easily available in large quantities 
Its importance as a cryogen has declined considerably since then, so that 
for example, in Great Britain it is no longer commerciaUy available 

Hydrogen gas is produced on a large scale by the reaction of steam with 
hydrocarbons, particulariy natural gas, or by the partial oxidation of natural 
gas or ftiel oil. The gasification of coal may also be used. On a smaller 
scale, electrolysis of water is used, in spite of its higher cost, which is 
due mainly to the higher binding energy of hydrogen in water than in 
hydrocarbons, to the high cost of electricity (itself often produced by 
burning hydrocarbons), and to the low efficiency of electrolytic cells 
Electrolytic hydrogen may cost twice as much as the cheapest 'chemical- 
hydrogen There is currently interest in developing hydrogen as a fuel, but 
since it clearly does not make sense to produce it from other fuels (with 
the resulting overall loss in available energy), there is widespread inves- 
tigation of methods for producing hydrogen from water using various 
thermochemical methods. 

Hydrogen may be liquefied using cycles similar to those in use for heUum 
(Chapters 13 and 15), except that the cycle pressures are about five times 
higher. A comphcation is that, because hydrogen exists in two forms, ortho 
and para (Chapter 2), the inclusion of catalysts to promote ortho-to-para 
conversion must be considered. Great care must be taken with safety, it 
being usual to provide a blast wall between the liquefier and its operators 
Care must also be taken to free the hydrogen from impurities, especially 
oxygen which can promote unwanted ortho-para conversion, and it is 
believed, cause an explosion if accumulated as solid in the lower tem- 
perature parts of the plant. 

Liquid hydrogen still finds two particular applications. In high-energy 
nuclear physics experiments, liquid hydrogen or deuterium may be used as 
a target for the particles produced from the accelerator. More interesting 
from the engineering point of view is the bubble chamber, which is used 
to measure the properties of charged particles and to elucidate their 
mteractions and decays. A bubble chamber consists essentiaUy of a closed 
volume of hquid held at a pressure well above saturation. On the passage 
of a charged particle, the pressure is rapidly reduced, usually by means of 
a piston in one wall of the chamber, so that the liquid is in the superheated 



16 

B. A. HANDS 

Ttaken 'and r ""h"^"' '^'"^^ P^'''''^- ^ ^'^^^^ Photograph 
^ taken, and tfie liquid is recompressed before bulk boiling occurs the 

tttZtVs'o r /r °' ^ '^^^^ Hiago'et^^rou^d 

ine cnamber so that the momentum of the particle can hp h^h.i^^h f 

favoured he'. •'"^ hydrogen and deuterium 'are paSarW 

favoured because their simpler nuclear structure allows a more str^St 

cnosen lor the fuel of the second and third stages of the rocket for th^ 

^ tonnes (1300 m ) of liquid hydrogen (Fig. 1.4): in the late 1960s the 
^encan space programme was using about 40 000 t/year1l SWn tt 

Ihr^Til.Tr^u'' t"""^ ^""^ ^y^^^g^'^ has a calorific value Zu 
three t mes higher than kerosene (which was used for the first sta Je of 
Apollo) Its calorific value per unit volume is about three ti^eslolXus 

^ZToZt^::^^^ ~' -^^h^y. Pa-icularly 

as ^ZH^f" widespread discussion of the possibility of using hydrogen 
a" irtiy meX^^^^ '"T^'!,"" " ^"^P"- diminish' IhoS 

hydrogen is however, a major problem. Storage as metal hydrfde iTO 
a large weight and cost penalty because of the metals use^and S^w 

larreteTtrnraTmf r 'T' ^'^^^'^ h"tXS 
(aoout 15%) can be made by using a mixture of solid and liquid-'slush 
hydrogen'. Considerable care would have to be taken in the di^sa^of 
^^il-off in a safe way. Perhaps a more serious drawback's theTe ° 
required for liquefaction, which may amount to as much as a third of £ 



B. A. HANDS 



o photograph 
g occurs, the 
let surrounds 
leduced from 
ocarbons and 
; particularly 
lore straight- 
rogen bubble 
lining several 
led by other 
ler chambers 

produced in 
gen, it has a 
for instance, 
)cket for the 
jumed about 
e 1960s, the 
[1.5]. In the 

120 tonnes 
value about 
irst stage of 
lower. Thus 
fuelled with 

particularly 

ag hydrogen 
h, although 
f producing 
:he question 
isily ignited 
;e hydrogen 
that overall 
; storage of 
des imposes 
id their low 
>ut requires 
in volume 
uid — 'slush 
disposal of 
the energy 
hird of the 



5 




'° B. A. HANDS 

calorific value of the fuel liquefied. This, together with the present high 
cost of production from non-hydrocarbon sources, makes hydrogen econ- 
omically unattractive, although several experimental automobiles have 
been successfully run with hquid hydrogen as fuel for a number of years. 



