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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, 1994 



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, James W. Leonard, being duly sworn, do hereby depose and state: 

I received a A.B. degree in Physics from the University of California at Santa Barbara 
(1962), and a M.S. and PhD. degree in Physics (1968) from the University of Oregon, 
Eugene, and an M.LS. in Library Science from the University of Western Ontario 
(1972), London. 

I have worked as a science librarian in the Thomas J. Watson Research Center from 
1978 to the present. On December 2, 1998, 1 did a citation search in the SciSearch 
database on the Dialog on line system of the article J. G. Bednorz and K. A. Muller, 
Zeitschrift fur Physik B- Condensed Matter, 64 , pp. 189-193 (Sept. 1986). The result 
YO987-074BY 1 



AFFIDAVIT UNDER 37 CFR 1.132 





of that search is below. There are a total of 5689 articles which refer to 1986 article of 
Bednorz and Muller: 1 in 1986, 839 in 1987, 1163 in 1988, 793 in 1989, 594 in 1989 
and the remainder in the years from 1990 to the present. 



SYSTEM; OS - DIALOG OneSearch 

File 434:SciSearch(R) Cited Ref Sci 1974 - 1989/Dec 

(c) 1998 Inst for Sci Info 

File 34:SciSearch(R) Cited Ref Sci 1990 - 1998/Nov W4 

(c) 1998 Inst for Sci Info 



Set 


Items 


Description 


SI 


5689 


CR=BEDNORZ JG, 1986, V64, P189, ? 


S2 


1 


SI AND PY=1986 


S3 


839 


SI AND PY=1987 


S4 


1163 


SI AND PY=1988 


SB 


793 


SI AND PY=1989 


S6 


594 


SI AND PY=19 9 0 



SEARCH RESULTS 





^4 



No. -ro ;8676 
Qualified in Westchester County 
Commission Expires March \G 19,^7 



DANIEL P. MORRIS 
NOTARY PUBI. l c state of New York 



YO987-074BY 



2 



COPPER OXIDE 
SUPERCONDUCTORS 



Charles P. Poole, Jr. 
Timir Datta 
Horacio A. Farach 

with help from 

M. M. Rigney 
C. R. Sanders 

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




WILEY 

A Wiley-Intersciencc Publication 
JOHN WILEY & SONS 

New York • Chichester • Brisbane • Toronto • 



Copyright © 1988 by John Wiley & Sons, Inc. 



All rights reserved. Published simultaneously in Canada. 

Reproduction or translation of any part of this work 
beyond that permitted by Section 107 or 108 of the 
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 Department, John Wiley & Sons. Inc. 

Library of Congress Cataloging in Publication Data: 
Poole. Charles P. 

Copper oxide superconductors Charles P. Poole. Jr.. Timir Datta. 

and Horacio A. Farach: with help from M. M. Rigney and C. R. Sanders, 

p. cm. 

**A Wilcy-lntcrscionce publication." 
Bibliography: p. 
Includes index. 



I. Copper oxide superconductors. I. Datta. Timir. II. Farach. 
Horacio A. III. Title. 

OC61I.98.C64P66 1988 
539.6'23-dc 19 88-18569 CIP 
ISBN 0-471-62342-3 

Printed in the United States of America 



10 987654321 




PREFACE 



The unprecedented worldwide effort in superconductivity research that has 
taken place over the past two years has produced an enormous amount of experi- 
mental data on the properties of the copper oxide type materials that exhibit 
superconductivity above the temperature of liquid nitrogen. The time is now ripe 
to bring together in one place the results of this research effort so that scientists 
working in this field can better acquire an overall perspective, and at the same 
time have available in one place a collection of detailed experimental data. This 
volume reviews the experimental aspects of the field of oxide superconductivity 
with transition temperatures from 30 K to above 120 K, from the time of its 
discovery by Bednorz and Mailer in April 1986 until a few months after the 
award of the Nobel Prize to them in October 1987. During this period a consis- 
tent experimental description of many of the properties of the principal super- 
conducting compounds such as BiSrCaCuO. LaSrCuO, TIBaCaCuO, and YBa- 
CuO has emerged. At the same time there has been a continual debate on the 
extent to which the BCS theory and the electron-phonon interaction mechanism 
apply to the new materials, and new theoretical models are periodically pro- 
posed. We discuss 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 evolving, and some 
ideas 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 work, 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. 



Ti PREFACE 

The literature has been covered almost to the end of 1987, and some 1988 
work has been discussed. This has been an enormous task, and we apologize for 
'any omissions in the citing and discussion of articles* 

We wish to thank the following for giving us some advanced notice about their 
work: R. Barrio, B. Battlogg, L. A. Boatener, G. Bums, J. Drumheller, H. Eno- 
moto, P. K. Gallagher, R. Goldfarb, J. E. Graebner, R. L. Greene, J. Here- 
mans, T. C. Johnson, J, K. Karamas, M. Levy, J. W. Lynn, A. Malozemoff, K. 
A. MCiller, T. Nishino, N. Nucker, J. C Phillips, R. M. Silver, G. Shirane, J. 
Stankowski. B. Stridzker, S. Tanigawa, G. A. Thomas, and W* H. Weber. We 
appreciate comments on the manuscript from S. Alterowitz, C. L, Chien, D. K. 
Finnamore, J. Goodenough, J. R. Morton, and C Uher, and helpful discussions 
with L Budnick, M. H. Cohen, M. L. Cohen, R. Creswick, S. Deb, M. Fluss, A. 
Freeman, D. U. Gubser, A. M. Hermann, V. Z. Kresin, H. Ledbetter, W. E. 
Pickett, M. Tinkham, C. E. Violet, and S. A. Wolf. Support from the University 
of South Carolina, the Naval Research Laboratory, and the National Science 
Foundation Grant ISP 80 11451 is gratefully acknowledged. 

Michael A. Poole helped to develop the computer data storage techniques 
that were used. Jesse S. Cook is thanked for editorial comments on the manu- 
script. C. Aimasan, S. Atkas, J. Estrada, N. Hong, O. Lopez, M. Mesa, T. 
Mouzghi, and T. Usher are thanked for their interest in this project. 



Charles P. Poole, Jr. 
Timir Datta 
Horacio A. Farach 



Columbia. South Carolina 
July 1988 




" * 7 . *' - ; 




•ects of the BCS theory, however, 

'd detailed treatment of the prop- 
see the extent to which they con- 
ey agree with some of the other 
n these two chapters. 



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. 

The superconducting properties of the copper oxide compounds are quite 
sensitive to the method of preparation and annealing. Multiphase samples con- 
taining fractions with T c 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-l 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 T c of a BiSrCa- 
CuO pellet, a related copper-enriched specimen, and an aluminum-doped coun- 

59 




60 PREPARATION AND CHARACTERIZATION OF SAMPLES 




Fig V-l. Effects of heat treatments on the resistivity transition of BiSrCaCuOn U) 
calcined at 860°C, (b) calcined at 885°C, (c) calcined at 901 °C. (</) aluminum-dopd 
sample calcined at 875°C, prolonged annealing, (e) copper-rich sample calcined 1* 
860°C, (/) aluminum-doped sample calcined at 885°C, slow quenching and (g) aScuti 
at 885°C. prolonged annealing, and slow quenching (Chuz5). 



terpart (Chuz5). These samples were all calcined and annealed in the same tern- 
perature range and air-quenched to room temperature. 

Polycrystalline samples are the easiest to prepare, and much of the early w« 
was carried out with them. Of greater significance is work carried out with Una 
films and single crystals, and these require more specialized preparation tech- 
niques. More and more of the recent work has been done with such « m P«V 
Many authors have provided sample preparation information, and owen 
have detailed heat treatments and oxygen control. Some representative tee* 
niques will be discussed. 

The beginning of this chapter will treat methods of preparing bulk supertax 
ducting samples in general, and then samples of special types such as 
and single crystals. The remainder of the chapter will discuss ways of ch«*«j 
the composition and quality of the samples. The thermodynamic or subsow* 
phase diagram of the ternary Y-Ba-Cu oxide system illustrated .n Fig. v z o» 
tains several stable stoichiometric compounds such as the ^P^fjj 
Y,0,, BaO, and CuO at the apices, the binary oxides stable at 950 , ■ 
BaiCuO, BaCuO, Y 2 Cu 2 O s , Y 4 Ba 3 0„ Y 2 Ba0 4 , and (Y^W. *J* 
edges, and ternary oxides such as (YBa 3 Cu 2 0 7 ), the semiconducting green pn- 
Y 2 BaCuO s , and the superconducting black solid YBa 2 Cu 3 0,. 4 in the mi 
(Beye2, Bour3, Capol, Eagll, Frase, Hosoy, Jonel, Raise, Kurth. 
Leez3, Lianl, Malil, Schni, Schnl, Schul, Takay. Torra, Wagne). Compoo^ 
in parentheses are not on the figure, but are reported by other »° r * 
existence of a narrow range of solid solution was reported (Pansoj. 
argued against (Wagne) by the same group. 



vMPLES 



METHODS OF PREPARATION 61 



CuO 



300 




Y 2 Cu20 5 



ransition of BiSrCaCu0 7 ^ (a) 
t 901 °C f (d) aluminum-doped 
'pper-rich sample calcined at 
3w quenching and (g) calcined 
iz5). 



annealed in the same tern- 
re. 

tnd much of the early work 
work carried out with thin 
cialized preparation tech- 
done with such samples, 
i information, and others 
Some representative tech- 
preparing bulk supercon- 
ial types such as thin films 
I discuss ways of checking 
modynamic or subsolidus 
llustrated in Fig. V-2 con- 
as the end-point oxides 
.table at 950°, (Ba 3 Cu0 4 ), 
nd (Y 2 Ba 4 0 7 ), along the 
Tiiconducting green phase 
!a 2 Cu 3 07-4 in the interior 
I, Kaise, Kurth, Kuzzz, 
rra, Wagne). Compounds 
d by other workers. The 
sorted (Panso), and then 



BaO 




Ba 3 Y 4 09 BaY 2 Q 4 



Compound 


Slowly cooled 
to room temperature 


123 


- YBaaCuaOej^ 


o 7 


143 


- YBa4Cu 3 O flJ+6 


O9 


385 


- YaBaeCusOt/i^ 


o 1B 


152 


YBa5Cu20 ej+4 




211- 


Y 2 BaCuO s 






Ba2Cu0 3+4 





Stc^iSo 7 Sm.t gram ° f ** A Yj °- Ba0 - Cu0 « 950OC. The green 

Fiiase |i 2 Ba<_uU s , (211)] the superconducting phase [YBa,Cu.O, , *„a .u 

other compounds are shown in the interior of fhe diagram (Del£) 



B. METHODS OF PREPARATION 

!t n at t e hiS »n e e C l° n thre * n \ ethods of Preparation will be described, namely, the solid 
Sid s t?T C ' P ° n ' thC **-** techni <^ (Hatfi). The widely used 
»W-state techmque permits off-the-shelf chemicals to be directly calcined into 
superconductors, and it requires little familiarity with the subtle physicochent 

iSSTSr 1 " tranSf0rmati0n ° f 3 °< comUndstr 

•to^S^?* CO f preC,p,ta !' 0n teChniqUC mixes the constituents on an 
atom.c scale and forms f.ne powders, but it requires careful control of the P H 
and some fam.harity with analytical chemistry. The sol-gel procedure requires 
more competence in analytical procedures. ceaure requires 

of the!" ^V 1 -^ rCaCti0n techni <J ue one «arts with oxygen-rich compounds 
T Y C ° m P°" ents »«* « oxides, nitrates, or carbonates of Ba, Bi, £ 
o 'iH 0F elements " Sometimes nitrates are formed first by dissolving 
ox.des ,n n.tnc ac.d and decomposing the solution at S00°C before cZnZt 



62 PREPARATION AND CHARACTERIZATION OF SAMPLES 

(e g., Davis, Holla, Kelle). These compounds are mixed in the desired atomic 
rat.os and ground to a fine powder to facilitate the calcinat on process Sn 

Hod( Thr)7 T U :T blC S3ltS ^ reaCted by Ca,ci " in « an' xtondeJpe 
nod ( ~ 20 hr) at efcvated temperatures ( « 900°C). This process may be repeated 

each step. As the reaction proceeds, the color of the charge changes The process 
usually ends w.th a final oxygen anneal followed by a slow cif down to7«Sm 
temperature of the powder, or pellets made from the powder, by ZZZeTn a 
cold or hot press. Sintering is not essential for the cLmica p^ ss bSt for 
ran S rt d oth measurements ft ^ tQ J^/^^ 

aed. A number of researchers have provided information on this solute re- 
act.on approach (e.g.. Allge. Finez. Galla. Carta. Gopal. Gubse H* kl win 
Hem„ Hikal Hirab. Jayar. Maenl. Moodl. M00S2, N eU me'. Polo 

sle m RU r iC ' '"I 0 ' Saitl> SaWa1 ' Sham °' Takit ' Toth;. Wu^r ' 
Some of the earher works on foils, thick films, wires, or coatings employed a 
suspense of the calcined powder in a suitable organic binder, and the Sred 

s7a d y r g ,Tcts ed by — ai ***** ~ - 

In the second or coprecipitation process the starting materials for calcination 

Ue Z 7wl1 2 ^ P S it t 8 T m t08ethCr fr ° m S0, " ti0n < e *. n n °o 
sea" In adltion n '^f anta S e ° f the constituents on an atomi 

D e con " Herf ^ P^ftates ™y form fine powders whose uniformity can 
be controlled, wh.ch can ehminate some of the labor. Once the precipitate ha, 
been dned calcining can begin as in the solid-state reaction p^edure ? A di^T 

tist ; is concerned, Is that it requires considerable skill in chemical procedures 

Another procedure for obtaining the start-up powder is the «£SS5e 
.n wh.cn an aqueous solution containing the proper ratios of Ba Cu and V 
t" 'add" I 5 em f if h iet ! b an °* a ™ P«-e and the resulting drop.* ^'are geJed by 
ac d 3 h,gh - m0,ecu,a — W Primary amine which extracts the nitric 

Z ted to Y P Ba C CO WaS "TS? 3PPlied t0 ^ U materiaIs ' but has b -" 
rectea tor YBaCuO as well (Cimaz, Hatfi). 

cess^orw^rr't' ChCmiCaI SUpP " eS t0 faci,itate the calcination pro- 
cess a dry or wet (acetone) pregrinding with an agate mortar and pestle or a ball 
m... ,s recommended. Gravimetric amounts of the powdered p«cu^ m reriah 
are thorough., m.xed and placed in a platinum or^ramic cLio^T" 
be taken to ensure the compatibility of the ceramic crucible with the chemTcaTs to 
obv.ate reaction and corrosion problems. cnemicals to 

Complete recipes for the YBa* material have been described (e g Gran2) 

green Y°B a CuO oh?* ^ Ch ™^ CO,or f ™ the 

chZ* f 1 5 P C '° the d3rk gra * YBa^O,^ compound. Then the 

warrf n ;id a h r Ut ' ^ * to ^ine its pu *y I 

u arranted by the powder pattern X-ray scan, the calcination process is repeated 
Often, at th.s stage the material is very oxygen poor, and e.e'ctrica ly i Tsemt 



COPPER OXIDE 
SUPERCONDUCTORS 



Charles P. Poole, Jr. 
Timir Datta 
Horacio A. Farach 

with help from 

M. M. Rigney 
C. R. Sanders 

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




WILEY 

A Wiley- Interscience Publication 
JOHN WILEY & SONS 

New York • Chichester * Brisbane • Toronto • Singapore 

j 

HI 



Copyright © 1988 by John Wiley & Sons. Inc. 



All rights reserved. Published simultaneously in Canada. 

Reproduction or translation of any part of this work 
beyond that permitted by Section 107 or 108 of the 
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 Department, John Wiley & Sons. Inc. 

Library of Congress Cataloging in Publication Data: 
Poole. Charles P. 

Copper oxide superconductors Charles P. Poole. Jr.. Timir Datta. 
and Horacio A. Farach; with help from M. M. Kigncy and C. R. San 
p. cm. 

"A Wiley- Imcrscience publication." 
Bibliography: p. 
Includes index. 

1. Copper oxide superconductors. I. Datta. Timir. II. Farach. 
Horacio A. III. Title. 

QC611.98.C64P66 1988 
S39.6'23-dc 19 88 18569 CIP 
ISBN 0-471-62342-3 

Printed in the United States of America 



10 987654321 




PREFACE 



The unprecedented worldwide *fWt ;~ 

mental data on the pro^ni of the £ ^"^^"^"^'"ountofexperi- 
superconductivityaboveCll atu Zf r r that e * hibi ' 

to bring together in one ptl tTr«uks ^ 'h" ""T ^ ^ " "° W r '> e 
working in this field can Abetter acauirl \ T""* ^ S ° that Scientis,s 

time have avai.able in one p£ a co ectbn^T FT**™' ^ " the Same 
volume reviews the exneriml? f °" ect,on of deta,,ed experimental data. This 

d.scovery by Bednorz and Muller in Anril io»T , m the t,me of ils 

^^^P^u^^^ 1 ^^ a ^ months after the 
tent experimental description of manv of the g ,h ' S PCri ° d a consis - 

conducting compounds such a K^C r n ^, P ™P erU ™ of the principal super- 
CuO has emerged. M ^£^£*™' ^ and yL- 
extent to which the BCS theory an^he eStron oho ' """""^ ^ 0 " the 
apply to the new materials and lw th™ ? ? °" '"faction mechanism 
posed. We discuss these 1,1 Z h are p ro - 

with transition metal and oThe? D "evr ou ;. W I en appr ° pria,e - ™* comparisons 

^as ^^™^~^vi t y is stiH evo.ving, and some 

Nevertheless, it is helpful to discuss fheJ h . ■ "** 3ppear in P rint 
progress, to give coherence ^^Z^^ m ° i" 
future work. It is hoped that in the noTtL h / ? t0 Pr ° V ' de guidance for 
down enough to pern£ a ^ ~ 



V 

H3 




vi PREFACE 

The literature has been covered almost to the end of 1987, and some 1988 
work has been discussed. This has been an enormous task, and we apologize for 
any omissions in the citing and discussion of articles. 

We wish to thank the following forgiving us some advanced notice about their 
work: R. Barrio, B. Battlogg, L. A. Boatener, G. Burns, J. Drumheller, H. Eno- 
moto, P. K. Gallagher, R. Goldfarb, J. E. Graebner, R. L. Greene, J. Here- 
mans, T. C. Johnson, J. K. Karamas, M. Levy, J. W. Lynn, A. Malozemoff, K. 
A. MUller, T. Nishino, N. Nucker, J. C. Phillips, R. M. Silver, G. Shirane, J. 
Stankowski, B. Stridzker, S. Tanigawa, G. A. Thomas, and W. H. Weber. We 
appreciate comments on the manuscript from S. Alterowitz, C. L. Chien, D. K. 
Finnamore, J. Goodenough, J. R. Morton, and C. Uher, and helpful discussions 
with J. Budnick, M. H. Cohen, M. L. Cohen, R. Creswick, S. Deb, M. Fluss, A. 
Freeman, D. U. Gubser, A. M. Hermann, V. Z. Kresin, H. Ledbetter, W. E. 
Pickett, M. Tinkham, C. E. Violet, and S. A. Wolf. Support from the University 
of South Carolina, the Naval Research Laboratory, and the National Science 
Foundation Grant ISP 80 11451 is gratefully acknowledged. 

Michael A. Poole helped to develop the computer data storage techniques 
that were used. Jesse S. Cook is thanked for editorial comments on the manu- 
script. C. Almasan, S. Atkas, J. Estrada, N. Hong, O. Lopez, M. Mesa, T. 
Mouzghi, and T. Usher are thanked for their interest in this project. 

Charles P. Poole, Jr. 
Timir Datta 
Horacio A. Farach 

Columbia. South Carolina 
July 1988 



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MORRIS, DAN 

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Magnetic and nonmagnetic particles and fluid, methods of 
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INVENTOR: Ziolo, Ronald F., Webster, New York 

DETDESC : 

"~ ... described in U.S. Pat. No. 4,474,886 to Ziolo. Examples of the precursor 
ions which may be used includes those derivable from transition metal ions, such 
as iron, cobalt, nickel, manganese, vanadium, chromium, rare earths and the 
like. In the case of a non-magnetic colloid, this may include ions of, for 
example, sulfur, selenium, gold, barium, cadmium, copper, silver, manganese, 
molybdenum, zirconium, gallium, arsenic, indium, tin, ... 

. . . ions which can be incorporated into the resin beads to form both 

Al- 



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Probe compositions for chromosome identification and methods 

INVENTOR: Bittner, Michael L., Naperville, Illinois 
Morrison, Larry E., DuPage County, Illinois 
Legator, Mona S., Chicago, Illinois 

SUM: 

... capable of reacting, and a fluorophore group may have already reacted, 
with a linking group. A fluorescent compound may include an organic chelator 
which binds a luminescent inorganic ion such as a rare earth like terbium, 
europium, ruthenium, or the like. 

The term "linking compound" or "linking group" as used herein generally 
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Memory disk sheet stock and method 

INVENTOR: Bartges, Charles W., Delraont, Pennsylvania 
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Hyland, Jr., Robert W., Oakmont, Pennsylvania 
Jensen, Craig L. , Pittsburgh, Pennsylvania 
Tarcy, Gary P., Plum, Pennsylvania 
Vinnedge, K. Dean, Bettendorf, Iowa 
Skeen, Troy C, Bettendorf, Iowa 

DETDESC : 

. . . automatically grouped with this same series of elements even though it 
often performs the same function as scandium, or other "true" rare earths in an 
alloy composition. It is believed that minor amounts of still other rare 
earths, like erbium, thulium, lutetiura^ ytterbium, or another rare earth 
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Epitaxy of high T[C ] superconductors on silicon 

INVENTOR: Himpsel, Franz J., Mt . Kisco, New York 

SUM: 

... as well as to understand the basic mechanisms for superconductivity in 
this class of materials. 

A2. 



Bednorz and Mueller ^rst showed superconducting beha^Rr in mixed 
copper-oxides, typically including rare earth and/or rare earth- like elements 
and alkaline earth elements, for example La, Ba, Sr, , . . , and having a 
perovskite- like structure. 

Materials including the so called "1-2-3" phase in the Y-Ba-Cu-0 ... 

DETDESC : 

• . • EMBODIMENTS 

A technique is provided for depositing high T[c ] superconducting copper-oxide 
based materials epitaxially on Si (001). Typically, these classes of 
superconducting materials include a rare earth or rare earth- like element and/or 
an alkaline earth element. Representative formulas for such materials are the 
following : 

(A[l- chi ]B chi )2Cu oraicron [A- epsilon ] 
and 

AlB2Cu30[7- epsilon ] 

where A is a trivalent element ( e.g., ... 

... in the art that the present invention applies to epitaxial structures 
including silicon (001) surfaces and any copper oxide superconductor thereon. 
Thus, the teaching of this invention can include copper-oxide based compositions 
having any combinations of rare earth or rare earth- like elements and/or 
alkaline earth elements as well as copper oxide superconductors which do not 
contain rare earth elements. Further , it will be apparent to those of skill in 
the art that the Si (001) surface is ... 

LEVEL 1 - 5 OF 68 PATENTS 

5,573,574 

Nov. 12, 1996 

Electroref ined aluminium with a low content of uranium, 
thorium and rare earths 

INVENTOR: Leroy, Michel, St. Egreve, France 

SUM: 

... applications specifies a minimum Al content of above 99.9995%, (and even 
sometimes above 99.9997%) and a U + Th content of less than 1 ppb, and even 
sometimes less than 0.3 or 0.1 ppb. 

Rare earths, some of which, like samarium, have a significant alpha 
radioactivity, are also undesirable. By way of example, 10 ppb of natural 
samarium emits as many alpha particles as 0.1 ppb of uranium 238. The high 
purity . . . 

LEVEL 1 - 6 OF 68 PATENTS 

5,569,759 

<=2> GET 1st DRAWING SHEET OF 25 

Oct. 29, 1996 

Water soluble texaphyrin metal complex preparation 

INVENTOR: Sessler, Jonathan L. , Austin, Texas 
Hemmi, Gregory W., Austin, Texas 
Mody, Tarak D. , Austin, Texas 

DETDESC: 

fv2> 



... C), 10.24 (s, 2^ArH), 12.23 (s, 2 H, CH=N); U.fl^s: lambda [max 
]420.0, 477.5, 730.0; FAB MS M< + > 811. 



Other lanthanide and rare earth- like metal complexes may be synthesized 
including the Gd< + 3> , Lu< + 3> , La< + 3> , In< + 3> , and Dy< + 3 > 
complexes . 

EXAMPLE 4 

Synthesis of B2T2 TXP, see FIGS. 7A and ... 

LEVEL 1 - 7 OF 68 PATENTS 

5,567,564 

<=2> GET 1st DRAWING SHEET OF 7 

Oct. 22, 1996 

Liquid development composition having a colorant comprising 
a stable dispersion of magnetic particles in an aqueous 

medium 

INVENTOR: Ziolo, Ronald F. , Webster, New York 
DETDESC: 

... described in U.S. Pat. No. 4,474,886 to Ziolo. Examples of the precursor 
ions which may be used includes those derivable from transition metal ions, such 
as iron, cobalt, nickel, manganese, vanadium, chromium, rare earths and the 
like. In the case of a non-magnetic colloid, this may include ions of, for 
example, sulfur, selenium, gold, barium, cadmium, copper, silver, manganese, 
molybdenum, zirconium, gallium, arsenic, indium, tin, ... 

. . . ions which can be incorporated into the resin beads to form both 
single-domain and multidomain magnetic particles include: those derivable from 
transition metal ions, such as iron, cobalt, nickel, manganese, vanadium, 
chromium, rare earths and the like. These ions generally exist in the form of 
chlorides of the metal involved such as ferrous chloride, ferric chloride, 
copper chloride, nickel chloride, and the like. The corresponding iodides, 
bromides and fluorides may also be suitable. ... 

LEVEL 1 - 8 OF 68 PATENTS 

5,554,428 

Sep. 10, 1996 

Memory disk sheet stock and method 

INVENTOR: Bartges, Charles W., Delmont, Pennsylvania 
Hay land, Jr., Robert W., Oakmont, Pennsylvania 
Jensen, Craig J., Pittsburgh, Pennsylvania 

Baumann, Steven F. , Penn Hills, Pennsylvania (Rule 47 Application) 
SUM: 

... automatically grouped with this same series of elements even though it 
often performs the same function as scandium, or other "true" rare earths in an 
alloy composition. It is believed that minor amounts of still other rare 
earths, like erbium, thulium, lutetium, ytterbium, or another rare earth 

act-alike", like hafnium, may be substituted for, or possibly even combined 
with scandium (or with each other) in varying quantities to achieve the . . . 

LEVEL 1 - 9 OF 68 PATENTS 

5,504,205 

<=2> GET 1st DRAWING SHEET OF 25 

Apr. 2, 1996 



Reduced sp<3 > texaphyrins 

INVENTOR: Sessler, Jonathan L., Austin, Texas 
Hemmi, Gregory W., Austin, Texas 
Mody, Tarak D., Austin, Texas 

DETDESC : 

... 2H, CH=C), 10.24 (s, 2H, ArH), 12.23 (s, 2H, CH=N); UV/vis : lambda max 
420.0, 477.5, 730.0; FAB MS M< + > 811. 

Other lanthanide and rare earth- like metal complexes may be synthesized 
including the Gd< + 3> , Lu< + 3> , La< + 3> , In< + 3 > and Dy< + 3 > 
complexes . 
EXAMPLE 4 



Synthesis of B2T2 TXP, see FIG. 7, 



PAGE 



LEVEL 1 - 10 OF 68 PATENTS 
5,491,224 
Feb. 13, 1996 

Direct label transarainated DNA probe compositions for 
chromosome identification and methods for their manufacture 

INVENTOR: Bittner, Michael L. , 1768 Brookdale Rd., Naperville, Illinois 60563 
Morrison, Larry E., 21 W. 559 Kensington Rd . , Glen Ellyn, Illinois 60137 
Legator, Mona S., 6540 N. Francisco, Chicago, Illinois 60645 

DETDESC: 

. . . capable of reacting, and a fluorophore group may have already reacted, 
with a linking group. A fluorescent compound may include an organic chelator 
which binds a luminescent inorganic ion such as a rare earth like terbium, 
europium, ruthenium, or the like. 

The term "linking compound 11 or "linking group" as used herein generally 
refers to a hydrocarbonaceous moiety. A linking compound is capable of reacting, 
and a linking group may have . . . 