1.7 Liquid Helium 

The importance of helium to the physicist and cryogenic engineer is that it 
is the only route to temperatures below about 10 K, apart from magnetic 
cooUng methods which are unUkely to become practical on anything but a 
very small scale. The provision of helium refrigeration is, therefore, a 
necessary adjunct to the use of superconducting magnets. 

The largest sources of helium in the western world are currently the 
natural gas wells of the states of Texas and Kansas in the United States. 
Wells in Poland, Northern Germany and the USSR (at Orenburg) also 
produce large quantities. Helium is present in these wells at a concentration 
of about 0.2-0,7% and is extracted by Hquefying the other constituents. 
Although at present there is plenty of helium available, there are worries 
that if the growth in both size and number of superconducting magnets 
continues at the present pace, there could be a severe shortage in a few 
decades as natural gas wells become exhausted, even though the United 
States has considerable quantities of hehum stored in underground porous 
rock— a result of the so-called 'conservation' programme which has now 
been discontinued [1.6]. Outside America, 'conservation' has a rather 
different connotation— that of recycling the gas after use, rather than 
exhausting it to the atmosphere. Such recovery is usually justifiable on 
economic grounds alone, since gaseous hehum is not cheap, but it is worth 
noting that large quantities are used in welding and in oxygen-helium 
atmospheres for diving, from which helium recovery is not feasible. 

A major landmark in the development of helium technology came in 
1946 with the design by Professor Sam CoUins of a liquefier which did not 
require the feed helium to be pre-cooled and which could be operated 
continuously for long periods. Previous to this, small-scale experiments 
were done by liquefying helium in situ, for example, by precooling with 
liquid hydrogen (sometimes itself produced in situ) and then adiabatically 
expanding. Continuous liquefaction was achieved using cascade cooling 
with Hquid air (or nitrogen) and hydrogen followed by Joule-Thomson 
expansion. The latter method could produce a few litres of helium per 
hour, but required the simultaneous operation of both a hydrogen and a 
hehum liquefier, the Hquid air or nitrogen usually being available from a 
commercial source, 



1. A SURVEY OF 

The ColUns : 
proved to be a 
meant that fairi 
still marketed to 
bearings were d 
Uquefiers, and s> 
refrigerators. Tl 
engine, have no 
high efficiency. ' 
liquefiers. 

Another probi 
to compress the 
since all will fret 
is especiaUy imf 
to be run contij 
contaminations 1 
believed that wj 
blockages in one 
received general 
based, piston rin 
compressors, bei 
reciprocating cor 
require a sophisti 
for a malfunctior 
refrigerator itseli 
more frequent m 
for more massivi 
tamination is sim 



1.8 Superconduct 

Perhaps the one ; 
has been the exj 
conductivity or tl 
phenomenon was 
major part in elect 
was destroyed, by 
presence of a mag 
remained unfulfii: 
'high-field' supero 
remain supercond 



B. A. HANDS 



1. A SURVEY OF CRYOGENIC ENGINEERING 



19 



present high 
Irogen econ- 
lobiles have 
ber of years. 



leer is that it 
3m magnetic 
lything but a 
therefore, a 

:urrently the 
nited States, 
inburg) also 
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The Collins liquefier, which used a reciprocating expansion engine, 
proved to be a reliable machine, although the presence of rubbing seals 
meant that fairly frequent maintenance was required; its derivatives are 
still marketed today. During the 1950s, high-speed turbines running on gas 
bearings were developed as the external work components for hydrogen 
liquefiers, and soon afterwards this technique was incorporated in helium 
refrigerators. These turbines, although less robust than a reciprocating 
engine, have no rubbing surfaces and can achieve a large throughput at 
high efficiency. They are now usually specified for large refrigerators and 
liquefiers. 

Another problem in the design of refrigerators arises from the necessity 
to compress the gas. The helium feed must be free of oil, water and air, 
since all will freeze at some point in the system and cause blockages: this 
is especially important today, when superconducting systems may have 
to be run continuously for many months. To achieve such service, oil 
contaminations less than 1 part in 10^ may have to be specified, and it is 
believed that water contamination of about 3 parts in 10^ has caused 
blockages in one system [1.7]. Two types of compressor appear to have 
received general acceptance, reciprocating compressors with dry, polymer- 
based, piston rings, and oil-flooded screw compressors. Oil-flooded screw 
compressors, being rotating machines, suffer from fewer problems than 
reciprocating compressors and are more compact and vibration-free, but 
require a sophisticated oil-removal system. Furthermore, it is not unknown 
for a malfunction to occur such that much of the oil is deUvered into the 
refrigerator itself. Reciprocating compressors have the disadvantage of 
more frequent maintenance intervals, more vi