LEVEL 1 - 11 OF 68 PATENTS 

5,475,104 

<=2> GET 1st DRAWING SHEET OF 26 

Dec. 12, 1995 

Water soluble texaphyrin metal complexes for enhancing 

relaxivity 

INVENTOR: Sessler, Jonathan L., Austin, Texas 
Hemmi, Gregory W., Austin, Texas 
Mody, Tarak D. , Austin, Texas 

DETDESC: 

... 2H, CH=C), 10.24 (s, 2H, ArH), 12.23 (s, 2H, CH=N); UV/vis lambda max 
420.0, 477.5, 730.0; FAB MS M< + > 811. 

Other lanthanide and rare earth- like metal complexes may be synthesized 
including the Gd< + 3> , Lu< + 3> , La< + 3> , In< + 3 > and Dy< + 3 > 
complexes . 
EXAMPLE 4 

Synthesis of B2T2 TXP, see FIGS. 7A and ... 

LEVEL 1 - 12 OF 68 PATENTS 



5,457,183 



# • 

~2> GET 1st DRAWING SHEET OF 51 

Oct. 10, 1995 

Hydroxy lated texaphyrins 

INVENTOR: Sessler, Jonathan L. , Austin, Texas 
Mody, Tarak D. , Sunnyvale, California 
Hemmi, Gregory W., Sunnyvale, California 
Krai, Vladimir, Na Kozaaoa, Czechoslovakia 

DETDESC : 

... 2H, CH^C), 10.24 (s, 2H, ArH), 12.23 (s, 2H, CH=N); UV/vis : lambda max 
420.0, 477.5, 730.0; FAB MS M< + > 811. 

Other lanthanide and rare earth- like metal complexes may be synthesized in a 
similar manner including the La< + 3> , Nd< + 3> , Sm< + 3> , Eu< + 3> , Gd< + 
3> , Dy< + 3 > and Tm< + 3 > complexes. 

PAGE 

LEVEL 1 - 13 OF 68 PATENTS 
5,451,576 
<=2> GET 1st DRAWING SHEET OF 26 
Sep. 19, 1995 

Tumor imaging and treatment by water soluble texaphyrin 

metal complexes 

INVENTOR: Sessler, Jonathan L. , Austin, Texas 
Hemmi, Gregory W., Austin, Texas 
Mody, Tarak D., Austin, Texas 

DETDESC: 

... 2H, CH=C), 10.24 (s, 2H, ArH), 12.23 (s, 2H, CH=N); UV/vis: lambda max 
420.0, 477.5, 730.0; FAB MS M< + > 811. 

Other lanthanide and rare earth- like metal complexes may be synthesized 
including the Gd< + 3> , Lu< + 3> , La< + 3> , In< + 3> and Dy< + 3 > complexes. 
EXAMPLE 4 

Synthesis of B2T2 TXP, see FIGS. 7A and ... 

LEVEL 1 - 14 OF 68 PATENTS 

5,447,906 

Sep. 5, 1995 

Thin film high TC oxide superconductors and vapor deposition 
methods for making the same 

INVENTOR: Chaudhari, Praveen, Briarcliff Manor, New York 
Gambino, Richard J., Yorktown Heights, New York 
Koch, Roger H., Amawalk, New York 
Lacey, James A., Mahopac, New York 
Laibowitz, Robert B., Peekskill, New York 
Viggiano, Joseph M., Wappingers Falls, New York 

ABST: 

. . . films are produced by vapor deposition processes using pure metal sources 
for the metals in the superconducting compositions, where the metals include 
multi-valent nonmagnetic transition metals, rare earth elements and/or rare 
earth-like elements and alkaline earth elements. The substrate is exposed to 
oxygen during vapor deposition, and, after formation of the film, there is at 
least one annealing step in an oxygen ambient and slow cooling over several 



hours to room tern ^^ature . The substrates chosen a g^not critical as long as 
they are not adve^pLy reactive with the supercondJ^Ping oxide film. Transition 
metals include Cu,^Ni, Ti and V, while the rare earth- like elements include Y, 
Sc and La. The alkaline earth elements include Ca, Ba and Sr. 

SUM: 

. . . material in the last decade, wherein the critical transition temperature 
T c at which the material becomes superconducting was increased substantially. 

Bednorz and Mueller described copper oxide material including a rare earth 
element, or rare earth- like element, where the rare earth element could be 
substituted for by an alkaline earth element such as Ca, Ba or Sr. 

The work of Bednorz and Mueller has led to intensive investigation in many 
laboratories in ... 

... 40o K. and methods for making these films, where the films exhibit 
perovskite- like structure. 

It is another object of this invention to provide transition metal oxide 
superconductive films including a rare earth element, or rare earth- like 
element, where the films exhibit superconductivity at temperatures greater than 
40o K., and methods for making these films. 

It is another object of the present invention to provide films having the 
nominal composition ABO 3 - y or ABO y ... 

. . . provide superconductive oxide films having the nominal composition AB2 
Cu30 9 - y , and methods for making these films, where the films are 
superconducting at temperatures in excess of 40o K. and A is a rare earth or 
rare earth- like element, B is an alkaline earth element, and y is sufficient to 
satisfy valence demands of the composition. 

Pat. No. 5447906, * 

It is another object of the present invention to provide smooth, continuous 
copper oxide superconducting films having a perovskite- like ... 

. . . films being smooth and continuous and exhibiting substantial 
compositional uniformity. In particular, the films are comprised of transition 
metal oxides containing a superconducting phase, and typically include a rare 
earth element or rare earth- like element. These rare earth- like elements include 
Y, Sc and La. Additionally, the rare earth or rare earth- like elements can be 
substituted for by an alkaline earth element selected from the group consisting 
of Ca, Ba, and Sr. The transition metals are multi-valent , non-magnetic elements 
selected from the group consisting of ... 

DETDESC : 

... especially a T c in excess of liquid nitrogen temperatures. These films 
are characterized by the presence of a transition metal oxide and typically by 
the presence of a rare earth element and/or a rare earth- like element which can 
be substituted for by an alkaline earth. The transition metal element is a 
multi-relent nonmagnetic element while the alkaline earth element is selected 
from the group consisting of Ca, Ba, and Sr. The rare earth- like elements 
include Y, Sc, and La. The nonmagnetic transition metal is selected from the 
group consisting of Cu, Ni, Ti, and V. Of these, Cu is the most favorable, 
yielding film properties which are unique and unexpected. 

In the further . . . 

LEVEL 1 - 15 OF 68 PATENTS 
5,439,570 
<=2> GET 1st DRAWING SHEET OF 26 
Aug. 8, 1995 

Water soluble texaphyrin metal complexes for singlet oxygen 



A7 



t production 
n L. , Austin, Texas 
Herami, Gregory W., Austin, Texas 
Mody, Tarak D., Austin, Texas 

DETDESC : 

... 2H, CH=C), 10.24 (s, 2H, ArH), 12.23 (s, 2H, CH=N); UV/vis: lambda max 
420.0, 477.5, 730.0; FAB MS M< + > 811. 

Other lanthanide and rare earth- like metal complexes may be synthesized 
including the Gd< + 3> , Lu< + 3> , La< + 3> , In< + 3 > and Dy< + 3 > 
complexes . 
EXAMPLE 4 

Synthesis of B2T2 TXP, see FIGS. 7A and ... 

LEVEL 1 - 16 OF 68 PATENTS 

5,432,171 

<=2> GET 1st DRAWING SHEET OF 26 

Jul. 11, 1995 

Water soluble texaphyrin metal complexes for viral 

deactivation 

INVENTOR: Sessler, Jonathan L., Austin, Texas 
Hemmi, Gregory W., Austin, Texas 
Mody, Tarak D. , Austin, Texas 

DETDESC : 

... 2H, CH=C), 10.24 (s, 2H, ArH), 12.23 (s, 2H, CH=N); UV/vis: lambda max 
420.0, 477.5, 730.0; FAB MS M< + > 811. 

Other lanthanide and rare earth- like metal complexes may be synthesized 
including the Gd< + 3> , Lu< + 3> , La< + 3> , In< + 3 > and Dy< + 3 > 
complexes . 
EXAMPLE 4 

Synthesis of B2T2 TXP, see FIGS. 7A and ... 

LEVEL 1 - 17 OF 68 PATENTS 

5,362,582 

Nov. 8, 1994 

Battery separator 

INVENTOR: Chang, Victor S., Ellicott City, Maryland 

Hartwig, Richard C, Laurel, Maryland 

Lundquist, Joseph T., Gilroy, California 

Parham, Marc E., Bedford, Massachusetts 

Kung, James K., Lexington, Massachusetts 

Avtges, James A., Belmont, Massachusetts 

Laccetti, Anthony J., North Andover, Massachusetts 

SUM: 

. . . say the particulate filler must be inert with respect to such end use 
battery environment. Therefore, alkali insoluble particulate such as zirconia 
and titanium dioxide (preferred), oxides, hydroxides and carbonates of calcium, 
magnesium, iron, rare earth and the like should be used only in sheet products 
which ultimately are formed into battery separators for alkaline batteries. 
Similarly, acid insoluble particulates such as silica (a precipitated silica is 
preferred), and the like should be ... 

LEVEL 1 - 18 OF 68 PATENTS 




5,358,659 



<=2> GET 1st DRAWING SHEET OF 5 
Oct. 25, 1994 

Magnetic materials with single-domain and multidomain 
crystallites and a method of preparation 

INVENTOR: Ziolo, Ronald F. , Webster, New York 

DETDESC : 

. . . Ions which can be incorporated into the resin beads to form both 
single-domain and multidomain magnetic particles include: those derivable from 
transition metal ions, such as iron, cobalt, nickel, manganese, vanadium, 
chromium, rare earths and the like. These ions generally exist in the form of 
chlorides of the metal involved such as ferrous chloride, ferric chloride, 
copper chloride, nickel chloride, and the like. The corresponding iodides, 
bromides and fluorides may also be suitable. ... 

PAGE 20 

LEVEL 1 - 19 OF 68 PATENTS 
5,322,756 
<=2> GET 1st DRAWING SHEET OF 3 
Jun. 21, 1994 
Magnetic fluids and method of preparation 
INVENTOR: Ziolo, Ronald F., Webster, New York 
DETDESC : 

... several different ions including ferrous or ferric ions. Examples of the 
precursor ions which may be used includes those derivable from transition metal 
ions, such as iron, cobalt, nickel, manganese, vanadium, chromium, rare earths 
and the like. These ions generally exist in the form of chlorides of the metal 
involved, such as ferrous chloride, ferric chloride, copper chloride, nickel 
chloride, and the like. The corresponding iodides, bromides and fluorides may 
also be suitable. ... 

LEVEL 1 - 20 OF 68 PATENTS 

5,304,966 

<=2> GET 1st DRAWING SHEET OF 4 

Apr. 19, 1994 

Method of adjusting a frequency response in a 
three- conductor type filter device 

INVENTOR: Hino, Seigo, Nagoya, Japan 
I to, Kenji, Nagoya, Japan 

SUM: 

... each other. Each of the dielectric substrates 1 and 2 may be of 
dielectric ceramic material having a high dielectric constant and a lower 
dielectric loss such as Ba0-Ti02, Ba0-Ti02-rare earth or the like. The lower 
dielectric substrate 1 is provided with an external ground conducting layer 3 on 
the peripheral portion and bottom surface thereof. Similarly, the upper 
dielectric substrate 2 is provided with an external ground conducting layer 4 on 
the . . . 

DETDESC : 

... assembling of the filter. Each of the dielectric substrates 21 and 22 may 
be of dielectric ceramic material having a high dielectric constant and a lower 



dielectric loss such as<Bpo-Ti02, Ba0-Ti02-rare earth or^^e like. The lower 
dielectric substrate 21 is provided with an external ground conductor layer 23 
on the peripheral portion and outer surface thereof. Similarly, the upper 
dielectric substrate 22 is provided with an external ground conductor layer 24 
on the . . . 

LEVEL 1 - 21 OF 68 PATENTS 
5,296,458 
<=2> GET 1st DRAWING SHEET OF 4 
Mar. 22, 1994 

Epitaxy of high T c superconducting films on (001) silicon 

surface 

INVENTOR: Himpsel, Franz J., Mt . Kisco, New York 
SUM: 

... as well as to understand the basic mechanisms for superconductivity in 
this class of materials. 

Bednorz and Mueller first showed superconducting behavior in mixed 
copper-oxides, typically including rare earth and/or rare earth- like elements 
and alkaline earth elements, for example La, Ba, Sr, . . . , and having a 
perovskite-like structure. Materials including the so called "l-2-3 ft phase in 
the Y-Ba-Cu-0 . . . 

DETDESC : 

. . . EMBODIMENTS 

A technique is provided for depositing high T c superconducting copper-oxide 
based materials epitaxially on Si (001). Typically, these classes of 
superconducting materials include a rare earth or rare earth- like element and/or 
an alkaline earth element. Representative formulas for such materials are the 
following: 

(A 1 - x B x )2Cu04 - epsilon and AlB2Cu30 7 - epsilon 
where A is a trivalent element (e.g., La, Y, and ... 

... in the art that the present invention applies to epitaxial structures 
including silicon (001) surfaces and any copper oxide superconductor thereon. 
Thus, the teaching of this invention can include copper-oxide based compositions 
having any combinations of rare earth or rare earth- like elements and/or 
alkaline earth elements as well as copper oxide superconductors which do not 
contain rare earth elements. Further, it will be apparent to those of skill in 
the art that the Si (001) surface is . . . 

LEVEL 1 - 22 OF 68 PATENTS 

5,291,162 

<=2> GET 1st DRAWING SHEET OF 7 

Mar. 1, 1994 

Method of adjusting frequency response in a microwave 
strip- line filter device 

INVENTOR: Ito, Kenji, Nagoya, Japan 
Shimizu, Hiroyuki, Nagoya, Japan 
Oguchi, Hotaka, Nagoya, Japan 

SUM: 

. . • type which comprises a pair of dielectric substrates la and lb made of 
dielectric ceramic material having a high dielectric constant and a lower 
dielectric loss such as Ba0-Ti02 or Ba0-Ti02-rare earth or the like, the 

fitO 



dielectric substrates l^Bnd lb being stacked to each ot^ft. The dielectric 
substrates la and lb are^rovided with external ground conducting layers 2a and 
2b on the peripheral portion and bottom surface thereof, respectively. On the 
upper ... 

DETDESC : 

... assembling of the filter. Each of the dielectric substrates 11 and 12 may 
be of dielectric ceramic material having a high dielectric constant and a lower 
dielectric loss such as Ba0-Ti02, Ba0-Ti02-rare earth or the like. The lower 
dielectric substrate 11 is provided with an external ground conducting layer 13 
on the peripheral portion and outer surface thereof. Similarly, the upper 
dielectric substrate 12 is provided with an external ground conducting layer 14 
on the ... 

... a pair of piezoelectric substrates 11 and 12 each of which may be of 
dielectric ceramic material having a high dielectric constant and a lower 
dielectric loss such as BaO~Ti02, Ba0-Ti02-rare earth or the like. The 
dielectric substrates 11 and 12 are provided with external ground conducting 
layers 13 and 14 on the peripheral portions and outer surfaces thereof, 
respectively. These ground conducting layers 13 and 14 may be formed by . . . 

LEVEL 1 - 23 OF 68 PATENTS 

5,278,140 

<=2> GET 1st DRAWING SHEET OF 5 

Jan. 11, 1994 

Method for forming grain boundary junction devices using 
high T c superconductors 

INVENTOR: Chaudhari, Praveen, Briarcliff Manor, New York 
Chi, Cheng-Chung J., Yorktown Heights, New York 
Dimos , Duane B., Montclair, New Jersey 

Mannhart, Jochen D., Metzingen, New York, Federal Republic of Germany 
Tsuei, Chang C, Chappaqua, New York 

SUM: 

... as well as to understand the basic mechanisms for superconductivity in 
this class of materials. 

Bednorz and Mueller first showed superconducting behavior in mixed 
copper- ox ides, typically including rare earth and/or rare earth- like elements 
and alkaline earth elements, for example La, Ba, Sr, . . . , and having a 
perovskite-like structure. Materials including the so called "1-2-3" phase in 
the Y-Ba-Cu-0 ... 

... excess of about 30o K are generally known as "high T c superconductors", 
and will be referred to in that manner throughout the specification. This 
designation is meant to include both the materials having rare earth or rare 
earth- like elements in their crystalline structure, as well as the more recently 
reported materials which do not contain rare earth or rare earth-like elements. 
Generally, all these materials are copper oxide based superconductors having 
Cu-0 planes that appear to be primarily responsible for carrying the 
supercurrents , where the copper oxide planes are separate or in groups separated 
by the ... 

LEVEL 1 - 24 OF 68 PATENTS 
5,252,720 
<=2> GET 1st DRAWING SHEET OF 25 
Oct. 12, 1993 
Metal complexes of water soluble texaphyrins 
INVENTOR: Sessler, Jonathan L., Austin, Texas 



12 FtU 



Hemmi, Gregory W., Aust^^, Texas 
Mody, Tarak D., Austin ,^fexas 



DETDESC : 

... 2H, CH=C), 10.24 (s, 2H, ArH) , 12.23 (s, 2H, CH=N) ; UV/vis : lambda max 
420.0, 477.5, 730. 0; FAB MS M< + > 811. 

Other lanthanide and rare earth- like metal complexes may be synthesized 
including the Gd< + 3> , Lu< + 3> , La< + 3> , In< + 3 > and Dy< + 3 > 
complexes . 
EXAMPLE 4 

Synthesis of B2T2 TXP, see FIG. 7 

PAGE 

LEVEL 1 - 25 OF 68 PATENTS 
5,235,298 
<=2> GET 1st DRAWING SHEET OF 2 
Aug. 10, 1993 

Temperature compensated stripline filter for microwaves 

INVENTOR: Banno, Hisao, Nagoya, Japan 
Nishiki, Masahiro, Nagoya, Japan 

SUM: 

... 4,785,271 and Japanese Patent Prepublication No. 62-263702. 

With the microwave stripline filter of the abovementioned type, generally, 
each dielectric ceramic substrate is made of ceramic material such as Ba0-Ti02, 
Ba0-Ti02-rare earth or the like. 

However, there is disadvantage that the commonly used ceramic material has a 
resonant frequency which is decreased as the temperature is risen because the 
temperature coefficient of the resonant frequency is of a negative 
characteristic . 

It is therefore an object of the present invention to provide a stripline . . . 

LEVEL 1 - 26 OF 68 PATENTS 

5,188,809 

<=2> GET 1st DRAWING SHEET OF 4 

Feb. 23, 1993 

Method for separating coke from a feed mixture containing 
zirconium and radioactive materials by flotation process 

INVENTOR: Crocker, William A., Salem, Oregon 
Haygarth, John C, Corvallis, Oregon 
Riesen, Jon A., Albany, Oregon 
Peterson, John R., Salem, Oregon 

DETDESC: 

. . . radium removal. 

b) Sodium sulfate or any other source of soluble sulfate is then added in 
excess of the concentration of the barium plus radium ion equivalents and any 
other cations which might combine with the sulfate ions, i.e. calcium, rare 
earths, or the like. If the solution is cold, it should be heated and a 
digestion allowed to take place which can range from a fairly short time up to 
hours or days. The preferred digestion period would be a few hours with ... 

LEVEL 1 - 27 OF 68 PATENTS 



5,162,298 



<=2> GET 1st DRAWING SHEET OF 5 

Nov. 10, 1992 

Grain boundary junction devices using high T c 
superconductors 

INVENTOR: Chaudhari, Praveen, Briarcliff Manor, New York 
Chi, Cheng-Chung J., Yorktown Heights, New York 
Diraos, Duane B., Upper Montclair, New Jersey 

Mannhart, Jochen D. , Metzingen, New York, Federal Republic of Germany 
Tsuei, Chang C, Chappaqua, New York 

SUM: 

... as well as to understand the basic mechanisms for superconductivity in 
this class of materials. 

Bednorz and Mueller first showed superconducting behavior in mixed 
copper- oxides, typically including rare earth and/or rare earth-like elements 
and alkaline earth elements, for example La, Ba, Sr, . . • , and having a 
perovskite-like structure. Materials including the so called 1-2-3 phase in 
the Y-Ba-Cu-0 . . . 

excess of about 30o K. are generally known as "high T c superconductors", 
and will be referred to in that manner throughout the specification. This 
designation is meant to include both the materials having rare earth or rare 
earth- like elements in their crystalline structure, as well as the more recently 
reported materials which do not contain rare earth or rare earth- like elements. 
Generally, all these materials are copper oxide based superconductors having 
Cu-0 planes that appear to be primarily responsible for carrying the 
supercurrents , where the copper oxide planes are separate or in groups separated 
by the ... 

[*4] copper oxide material having a superconducting onset temperature 
greater than 77 K. 

f*5] 5. The device of claim 4, where said superconducting material includes 
an atom selected from the group consisting of rare earth atoms and rare 
earth- like atoms. 

[*6] 6. The device of claim 4, where said superconducting material includes 
an alkaline earth atoms. 

[*7] 7. The device of claim 4, where said superconducting material includes 
bismuth . 

[*81 8. The device of claim 1, where ... 

1 J LEVEL 1 - 2S~ OF 68 PATENTS 

5,160,482 

<=2> GET 1st DRAWING SHEET OF 8 

Nov. 3, 1992 

Zirconium-hafnium separation and purification process 

INVENTOR: Ash, Kenneth C, Corvallis, Oregon 
Crocker, William A., Salem, Oregon 
Haygarth, John C, Corvallis, Oregon 
Lee, David R., Lebanon, Oregon 
Morris, Donald, Corvallis, Oregon 
Peterson, John R., Salem, Oregon 
Riesen, Jon A., Albany, Oregon 
Yih, Robert S., Salem, Oregon 



DETDESC : w 
... system or solution. 



b) Sodium sulfate or any other source of soluble sulfate is then added in 
excess of the concentration of the barium plus radium ion equivalents and any 
other cations which might combine with the sulfate ions, i.e. calcium, rare 
earths, or the like. If the solution is cold, it should be heated and a 
digestion allowed to take place which can range from a fairly short time up to 
hours or days. The preferred digestion period would be a few hours with ... 

LEVEL 1 - 29 OF 68 PATENTS 

5,112,795 

May 12, 1992 

Supported silver catalyst, and processes for making and 

using same 

INVENTOR: Minahan, David M. , Cross Lanes, West Virginia 
Thorsteinson , Erlind M., Charleston, West Virginia 
Liu, Albert C, Charleston, West Virginia 

SUM: 

. . . metal promoter employed is not critical and may include the one or more 
alkali metals; one or more alkaline earth metals; or one or more other 
promoters, such as thallium, gold, tin, antimony, rare earths and the like. The 
catalysts produced are said to be equally as efficient as catalysts produced by 
coincidental methods of preparation. 

Supported, silver-containing, alkylene oxide catalysts often include one or 
more metal- . . . 

LEVEL 1 - 30 OF 68 PATENTS 

5,084,684 

<=2> GET 1st DRAWING SHEET OF 5 

Jan. 28, 1992 

Method of adjusting a frequency response in a 
three-conductor type filter device 

INVENTOR: Shimizu, Hiroyuki, Nagoya, Japan 
I to, Kenji, Nagoya, Japan 
Wakita, Naomasa, Nagoya, Japan 

SUM: 

... each other. Each of the dielectric substrates 1 and 2 may be of 
dielectric ceramic material having a high dielectric constant and a lower 
dielectric loss such as Ba0-Ti02, Ba0-Ti02-rare earth or the like. The lower 
dielectric substrate 1 is provided with an external ground conducting layer 3 on 
the peripheral portion and bottom surface thereof. Similarly, the upper 
dielectric substrate 2 is provided with an external ground conducting layer 4 on 
the . . . 

DETDESC : 

... assembling of the filter. Each of the dielectric substrates 11 and 12 may 
be of dielectric ceramic material having a high dielectric constant and a lower 
dielectric loss such as Ba0-Ti02, Ba0-Ti02-rare earth or the like. The lower 
dielectric substrate 11 is provided with a ground conducting layer 13 on the 
lower or outer surface thereof. Similarly, the upper dielectric substrate 12 is 
provided with a ground conducting layer 14 on the upper or ... 

LEVEL 1 - 31 OF 68 PATENTS 

5,084,312 



> GET 1st DRAWING SHEET OF . 



Jan. 28, 1992 

Molten metal containment vessel with rare earth oxysulfide 
protective coating thereon and method of making same 

INVENTOR: Krikorian, Oscar H . , Danville, California 
Curtis, Paul G . , Tracy, California 

SUM: 

... same. More particularly, this invention relates to an improved 
containment vessel for molten raetals formed by coating at least the inside 
surface of a containment vessel with an oxysulfide or sulfide of a rare earth or 
rare earth- like element. 

Molten metals such as uranium, plutoniura, aluminum, and calcium are usually 
contained in vessels or crucibles made from graphite or a refractory metal such 
as, for example, niobium, tantalum, molybdenum, or tungsten. ... 

... in which wetting of the vessel's surfaces by molten metal is inhibited by 
coating the surfaces of at least the inner walls of the containment vessel with 
one or more compounds comprising an oxysulfide of a rare earth or a rare 
earth-like element to inhibit such wetting and or adherence by the molten metal. 

It is a further object of this invention to provide a method for making an 
improved molten metal containment vessel in which wetting of the surfaces by . . . 

DETDESC : 

rare earth oxysulfide or sulfide compound include the lanthanide elements 
La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; as well as the rare 
earth- like elements Sc and Y; and actinides such as Th and U. The term rare 
earth" and "rare earth elements", as used herein, are therefore intended to 
define any of the above listed elements. 

The rare earth oxysulfide and sulfide coatings of the . . . 

LEVEL 1 - 32 OF 68 PATENTS 

5,075,653 

Dec. 24, 1991 

Method of adjusting a frequency response in a 
three- conductor type filter device 

INVENTOR: I to, Kenji, Nagoya, Japan 
Shimizu, Hiroyuki, Nagoya, Japan 

SUM: 

... each other. Each of the dielectric substrates 1 and 2 may be of 
dielectric ceramic material having a high dielectric constant and a lower 
dielectric loss such as Ba0-Ti02, Ba0-Ti02-rare earth or the like. The lower 
dielectric substrate 1 is provided with an external ground conducting layer 3 on 
the peripheral portion and bottom surface thereof. Similarly, the upper 
dielectric substrate 2 is provided with an external ground conducting layer 4 on 
the . . . 

DETDESC: 

... assembling of the filter. Each of the dielectric substrates 11 and 12 may 
be of dielectric ceramic material having a high dielectric constant and a lower 
dielectric loss such as Ba0-Ti02, Ba0-Ti02-rare earth or the like. The lower 
dielectric substrate 11 is provided with an external ground conducting layer 13 
on the peripheral portion and outer surface thereof. Similarly, the upper 
dielectric substrate 12 is provided with an external ground conducting layer 14 
on the . . . 

LEVEL 1 - 33 OF 68 PATENTS 



5,066,934 ^ 
<=2> GET 1st DRAWING SHEET OF 6 
Nov. 19, 1991 

Method of adjusting a frequency response in a stripline 

filter device 

INVENTOR: I to, Kenji, Nagoya, Japan 
Shimizu, Hiroyuki, Nagoya, Japan 
Wakita, Naomasa, Nagoya, Japan 

SUM: 

. . . each other. Each of the dielectric substrates 1 and 2 may be of 
dielectric ceramic material having a high dielectric constant and a lower 
dielectric loss such as Ba0-Ti02, Ba0-Ti02-rare earth or the like. The lower 
dielectric substrate I is provided with an external ground conducting layer 3 on 
the peripheral portion and bottom surface thereof. Similarly, the upper 
dielectric substrate 2 is provided with an external ground conducting layer 4 on 
the . . . 

DETDESC : 

... assembling of the filter. Each of the dielectric substrates 11 and 12 may 
be of dielectric ceramic material having a high dielectric constant and a lower 
dielectric loss such as Ba0-Ti02, Ba0-Ti02-rare earth or the like. The lower 
dielectric substrate 11 is provided with an external ground conducting layer 13 
on the peripheral portion and outer surface thereof. Similarly, the upper 
dielectric substrate 12 is provided with an external ground conducting layer 14 
on the . . . 

LEVEL 1 - 34 OF 68 PATENTS 
5,045,289 
<=2> GET 1st DRAWING SHEET OF 4 
Sep. 3, 1991 

Formation of rare earth carbonates using supercritical 

carbon dioxide 

INVENTOR: Fernando, Quintus , Tucson, Arizona 
Yanagihara, Naohisa, Zacopan, New Mexico, Mexico 
Dyke, James T., Santa Fe, New Mexico 
Vemulapalli, Krishna, Tuscon, Arizona 

SUM: 

... invention. This technique finds use in facilitating the extraction of* 
these materials from rare earth containing mineral ores by providing a scheme 
for separating these particular rare earths from other rare earth and rare 
earth- like materials which do not react to form carbonates. 

2. Description of the Prior Art 

The rare earths, also known as the lanthanides or as lanthanons, and meaning 
here those elements having atomic numbers 57 to 71, are substances finding 
utility . . . 

DETDESC : 

. . . synthesis of rare earth carbonates from certain select rare earths in the 
trivalent ( + 3) state as normally found in, for example, rare earth oxides or 
hydroxides, from other rare earths or rare earth- like materials. Rare 
earth-like materials are those compounds associated with, normally present in, 
or formed during the processing of, the various source ores from which the 
lanthanides are derived. These materials, while not true rare earths are 
analogous to the lanthanides in structure and behavior and are therefore of 
concern during processing and separation. Included among these rare earth- like 

Ai 6 



materials are compound s^prmed from the actinides, (elenJWs of atomic numbers 
89 to 103, such as thorium), titanium, yttrium, and zirconium. In general, these 
elements, which form the rare earth- like compounds, are present in their + 4 
oxidation state; examples include Th02 and Zr02 . The process of the invention 
has utility in the quantitative precipitation of the particular reactive 
lanthanides in the + 3 oxidation state and in the separation of these . . . 

... about 40o C. High yields of 95% or better are obtained in approximately 
one hour. These particular rare earth oxides or hydroxides can thus be readily 
separated from the oxides or hydroxides of rare earth or rare earth- like 
elements such as praseodymium (Pr), terbium (Tb), erbium (Er), ytterbium (Yb), 
zirconium (Zr) , cerium (Ce), and thorium (Th) because these latter rare earth 
and rare earth- like oxides (or hydroxides) do not form carbonates under the 
above conditions despite the fact that some are in the trivalent state. It is 
believed that the oxides of these elements are particularly complex and as such 
do not readily react under the conditions of the invention. 

This ... 

Pat. No. 5045289, * 

... through appropriate valves and the reaction solution is then filtered. 
The solids which remain are then washed with deionized water and dried in air. 
These solids comprise both the rare earth materials which have reacted to form 
carbonates and also those rare earth and/or rare earth- like materials which did 
not react, or did not react significantly, and have thus remained in their oxide 
or hydroxide form. 

The solid precipitate obtained above is next treated with a dilute acid such 
as HC1 in a concentration of between 0.1 and 3.0M. Preferrably 0.5M HC1 is used 
at ambient temperature and pressure. This acid treatment solubilizes the rare 
earth carbonates, leaving the unreacted rare earth and rare earth- like oxides 
and/or hydroxides behind in their solid form. The resultant solution is filtered 
and the carbonate fraction can be further broken down into individual rare earth 
carbonates by techniques such as ion exchange or ... 

... La203(49.72%), Nd203(20 . 02%) , Tb407(5 . 08%) , Yb203(5.10%) and 
Th02(20 . 07%) , a high degree of separation of La and Nd was obtained-namely , 
between 94.3% and 99.8%. Notably, the other rare earth or rare earth- like oxides 
in this mixture are among those which do not react to form carbonates with 
supercritical carbon dioxide or by the process of the invention. 

The following example will illustrate and describe without limiting the 
invention. The example illustrates the carbonation process of the invention 
using essentially pure rare earth oxides. 
EXAMPLE 

Synthesis of Lanthanide Carbonates 

The oxides of the following rare earths and rare earth- like materials, La203, 
Ce02, Pr6011, Nd203,Sm203, Eu203, Gd203, Tb407, Dy203, Ho203, Er203, Yb203 and 
Zr02, were obtained from Alfa Division 7 Danvers, MA, and were 99.9% pure. The 
carbon dioxide used in this . . . 

LEVEL 1 - 35 OF 68 PATENTS 

4,977,937 

<=2> GET 1st DRAWING SHEET OF 4 

Dec. 18, 1990 

Multiple angle jointer and planer knives 

INVENTOR: Hessenthaler , George D. } 585 W. 3900 South, #6, Murray, Utah 84123 

DETDESC : 

... gibe or locking bars, not shown, are tightened, the blade magnets 53 are 
selected to attract even minimally magnetic material, such as carbide. To 
provide such magnetic attraction the selected magnets should be very strong, 

/vn 



such as rare earth, or ^P-e magnets. 

Like the jointer jig 40, a planer jig 60, shown in FIGS. 9 and 10 also 
utilizes magnets for maintaining blade positioning in a cylindrical cutterhead 
61 . . . PA( 

LEVEL 1 - 36 OF 68 PATENTS 
4,962,086 
<=2> GET 1st DRAWING SHEET OF 2 
Oct. 9, 1990 

High T c superconductor - gallate crystal structures 

INVENTOR: Gallagher, William J., Ardsley, New York 
Giess, Edward A., Purdys, New York 
Gupta, Aranava, Valley Cottage, New York 
Laibowitz, Robert B., Peekskill, New York 
0 Sullivan, Eugene J., Peekskill, New York 
Sandstrom, Robert L., Chappaqua, New York 

ABST: 

High T c oxide superconductive films can be formed on gallate layers, where 
the gallate layers include a rare earth element or a rare earth- like element. 
Combinations of rare earth elements and rare earth- like elements can also be 
utilized. The superconductive films can be epitaxially deposited on these 
gallate layers to form single crystals or, in the minimum, highly oriented 
superconductive layers . Any high T c superconductive . . . 

SUM: 

. . . materials having Cu-0 planes therein which are responsible for carrying 
supercurrents in these materials. Epitaxial films of these high T c 
superconductors can be deposited on gallate substrates, where the substrates are 
rare earth gallates or rare earth- like gallates. These superconductor-substrate 
combinations are particularly suited for analog and digital signal processing 
devices including matched filters, correlators, Fourier transformers, spectrum 
analyzers, samplers, A/D converters, etc. 




... high T c superconductors . 

The high T c superconductors used with these gallate substrates are 
preferably those which include Cu-0 and Cu-0 like current carrying planes and 
can include rare earth and rare earth- like elements, as well as combinations of 
these elements. Also included are the non-rare earth high T c superconductors 
such as those having Bi-Sr-Ca-Cu-0 compositions and Tl-Ba-Ca-Cu- . . . 

... less than that when copper containing oxide superconductors are used. 
Lattice matching of the superconductor atomic spacing to the Ga-0 plane is 
especially good with the copper oxide superconductors which form unique 
combinations with these gallates. 

These rare earth and rare earth- like gallate substrates can be prepared in 
high quality crystal form and provide excellent lattice matches to the Cu-0 
based superconducting perovskites . This is important in device applications 
since for . . . 

DRWDESC: 

BRIEF DESCRIPTION OF THE DRAWINGS 

Pat. No. 4962086, * 

FIG. 1 illustrates a high T c superconducting film epitaxially deposited on a 
rare earth or rare earth- like gallate substrate. 

FIG. 2 illustrates a structure including a high T c superconducting strip 

A/0 



line surrounded by a g^~9me lattice-matched insulator, -^Jfurther including 
high . . . 



DETDESC : 

... 10 has been deposited on the crystal substrate 12. A cooling means, if 
needed, is not shown but is well known in the art. 

Substrate 12 is a gal late substrate comprised of a rare earth or rare 
earth- like element, gallium, and oxygen. Examples include LaGa03 and NdGa03 . A 
mixed gallate can also be used, such as one prepared from La-Y solid solutions. 
This technique is used to provide different lattice . . . 

. . . for use in the substrate include elements 58-71 of the periodic table, 
and in particular, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. The 
rare earth- like elements suitable for use in the gallate substrates include Y, 
La, Bi and Sc. As noted, combinations of these rare earth and rare earth- like 
elements can also be used. 

For the copper oxide superconductors the rare earth elements Tb, Dy, Ho, Er, 
Tm, Yb, and Lu may not provide atomic spacings that give lattice . . . 

. . . one which in preferred form is characterized by Cu-0 planes that are 
primarily responsible for carrying the supercurrents in these materials. They 
generally have a perovskite-related structure and can include rare earth and/or 
rare earth- like elements. These materials often include alkaline earth elements, 
as for example Ca, Ba, Sr, Mg, . . .An example of a 92o K. superconductor is 
the well known YBa2Cu30 7 - x , which is the so-called " ... 

... be difficult to stabilize the approximately llOo K. superconducting phase 
of Bi-Sr-Ca-Cu-0 superconductors. However, a favorable epitaxial substrate 
chosen from the class of gallates including a rare earth or rare earth- like 
element may aid in stabilizing this and other high T c phases. A cut along the 
[110] orthorhombic unit cell of GdGa03 would expose a surface with a favorable 
lattice match which . . . 

... While the unit cell of this superconducting thin film is rotated 45o with 
respect to the unit cell of the perovskite substrate, such rotation will not be 
needed for epitaxial matches of different superconductors to the rare earth and 
rare earth- like gallate substrates. One of skill in the art would use an 
orientation of the substrate such that good epitaxy and lattice matching will 
occur with the chosen superconducting film. In this example, the a and b axes 
are in the plane of the ... 

... approximates a (100) cubic perovskite surface. With this as a guide, the 
substrate boule material is cut to provide the desired orientation. 

It has been noted that the gallate substrates including a rare earth element 
or a rare earth- like element exhibit good hardness and tolerance to high 
temperatures. However, it may be preferable to process the superconducting film 
at temperatures less than the rhorabohedral- orthorhombic transition of the 
substrate in order to maintain the slight orthorhombicity of the substrate. 

Pat. No. 4962086, * 



. . . Lett. 58, 2684 (1987) . 

In the practice of this invention, highly oriented films of high T c oxide 
superconductors have been deposited on gallate substrates. These substrates are 
those which include at least one rare earth element or rare earth- like element. 
The superconducting epitaxial films are highly oriented and can approximate 
single crystals. 

In the further practice of this invention, these high T c oxide 
superconducting film-gallate substrate combinations are particularly suitable 



M1 



... apparent to tho. »f skill in the art that varia As can be made «■ w. • 
wxthout departing from We spirit and scope of the prese"in"ntion ^or 
example, the gallate substrate materials may include combinations of rare earth 
elements and rare earth-like elements, and may also be doped to slilhlll varv 
s ^«t^ ram ^? rS - F ^ th ^' su P«conductive films deposited on" tnese * 

substrates, while preferably being copper oxide-based superconductors, can 
Seient/ 3 ^ ??" ? * leraents ' earth-like elements, aSd alkaline earth 

elements. Still further, combinations of these elements may be present and 
also, rare earth elements need not be present in the superconducting film 

The best epitaxial matches occur when the 

LEVEL 1 - 37 OF 68 PATENTS 

4,882,718 

<=2> GET 1st DRAWING SHEET OF 3 

Nov. 21, 1989 

Single-head, direct overwrite magneto-optic system and 

method 

INVENTOR: Kryder, Mark H. , Pittsburgh, Pennsylvania 
Shieh, Han-Ping D. , Pittsburgh, Pennsylvania 

DETDESC : 

... domain will realign and not grow. Ferrimagnetic alloys including light 
rare earths such as gadolinium usually provide good mobility but generally 
require an approximately equal proportion of a heavy rare earth like terbium to 
increase coercivity to an effective operating level " t0 

A preferred formulation (in atomic %) tested in the laboratory is as follows: 

Gdl3 Tbl3 Fe59 Col5 having a compensation temperature of 90o 

LEVEL 1 - 38 OF 68 PATENTS 

4,882,067 

<=2> GET 1st DRAWING SHEET OF 1 

Nov. 21, 1989 

Process for the chemical bonding of heavy metals from sludge 

in the silicate structure of clays and shales and the 
manufacture of building and construction materials therewith 

INVENTOR: Johnson, Barrett, Sunnyvale, California 
Rubenstein, Charles B., Los Gatos, California 

DETDESC : 

... containing heavy metals which are generally considered to be toxic to 
humans and animal life, including arsenic, cobalt, cadmium, chromium, lead, 
nickel, selenium, thallium, zinc, magnesium, copper, antimony, barium, 
molybdenum, rare earths and the like and incidental organic toxins. In general, 
the invented process comprises a batch or continuous operation for the 
processing of industrial waste and contaminated water. The process developed as 
described m this patent is not ... H 

LEVEL 1 - 39 OF 68 PATENTS 

4,806,328 

Feb. 21, 1989 

Method of manufacturing monolithic glass members 

INVENTOR: Van Lierop, Joseph G., Eindhoven, Netherlands 
Bogeraann, Arnoldus B. M. , Eindhoven, Netherlands 

Aid 



Felder, Willy J. B - , Vi^fei, Netherlands 
Huizing, Albert, Eindhoven, Netherlands 



SUM: 



? V Fit the refractive index of the glass member obtained 

after densif ication of the gel at a given value and/or to control other physical 
properties Examples of such compounds are alkoxy compounds of aluminium 
titanium, boron germanium, rare earths and the like, of which the alkoxy groups 
each generally do not comprise more than 4 carbon atoms. Nitrates, carbonates 
acetates and other compounds which decompose easily while forming oxides may' 
optionally also be used. Fluorine ... ' y 

LEVEL 1 - 40 OF 68 PATENTS 
4,775,820 
<=2> GET 1st DRAWING SHEET OF 3 
Oct. 4, 1988 
Multilayer electroluminescent device 

INVENTOR: Eguchi, Ken, Yokohama, Japan 
Kawada, Haruki, Kawasaki, Japan 
Nishimura, Yukuo, Sagaraihara, Japan 

SUM: 

... composed of a material of EL function dispersed in a binder. 

As the material of EL function, there have been known heretofore inorganic 
metal materials such as ZnS containing Mu, Cu, ReF3 (Re: rare earths) or the 
like as an activating agent, and the like. 

In the case of a thin film type EL device, the structure is suitable for the 
following purposes, that is, a thin luminescent layer can be formed so as to 

LEVEL 1 - 41 OF 68 PATENTS 

4,734,338 

<=2> GET 1st DRAWING SHEET OF 3 

Mar. 29, 1988 

Electroluminescent device 

INVENTOR: Eguchi, Ken, Yokohama, Japan 
Kawada, Haruki, Kawasaki, Japan 
Nishimura, Yukuo, Sagamihara, Japan 

SUM: 

... layer composed of a material of^EL function dispersed in a binder. 

As the material of EL function, there have been heretofore inorganic metal 
materials such as ZnS containing Mn, Cu, ReF3 and (Re: rare earths) or the like 
as an activating agent, and the like. 

In the case of a thin film type EL device, the structure is suitable for the 
following purposes, that is, a thin luminescent layer can be formed so as to 

PAGE 46 

LEVEL 1 - 42 OF 68 PATENTS 
4,700,436 
<=2> GET 1st DRAWING SHEET OF 4 
Oct. 20, 1987 



Magnetic fastener 



INVENTOR: Morita, Tamao, 47-1, Arakawa 6-Chome, Arakawa-ku, Tokyo, Japan 
SUM: 

BACKGROUND OF THE INVENTION 

1. Field of the Invention 

The present invention relates to the utilization of permanent magnets made of 
hard magnetic powder of ferrite, alnico, rare-earth and the like materials 
solidified with synthetic resin and then magnetized. More particularly, it 
relates to an improvement is magnetic material fastener means made of permanent 
magnet which is provided with magnetic plates at its magnetic poles. 

2. Description of the Prior Art 

PAGE 

LEVEL 1 - 43 OF 68 PATENTS 
4,681,625 
<=2> GET 1st DRAWING SHEET OF 11 
Jul. 21, 1987 

Methods for simultaneously desulfurizing and degassing 

steels 

INVENTOR: Wilson, William G., 820 Harden Dr., Pittsburgh, Pennsylvania 15229 
SUM: 

. . . difficult to get into solution and also those whose recoveries from their 
addition have been less than the amount added to the steel such as electrolytic 
manganese, f erro-niobiura, ferro- tungsten and the like. The metals that may be 
added include aluminum, calcium, barium, rare earths and the like. The recovery 
of elements in the steel from additions of metals and ferro-alloys is reduced in 
many cases in conventional steel making technology by their contact with slags 
high in oxides such as iron . . . 

. . . [*21] metals to be added in the tube to enhance desulfurization are 
those which are known to have the ability to reduce the oxygen content of the 
steel, but also have the ability to form sulfides which would float out of the 
steel into the slag which include magnesium, calcium, barium, rare earths and 
the like. 

[*22] 22. The method as claimed in claims 1 or 5 wherein the ferro-alloys 
and elemental metals to be added in the tube are those necessary to obtain the 
desired chemical analysis of the finished steel such as ferro- . . . 

LEVEL 1 - 44 OF 68 PATENTS 

4,598,914 

<=2> GET 1st DRAWING SHEET OF 10 

Jul. 8, 1986 

Sealing and bearing means by use of ferrofluid 

INVENTOR: Furumura, Kyozaburo, Ninomiya, Japan 
Sugi, Hirorai, Fujisawa, Japan 
Murakami, Yasuo, Fujisawa, Japan 
Asai, Hiroraitsu, Fujisawa, Japan 

DETDESC : 

... polyaraide resin, fluorine resin, polyethersulf one resin, polypheny lene 



t'V The magnetic material to be .Med with the afore** -M 
synthetic resxn materxaTis made of barium ferrite powde^str^Jium ferrlte 



sulfide resin or the 1 
synthetic resin materi 
powder, rare earths or the like 



sub^LJe^rdirrer^f Syi *J etic resin and ««e aforesaid normal magnetic 
seaHnrpur^oses " " ^ 18 USed f ° r be " in S ™* 

In case the magnet is employed as bearing, it is to have enough 

LEVEL 1 - 45 OF 68 PATENTS 

4,582,688 

<=2> GET 1st DRAWING SHEET OF 1 

Apr. 15, 1986 

Process for recovery of mineral values 

INVENTOR: Venkatesan, Valadi N. , Arlington, Texas 

DETDESC: 

... present, molybdenum can be selectively leached from the ore utilizing a 
leaching solution containing sodium bicarbonate and oxygen. Thus, for example 
Ji-^^S SUC 5 f? v f?* diura > molybdenum, selenium, nickel, copper, uranium, the 
rare earths and the like may be recovered using the process of the present 
invention. The main criteria is that at least one of the minerals found in the 
ore may be solubilized without the solubilization of at least one other mineral. 

Thus, the present . . . 

... part of the uranium is present as a refractory uranium-mineral complex. 
*or example, other minerals found in the form of a uranium-mineral complex, 
include copper, nickel, thorium, scandium, the rare earths, and the like. 

Uranium minerals frequently occur in the highly siliceous rocks and 
sedimentary deposits, generally as a mixture of the insoluble tetravalent form 
and the soluble hexavalent form. Uranium is also found in association with the 
silicates , ... 

LEVEL 1 - 46 OF 68 PATENTS 
4,570,692 
<=2> GET 1st DRAWING SHEET OF 6 
Feb. 18, 1986 
Methods of pouring metal 
INVENTOR: Wilson, William G. , 820 Harden Dr., Pittsburgh, Pennsylvania 15229 
DETDESC : 

... teeming operation and good distribution throughout the entire ingot can 
be expected. When the stability of the oxides in the slags is high even the 
most reactive alloys such as aluminum, titanium, zirconium, raagnesum, calcium or 
rare earths and the like will be transferred to the steel from the slag with 
maximum retention of the alloying element in the metal being teemed. The 
addition of these alloys along with these stable oxides that will not react with 
these alloying elements, the elimination of the flow ... 

LEVEL 1 - 47 OF 68 PATENTS 

4,491,563 

Jan. 1, 1985 

Process for deodorizing a paraffinic hydrocarbon feedstock 



All 



INVENTOR: Reusser, Robc^fc., Bart lesville, Oklahoma 
Murtha, Timothy P., BartWsville, Oklahoma 
Todd, Elizabeth A., Bart lesville, Oklahoma 

DETDESC : 

. . . examples are given to provide a better and more complete disclosure of 
this invention but should not be interpreted to limit its scope 
EXAMPLE I 

This example describes a typical catalyst preparation whereby NiO and a 
rare earth like CeO is deposited on a support. This general procedure is also 
described in U.S. Pat. No. 4,217,248 column 7, line 49 to column 8, line 41. Two 
hundred grams of 13 x ... 

LEVEL 1 - 48 OF 68 PATENTS 
4,489,042 
Dec. 18, 1984 

Process for recovery of mineral values from subterranean 

formations 

INVENTOR: Savins, Joseph G. , Dallas, Texas 
Johnson, Warren F. , Dallas, Texas 

DETDESC: 

... formations. However, it should be clear that the invention is applicable 
to the solution leaching of other mineral values capable of forming soluble 
reaction products with leaching solutions. Thus, for example, substances such as 
vanadium, molybdenum, nickel, copper, the rare earths and the like are recovered 
using the process of the present invention. 

As an illustration, the leach chemistry of a uranium ore body can be 
described by the following equations using hydrogen peroxide (H202) as oxidant: 

PAGE 

LEVEL 1 - 49 OF 68 PATENTS 

4,486,026 

<=2> GET 1st DRAWING SHEET OF 10 

Dec. 4, 1984 

Sealing and bearing means by use of ferrofluid 

INVENTOR: Fururaura, Kyozaburo, Ninomiya, Japan 
Sugi, Hiromi, Fujisawa, Japan 
Murakami, Yasuo, Fujisawa, Japan 
Asai, Hiroraitsu, Fujisawa, Japan 

DETDESC : 

... polyamide resin, fluorine resin, polyethersulf one resin, polypheny lene 
sulfide resin or the like. The magnetic material to be mixed with the aforesaid 
synthetic resin material is made of barium ferrite powder, strontium ferrite 
powder, rare earths or the like. 

The mixture ratio of the synthetic resin and the aforesaid normal magnetic 
substance is different in case the magnet is used for bearing purposes and 
sealing purposes. 

In case the magnet is employed as bearing, it is to have enough . . . 

PAGE 54 

LEVEL 1 - 50 OF 68 PATENTS 
4,481,437 



<=2> GET 1st DRAWING SHEET OF 3 



Nov. 6, 1984 

Variable flux permanent magnets electromagnetic machine 
INVENTOR: Parker, Rollin J., Greenville, Michigan 
DETDESC : 

... cylindrical housing 12 in which is mounted, by any appropriate convenient 
means, a cylindrical tubular stator 14 comprising high strength permanent 
magnets such as ceramic, or ceramic rare earth, cobalt-rare earth, or the like 
[magents] magnets. Each one of a pair of end cap members 16 and 18 fastened at 
an end of the housing 12 by bolts or screws 20 supports respectively an end 
magnet ring 22 an ... 

LEVEL 1 - 51 OF 68 PATENTS 

4,455,392 

Jun. 19, 1984 

Process for preparing a supported silver catalyst 

INVENTOR: Warner, Glenn H., St. Albans, West Virginia 
Bhasin, Madan M. , Charleston, West Virginia 
Lieberman, Bernard, Kew Gardens, New York 

SUM: 

... as lithium, sodium, potassium, rubidium and/or cesium; one or more 
alkaline earth metals, such as, barium, magnesium and strontium; or one or more 
of the other known promoters, such as thallium, gold, tin, antimony and rare 
earths; and the like. For purposes of convenience, the catalyst preparation 
process of the invention is described below in terras of a silver-first method of 
preparation wherein the promoter is selected from among alkali metals, it being 
recognized that other promoters of ... 

LEVEL 1 - 52 OF 68 PATENTS 

4,438,077 

Mar. 20, 1984 

Two stage selective oxidative leach method to separately 
recover uranium and refractory uranium-mineral complexes 

INVENTOR: Tsui, Tien-Fung, Richardson, Texas 

SUM: 

. . . least part of the uranium is present as a refractory uranium-mineral 
complex. For example, other minerals found in a uranium- mineral complex include 
copper, nickel, thorium, scandium, the rare earths, and the like. 

Uranium minerals frequently occur in the highly siliceous rocks and 
sedimentary deposits, generally as a mixture of the insoluble tetravalent form 
and the soluble hexavalent form. Uranium is also found in association with the 
silicates , ... 

LEVEL 1 - 53 OF 68 PATENTS 
4,427,236 
Jan. 24, 1984 
In-situ uranium leaching 
INVENTOR: Dotson, Billy J., Grand Prairie, Texas 



DETDESC : 



... be clear that the^fcivention is applicable to the s^fcition mining of other 
mineral values capable of forming soluble reaction products with carbonated 
leaching solutions. Thus, for example, substances such as vanadium, molybdenum, 
nickel, copper, the rare earths and the like are recovered using the process of 
the present invention. 

Uranium minerals frequently occur in the highly siliceous rocks and 
sedimentary deposits, generally as a mixture of the insoluble quadrivalent form 
and the soluble sexivalent form. ... 

LEVEL 1 - 54 OF 68 PATENTS 

4,419,276 

Dec. 6, 1983 

Silver catalyst for the manufacture of ethylene oxide and a 
process for preparing the catalyst 

INVENTOR : Bhasin, Madan M. , Charleston, West Virginia 
Warner, Glenn H., St. Albans, West Virginia 

SUM: 

... as lithium, sodium, potassium, rubidium and/or cesium; one or more 
alkaline earth metals, such as, barium, magnesium and strontium; or one or more 
of the other known promoters, such as thallium, gold, tin, antimony and rare 
earths; and the like. For purposes of convenience, the catalyst preparation 
process of the invention is described below in terms of a silver-first method of 
preparation wherein the promoter is selected from among alkali metals, it being 
recognized that other promoters of ... 

PAGE 59 

LEVEL 1 - 55 OF 68 PATENTS 
4,405,380 
Sep. 20, 1983 

High strength, low alloy steel with improved surface and 
mechanical properties 

INVENTOR: Griffith, Cecil B . , North Royalton, Ohio 
Thomas, Jerry D., North Olmsted, Ohio 
Demianczuk, Dionisyj W., Parma, Ohio 
Abraham, John K. , Broadview Heights, Ohio 
Franklin, Joseph E., Medina, Ohio 

DETDESC : 

... present invention is directed to a steel with carbon in the range of 0.03 
to 0.06%, the last being an upper limit which also appears crucial for 
attainment of so-called auto-sulf ide-sfiape control and thus avoidance of the use 
of rare earths or the like with their consequent expense and tendency to produce 
unwanted non-metallic surface inclusions. 

The base metal may thus consist of the defined composition, with manganese in 
the range of 0.2 to 0.6%, very preferably not more than 0.45%, while the ... 

PAGE 60 

LEVEL 1 - 56 OF 68 PATENTS 
4,376,264 
<=2> GET 1st DRAWING SHEET OF 6 
Mar. 8, 1983 

Method of checking the authenticity of papers and physically 
identifiable paper for use in said method 



INVENTOR: Dokter, HendrilTD., Ugchelen, Netherlands 
Hildering, Roelof, Frederikslaan , Netherlands 
Mackor, Adrianus , Hollandsche Rading, Netherlands 

SUM: 

... be some which show a suitable ESR spectrum, although to the knowledge of 
the present inventors this has never been investigated. However, a further 
requirement is that a useful ESR spectrum should be obtained at room 
temperature. Many compounds of rare earths and the like show a useful ESR 
spectrum only at low temperatures, such as the temperature of liquid nitrogen, 
but of course an identification of banknotes and the like is hardly of any 
practical value, if it cannot be carried out at normal room ... 

PAGE 61 

LEVEL 1 - 57 OF 68 PATENTS 

4,367,163 

<=2> GET 1st DRAWING SHEET OF 1 

Jan. 4, 1983 

Silica-clay complexes 

INVENTOR: Pinnavaia, Thomas J., East Lansing, Michigan 
Mortland, Max M., East Lansing, Michigan 
Endo, Tadashi, East Lansing, Michigan 

DETDESC: 

... be used as a catalyst support for various catalytically active metals 
such as a Group VIII aetal such as platinum, palladium, nickel, iron or cobalt; 
molybdenum; tungsten; a rare-earth and the like. Moreover, the intercalated 
product can be used in admixture with other common adsorbents or matrix 
materials such as silica, alumina, silica-alumina hydrogel and the like. The 
catalysts which can be prepared by ... 

LEVEL 1 - 58 OF 68 PATENTS 

4,358,158 

<=2> GET 1st DRAWING SHEET OF 1 

Nov. 9, 1982 

Solution mining process 

INVENTOR: Showalter, William E. , Seal Beach, California 

DETDESC : 

. . . invention is applicable to the solution raining of other mineral values 
capable of forming soluble reaction products with the dilute carbonic acid 
leaching solution. Thus, for example, substances such as vandium, molybdenum, 
nickel, copper, the rare earths and the like can be recovered using the process 
of the present invention. 

Uranium minerals frequently occur in the highly siliceous rocks and 
sedimentary deposits, generally as a mixture of the insoluble quadrivalent form 
and the soluble . . . 

LEVEL 1 - 59 OF 68 PATENTS 
4,358,157 
<=2> GET 1st DRAWING SHEET OF 1 
Nov. 9, 1982 
Solution raining process 

/U7 




INVENTOR: Showalter, William E. , Seal Beach, California 



DETDESC : 

. . . invention is applicable to the solution raining of other mineral values 
capable of forming soluble reaction products with the dilute carbonic acid 
leaching solution. Thus, for example, substances such as vanadium, molybdenum, 
nickel, copper, the rare earths and the like can be recovered using the process 
of the present invention. 

Uranium minerals frequently occur in the highly siliceous rocks and 
sedimentary deposits, generally as a mixture of the insoluble quadrivalent form 
and the soluble . . . 

LEVEL 1 - 60 OF 68 PATENTS 
4,328,079 
<=2> GET 1st DRAWING SHEET OF 1 
May 4, 1982 

Method for pumping impurities, especially noble gases, from 
hydrogen or mixtures of hydrogen and its isotopes 

INVENTOR: Hemmerich, Johann, Stetternich, Federal Republic of Germany 

DETDESC : 

... 2 is adjusted by the fluid within the chamber 13 to the temperature for 
the desired hydrogen partial pressure. In this variation, the cathodes are 
formed from hydride- forming metals and alloys, for example, rare earth and 
rare earth- like metals and binary and ternary alloys of them with the addition 
of transition metals like iron, nickel, cobalt, etc. Upon formation of the 
sputtered film 12, hydrogen and its isotopes form hydrides with the film by 
chemisorption that can . . . 

LEVEL 1 - 61 OF 68 PATENTS 

4,279,668 

<=2> GET 1st DRAWING SHEET OF 7 

Jul. 21, 1981 

Directionally solidified ductile magnetic alloy 

INVENTOR: Kurz, Wilfried, Lausanne, California, Switzerland 
Glardon, Rerai, Berkeley, California 

SUM: 

. . . relates to a process for the fabrication of magnetic alloys for permanent 
magnets and to the magnetic bodies obtained by this process. 

More particularly the invention relates to ternary magnetic alloys consisting 
of rare-earth or rare-earth- like elements, cobalt and at least one metal 
selected from the group which consists of iron, nickel, aluminum, copper, 
molybdenum or manganese. Preferably the latter metal phase includes 0.1 to 10% 
(atomic) of the total alloy as . . . 

LEVEL 1 - 62 OF 68 PATENTS 

4,208,225 

<=2> GET 1st DRAWING SHEET OF 6 

Jun. 17, 1980 

Directionally solidified ductile magnetic alloys 
magnetically hardened by precipitation hardening 



INVENTOR: Kurz, Wilf rie<^PLausanne , Switzerland 
Glardon, Rerai, Corseaux, Switzerland 



SUM: 

... relates to a process for the fabrication of magnetic alloys for permanent 
magnets and to the magnetic bodies obtained by this process. 

More particularly the invention relates to ternary magnetic alloys consisting 
of rare-earth or rare earth- like elements, cobalt and at least one metal 
selected from the group which consists of iron, nickel, aluminum, copper 
molybdenum or manganese. ' 
BACKGROUND OF THE INVENTION 

Ferromagnetic alloys of the cobalt/rare-earth type have a high energy 

LEVEL 1 - 63 OF 68 PATENTS 

4,105,253 

<=2> GET 1st DRAWING SHEET OF 1 

Aug. 8, 1978 

Process for recovery of mineral values from underground 

formations 

INVENTOR: Showalter, William E . , Seal Beach, California 
DETDESC : 

... be clear that the invention is applicable to the solution mining of other 
mineral values capable of forming soluble reaction products with carbonated 
leaching solutions. Thus, for example, substances such as vanadium, molybdenum, 
nickel, copper, the rare earths and the like are recovered using the process of 
the present invention. 

Uranium minerals frequently occur in the highly siliceous rocks and 
sedimentary deposits, generally as a mixture of the insoluble quadrivalent form 
and the soluble sexivalent form. ... 

LEVEL 1 - 64 OF 68 PATENTS 

4,050,052 

<=2> GET 1st DRAWING SHEET OF 1 

Sep. 20, 1977 

Electrical temperature measuring resistor structure, 
particularly for resistance thermometers 

INVENTOR: Reichelt, Walter, Hanau, Germany, Federal Republic of 
Sauer, Gunter, Maintal, Germany, Federal Republic of 

DETDESC : 

... temperatures can be applied. This cover layer, shown in FIG. 2 
schematically at 3, may consist for example of an epoxy resin, glass, or metal 
oxides of the group of aluminum, beryllium, thorium, rare earths, or the like. 
The cover layer 3 may be applied by vapor deposition, dusting, or spraying; its 
primary characteristics should be to be resistant against thermal and mechanical 
effects. The cover layer should additionally, preferably, provide ... 

LEVEL 1 - 65 OF 68 PATENTS 

4,014,706 

Mar. 29, 1977 

Solid solution ceramic materials 

INVENTOR: Waldron, Robert D. , Scottsdale, Arizona 



SUM: 



... dimensions of said structure and all physical and chemical properties of 
-JF flre " ntinuous function, of composition. The lattice K2E£ L? 
ttrco^^rclangr 8111011 " nge by Unif0rn diSt ° rtion ° f the sLuc'Se^ 

numbS zT^^of S^T^ elementS 85 USed herela eleraents ° f at ™- 

number's"^ ^cr^w}" 0 elementS " USed meanS elementS ° f ato ™ ic 

PAGF 

LEVEL 1 - 66 OF 68 PATENTS 

3,983,077 

<=2> GET 1st DRAWING SHEET OF 2 

Sep. 28, 1976 

Process for making ceramic resistor materials 

INVENTOR: Fuller, Peter G., Lakeville, Massachusetts 
Stoeckler, Hans A., Woonsocket, Rhode Island 

DETDESC : 

oxide 'or^thf f?V a a 1S 2 t ^ iCa l ly inClUde additions °f silicon oxide or manganese 

?*. the llke fnd other dopants typically incorporated in such ceramit 
n?W lll° nS in ^ lude J 1 fn than «™» cerium, dysprosium, and praesodymium as well as 
other rare earths and the like commonly used in ceramic resistor materials of 
M^tl?, P S rat S r {! C °* fficient of resistivity. Typically, the ceramic titanate 
materials produced by the process are provided with stoichiometric or slightly 
titanium-rich compositions, the compositions preferably having an 

LEVEL 1 - 67 OF 68 PATENTS 

3,896,616 

<=2> GET 1st DRAWING SHEET OF 1 

Jul. 29, 1975 

Process and apparatus 

INVENTOR: Keith, Carl D., Summit, New Jersey 
Mooney, John J., Wyckoff, New Jersey 



DETDESC : 

... 0.1 to 1.5% The catalytic element may contain, with or without the 
platinum group metals, one or more catalytic materials which may include, for 
example, chromium, manganese, vanadium, copper, iron, cobalt, nickel, rare 
earths, and the like. 

.....w^^S 1 - 6 S± ? eS ° f tl ? G initial and subsequent catalytic elements may be 
such that their volume ratio, i.e. the superficial volume of the subsequent 
catalyst to the initial catalyst, including void spaces within the catalytic 
masses, is often at least about ... 

LEVEL 1 - 68 OF 68 PATENTS 

3,791,143 

<=2> GET 1st DRAWING SHEET OF 1 

Feb. 12, 1974 

PROCESS AND APPARATUS 



INVENTOR: Keith, Carl D. , Summit, New Jersey 
Mooney, John J., Wyckoff, New Jersey 

DETDESC : 

... 1.5 percent. The catalytic element may contain, with or without the 
platinum group metals, one or more catalytic materials which may include, for 
example, chromium, manganese, vanadium, copper, iron, cobalt, nickel rare 
earths, and the like. * 

The relative sizes of the initial and subsequent catalytic elements may be 
such that their volume ratio, i.e., the superficial volume of the subsequent 
catalyst to the initial catlyst, including void spaces within the catalytic 
masses, is often at least about ... 

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IBM CORPORATION 

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LEVEL 1 - 1 OF 4 PATENTS 
5,344,815 
<=2> GET 1st DRAWING SHEET OF 4 
Sep. 6, 1994 

Fabrication of high T C superconducting helical resonator 

coils 

INVENTOR: Su, Sophia R., Weston, Massachusetts 
O Connor, Margaret, Worcester, Massachusetts 
Butler, Scott, N. Oxford, Massachusetts 

■•• [*13] oxygen for at least 2 hr. 

[*14] 14. A method in accordance with rlai™ 11 • j 

comprises at least about 3 w/o grain alJJiJ wherein said mixture further 

barium copper oxide superconductor * clusters of a like rare earth 

[*15] 15. A method in accordance with claim 11 wherein said rare earth 



barium copper oxide inductor is an yttrium bariun. Aer oxide 

superconductor. 

[*16] 16. A ... 

LEVEL 1 - 2 OF 4 PATENTS 

5,236,091 

<=2> GET 1st DRAWING SHEET OF 5 

Aug. 17, 1993 

Eddy current separator and method of making a rotor 

INVENTOR: Kauppila, Raymond, Marquette, Michigan 
Nowak, Gregory, Girard, Pennsylvania 

... as follows : 

[*1] 1. A rotor for an eddy current separator comprising a rotor body 
having generally cylindrical, outer peripheral surfaces designed to be rotated 
at a design speed; 

plate- like rare earth permanent magnets; 

adhesive means attaching said plate- like rare earth permanent magnets to said 
outer peripheral surfaces of said rotor body at a bond line; 

said plate- like rare earth permanent magnets being disposed in longitudinal 
rows extending from one end of said rotor to the other; 

said plate- like rare earth permanent magnets in a particular row having a 
polarity on their outer end opposite the polarity of an outer end of said 
plate- like permanent magnets in adjacent rows; 

a fiber means . . . 

... [*3] equal to that of carbon. 

[*4] 4. A rotor for an eddy current separator comprising a rotor body 
having generally cylindrical, outer peripheral surfaces designed to be rotated 
at a design speed; 

plate- like rare earth permanent magnets; 

adhesive means attaching said plate- like rare earth permanent magnets to said 
outer peripheral surfaces of said rotor body at a bond line; 

said plate- like rare earth permanent magnets being disposed in longitudinal 
rows extending from one end of said rotor to the other; 

said plate- like rare earth permanent magnets in a particular row having a 
polarity on their outer end opposite the polarity of an outer end of said 
plate- like permanent magnets in adjacent rows; 

fiber means wrapped . . . 

... [*7] body having a polygonal outer periphery; 

said polygonal outer periphery having a plurality of circumferential ly 
disposed adjacent flat surfaces of equal width extending longitudinally of 

Pat. No. 5236091, *7 

said rotor from end to end thereof; 

plate- like rare earth permanent magnets having a width substantially equal to 
the width of sides of said polygonal outer periphery and attached to said flat 



surfaces by adhesive; 

to «" 1 ve e s. 1 iS^„?„!!? de ° f M ^"^cally non-conductive .atrial and adapts 

a heat shield being . . . 

LEVEL 1 - 3 OF 4 PATENTS 

5,162,298 

<=2> GET 1st DRAWING SHEET OF 5 

Nov. 10, 1992 

Grain boundary junction devices using high T c 
superconductors 

INVENTOR: Chaudhari, Praveen, Briarcliff Manor, New York 
Lhi, Cheng-Chung J., Yorktown Heights, New York 
Dimos, Duane B., Upper Montclair, New Jersey 

tSIo?* 1 ^ JOC J en Metzin S en > New York, Federal Republic of Germany 

Tsuei, Chang C, Chappaqua, New York *n.dny 

greater f thln 77°?^* raaterial havin 8 a superconducting onset temperature 

»„ lt 5] 5' P? device of claim 4, where said superconducting material includes 
an atom selected from the group consisting of rare earth atom! and lncludes 
eartn-like atoms. 

an ISlin^-elrtVa^s 6 . 0 ' Clalm *' **** " ld SU P— Acting material includes 
bismuth. ? " deVi ° e ° f Claim *' Where S3id su P ercond ^ting raaterial includes 

[*8] 8. The device of claim 1, where ... 

LEVEL 1 - 4 OF 4 PATENTS 

4,681,625 

<=2> GET 1st DRAWING SHEET OF 11 

Jul. 21, 1987 

Methods for simultaneously desulfurizing and degassing 

steels 

INVENTOR: Wilson, William G. , 820 Harden Dr., Pittsburgh, Pennsylvania 15229 

i-w" l* 2 l ] m f tals to be added in the tube to enhance desulfurization are 
those which are known to have the ability to reduce the oxygen content of the 

Itltl'&t a tt\^ Ve SV^f'J t0 f0rn SUlfid6S Which «™ ld float oJt of the 
the Jike 8 inc l" d e magnesium, calcium, barium, rare earths and 

flnH [ *? 2] }\- T J>e method as claimed in claims 1 or 5 wherein the ferro-allovs 
* 12:52 5 p P H? E STARTED *» ^g/',, I 



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Subject: LEXIS(R)/NEXIS(R) Print Request Job 97085, 1 of 2 

MORRIS, DAN 

IBM CORPORATION 

YORKTOWN PATENT OPERATIONS 

T. J. WATSON RESEARCH CENTER 

P.O. BOX 218 

YORKTOWN HEIGHTS, NEW YORK 10598-0218 
MAIL- IT REQUESTED: NOVEMBER 22, 1997 100G6J 

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IBM CORPORATION 
YORKTOWN PATENT OPERATIONS 
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P.O. BOX 218 

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A A A A A A A A A A A A A A A Ait A A A A A A A A A A A A A A A ft<rQ6Qfig- A M A A A A A A A A AAA-AAA A A A A 1 AAA A A A A A AAA ,V * ^fr 

FOCUS - 1 OF 107 PATENTS 



5,686,394 



<=2> GET 1st DRAWING SHEET OF 1 



Nov. 11, 1997 

Process for manufacturing a superconducting composite 

INVENTOR: Sibata, Kenichiro, Hyogo, Japan 
Sasaki, Nobuyuki, Hyogo, Japan 
Yazu, Shuji, Hyogo, Japan 
Jodai, Tetsuji, Hyogo, Japan 

SUM: 

. . . Ho-Cu-0 system or Ba-Dy-Cu-0 system compound oxide which possess the 
quasi-perovskite type crystal structure including an orthorhombically distorted 
perovskite or a distorted oxygen-deficient perovskite or the like. 



CI 



The abovementioned superconductors can be prepa. ~from a powder mixture 

Consisting of oxides and/or carbonates containing constituent elements of said 
superconductor. The powder mixture nay include optionally oxides and/or 
carbonates of at least ... 

FOCUS - 2 OF 107 PATENTS 

5,679,980 

<=2> GET 1st DRAWING SHEET OF 5 

Oct. 21, 1997 

Conductive exotic-nitride barrier layer for 
high-dielectric-constant material electrodes 

INVENTOR: Suramerfelt, Scott R. , Dallas, Texas 

DETDESC : 

TABLE 

* Conductive perovskite like 

FOCUS - 3 OF 107 PATENTS 

5,665,628 

<=2> GET 1st DRAWING SHEET OF 5 

Sep. 9, 1997 

Method of forming conductive amorphous-nitride barrier layer 
for high-dielectric-constant material electrodes 

INVENTOR: Summerfelt, Scott R., Dallas, Texas 

DETDESC: 

TABLE 

" Conductive perovskite like 

FOCUS - 4 OF 107 PATENTS 

5,661,112 

<=2> GET 1st DRAWING SHEET OF 3 

Aug. 26, 1997 

Superconductor 

INVENTOR: Hatta, Shinichiro, 201-1028, Higashinakafuri-2-chome, Hirakata-shi, 
Japan * 

Higashino, Hidetaka, A2-505, 117, Hitotsuyacho, Matsubara-shi , Japan 
Hirochi, Kumiko, 22, Keihanhondori- 1-chome, Moriguchi-shi, Japan 
Adachi, Hideaki, 3-1-505, Mitsuiminamimachi , Neyagawa-shi , Japan 

... [*1] film being a transition metal element selected from Pt, Au , Ag 
Pd, Ni and Ti the composition A-B-Cu-0 of said oxide film being in the form of 
layered perovskite- like structure. 

[*2] 2. A superconductor according to claim 1, wherein an additional metal 
film is formed on said oxide film, or the oxide films and metal films are 
laminated alternately to form a multi- layer structure. 

[*3] 

FOCUS - 5 OF 107 PATENTS 



5,648,114 
<=2> GET 1st DRAWING SHEET OF 4 
Jul. 15, 1997 

Chemical vapor deposition process for fabricating layered 
superlattice materials 

iK22: ir^tiZ^ A - Col °" do SM c ° IO " d ° 

Scott, Michael C, Colorado Springs, Colorado 
Mihara, Takashi, Saitaraa, Japan 

DETDESC: 

r+ " h ® re A1 » A2 ' • • A "present A-site elements in the perovskite- lik* 

such as oxygen, fluorine, chlorine and hybrids of these elements? such _ eiitS 

i>,r\*; [ * 14J s2 > . . . Sk[xk]< + sk> Bl[yll< + bl> B2r V 21< + b2 > 
Ki e^^e' J^/ 1 ' A2 Sk ^ "Pres-I-site'elements in a 
lements, Bl^ B2 Bl'r^resent B-si^e SEE' ^ i^vJ S?S£ 

^ H ni0n ' r PerSCriptS indicate valeicS S of tt 

respective elements, the subscripts indicate an average number of atoms of the 
element in the unit cell, and at least wl and y l are non-zero, and SlSeS said 

FOCUS - 6 OF 107 PATENTS 

5,647,904 

<=2> GET 1st DRAWING SHEET OF 2 

Jul. 15, 1997 

Method for manufacturing superconducting ceramics in a 

magnetic field 

INVENTOR: Yamazaki, Shunpei, Tokyo, Japan 

SUM: 

con ,;A; n -^° K - ty 3 me ! h ° d in which a fixture of chemicals in a suitable 
composition is compacted and fired. These superconducting ceramics form a 
quasi-molecular atomic unit in a perovskite- like structure wJose uni? cell is 

ITtirT t Wlth ° ne v 3yer ln Which elect ™ns have essentially one-dimensional 
motion, whereas a number of crystalline grains are arranged at randam wi?h 
diverse crystalline directions, and therefore the critic! 1 c^ren? densi^ is 

... cm from conventional several millimeters. The breadth and thickness mav 



PAG 



comparison with the prior art technique 

ilWrat^f r?£ T 6rialS & l e constructed in perovskite- like structures as 
co«?f«« ; accordance with the present invention. The structure 

sSndLg°?L er copper *! " intervenin * C °PP er "o- 3, oxygen atoms 5 and 6 



C3 



DRWDESC : W 

BRIEF DESCRIPTION OF THE DRAWINGS 



FIG. 1 is a schematic diagram showing the configuration of the 
perovskite-like molecular sturcture in accordance with the present invention. 

FIGS. 2(A) and 2(B) are top and side sectional views showing an apparatus for 
manufacturing superconducting ceramics in accordance with the present invention 

FOCUS - 7 OF 107 PATENTS 

5,646,094 

<=2> GET 1st DRAWING SHEET OF 4 

Jul. 8, 1997 

Rare earth substituted thallium-based superconductors 

INVENTOR: Tallon, Jeffrey Lewis, 3 Marine Drive, York Bay, Eastbourne, New 
Zealand 

Presland, Murray Robert, 4/1 Mahina Bay Road, Mahina Bay, Eastbourne, New 
Zealand 

ABST: 

... lanthanide rare earth elements and where 0.3 </= a,b </= 0.7, 0 05 </= c 
</= 1.1,2 - c </= d </= 1.95, 0.05 </= e </= 1, 1.9 </= f </= 2.1 and 6.5 </= g 
</- 7.5. These compounds, which are layered perovskite-like oxides, exhibit a 
high chemical stability, form readily into nearly single phase, do not require 
adjustment of oxygen stoichiometry after synthesis and compositions may be 
chosen allowing superconductivity at temperatures . . . 

SUM: 

... for example, do not require adjustment of oxygen stoichiometry after 
synthesis, and compositions may be chosen allowing superconductivity at 
temperatures exceeding 100 K. 

The novel compounds described herein have the same tetragonal layered 
perovskite-like structure of the parent compound T10 .5Pb0 . 5CaSr2Cu207 comprising 
in sequence: a T10.5Pb0.50 layer with Tl/Pb occupying square comer-shared sites 
and oxygen distributed about the face centre; a SrO layer with . . . 

FOCUS - 8 OF 107 PATENTS 

5,626,906 

<=2> GET 1st DRAWING SHEET OF 3 

May 6, 1997 

Electrodes comprising conductive perovskite-seed layers for 

perovskiter dielectrics 

INVENTOR: Summerfelt, Scott R., Dallas, Texas 
Beratan, Howard R., Dallas, Texas 

ABST: 

... layer and the conductive oxide layer each comprise the same metal. The 
metal should be conductive in its metallic state and should remain conductive 
when partially or fully oxidized. Generally, the perovskite-seed layer has a 
perovskite or perovskite-like crystal structure and lattice parameters which are 
similar to the perovskite dielectric layer formed thereon. At a given deposition 
temperature, the crystal quality and other properties of the perovskite 
dielectric will generally be enhanced by depositing it on ... 

SUM: 

... As used herein, the term "high-dielectric-constant" means ft dielectric 
constant greater than about 50 at device operating temperature. As used herein 
the term perovskite means a material with a perovskite or perovskite-like 



crystal structure. As ^fc herein the term "dielectric" ^ien used in reference 
to a perovskite, means a non- conductive perovskite, pyroelectric, ferroelectric, 
or high-dielectric-constant oxide material. The deposition of a 

... structure. To facilitate perovskite crystal formation, perovskite 
dielectrics such as PZT have been deposited on some conductive perovskites such 
as YBa2Cu30[7 - x ]and (La,Sr)Co03. Deposition of PZT on a substrate with a 
perovskite or perovskite- like crystal structure normally minimizes the formation 
of the pyrochlore phase and improves the properties of the perovskite 
dielectric. However, the materials used thus far for the deposition surface have 
several problems. For example, they typically involve new cations such ... 

... layer each comprise the same metal. The metal should be conductive in its 
metallic state and should remain conductive when partially or fully oxidized, 
and when in a perovskite. Generally, the perovskite-seed layer has a perovskite 
or perovskite- like crystal structure and lattice parameters which are similar to 
the perovskite dielectric layer formed thereon. At a given deposition 
temperature, the crystal quality and other properties of the perovskite 
dielectric will generally be enhanced by depositing it on ... 

DETDESC: 

TABLE 

ruthenate seed layer perovskite- like materials 

FOCUS - 9 OF 107 PATENTS 

5,611,854 

Mar. 18, 1997 

Seed crystals with improved properties for melt processing 
superconductors for practical applications 

INVENTOR: Veal, Boyd W., Downers Grove, Illinois 
Paulikas, Arvydas , Downers Grove, Illinois 
Balachandran, Uthamalingam , Hinsdale, Illinois 
Zhong, Wei, Chicago, Illinois 

DETDESC: 

... Although PbTi03 is shown in the Table, other perovskites of the form 
RTi03, when R is La or a rare earth are good candidates. EuTi03 has a lattice 
parameter of 3,897 [Angstrom] . NdGa03, and other perovskite- like oxides with 
the prototype GdFe03 structure should also serve well. NdGa03 is available as a 
commercial substrate material. Others may also be commercially available, 
particularly LaCr03 which has many industrial applications. 

Oxides with the GdFe03 ( ... 

FOCUS - 10 OF 107 PATENTS 

5,602,080 

<=2> GET 1st DRAWING SHEET OF 1 

Feb. 11, 1997 

Method for manufacturing lattice-matched substrates for 
high-T[c] superconductor films 

INVENTOR: Bednorz, Johannes G., Wolfhausen, Switzerland 
Mannhart, Jochen D. , Thalwil, Switzerland 
Mueller, Carl A., Hedingen, Switzerland 
Schlom, Darrell G., State College, Pennsylvania 

SUM: 

... a close match-preferably approaching an ideal match-of the lattice 
parameters of a substrate-without a buffer layer-to a selected high-T[c 



] superconductor raateri^having a perovskite or a perov te-like crystal 
structure can be achieved by a method comprising the following steps- 
Determining the relevant lattice constant or constants of the selected 
superconductor material; choosing a desired orientation of the superconductor 

... for the deposition of the superconductor. 

*„w™£ re 5 erred * ra ? th °^ ° f ^ G in Y ention for manufacturing a lattice-matched 

fl \°t a selected high-T[c ] superconductor material having a 
perovskite or perovskite- like crystal structure at a selected orientation 
relative to the film dimensions comprises the steps set forth below. 

The preferred method of the invention includes the step of determining a 
relevant lattice constant or constants of the selected 

... make the codeposition from separate sources each containing one or more 
ot the materials combined to form the buffer layer. 

Preferred substrate component materials include strontium titanate SrTi03 and 

JfS^n? alum " mte I^A103 for perovskite- like superconductor materials such as 

ii>azLu3U7 - delta . 

In the following description, a preferred method for manufacturing 
crystalline substrate material having essentially the same lattice constant as 
tne corresponding lattice constant of a 

FOCUS - 11 OF 107 PATENTS 

5,593,951 

<=2> GET 1st DRAWING SHEET OF 4 

Jan. 14, 1997 

Epitaxy of high T[C ] superconductors on silicon 

INVENTOR: Himpsel, Franz J., Mt. Kisco, New York 

SUM: 

... first showed superconducting behavior in mixed copper-oxides, typically 
including rare earth and/or rare earth- like elements and alkaline earth 
elements, for example La, Ba, Sr, . . . , and having a perovskite- like 
structure. 

Materials including the so called "1-2-3" phase in the Y-Ba-Cu-0 system have 
been found to exhibit a superconducting transition temperature in excess of 77K. 
R . B . ... 

FOCUS - 12 OF 107 PATENTS 

5,590,053 

<=2> GET 1st DRAWING SHEET OF 20 

Dec. 31, 1996 

Method of determining a space group 

INVENTOR: Ito, Tatsuya, Kawasaki, Japan 
Kawai, Masahito, Kawasaki, Japan 
Yasukawa, Yoshihito, Kawasaki, Japan 

DETDESC : 

... present invention will be described with reference to FIG. 15 to FIG 20 
Let it be assumed here that a crystal as a target of analysis is one of 
LaGdSrCu04. In the case of investigation into such a perovskite- like copper 
oxide superconductor, it is an effective technique of investigating a new 
substance to laminate partial structures to grasp a laminate structure 

C G 



characteristic of the ^itance. The structure analysis the target crystal by 
this technique will . . . 

FOCUS - 13 OF 107 PATENTS 
5,589,284 
<=2> GET 1st DRAWING SHEET OF 3 
Dec. 31, 1996 

Electrodes comprising conductive perovskite-seed layers for 

perovskite dielectrics 

INVENTOR: Summer felt, Scott R. , Dallas, Texas 
Beratan, Howard R . , Dallas, Texas 

ABST: 

... layer and the conductive oxide layer each comprise the same metal. The 
metal should be conductive in its metallic state and should remain conductive 
when partially or fully oxidized. Generally, the perovskite-seed layer has a 
perovskite or perovskite- like crystal structure and lattice parameters which are 
similar to the perovskite dielectric layer formed thereon. At a given deposition 
temperature, the crystal quality and other properties of the perovskite 
dielectric will generally be enhanced by depositing it on ... 

SUM: 

... As used herein, the term "high-dielectric-constant" means a dielectric 
constant greater than about 50 at device operating temperature. As used herein 
the term perovskite" means a material with a perovskite or perovskite- like 
crystal structure. As used herein the term "dielectric", when used in reference 
to a perovskite, means a non- conductive perovskite, pyroelectric, ferroelectric, 
or high-dielectric-constant oxide material. The deposition of a ... 

... structure. To facilitate perovskite crystal formation, perovskite 
dielectrics such as PZT have been deposited on some conductive perovskite such 
as YBa2Cu30[7-x ]and (La,Sr)Co03. Deposition of PZT on a substrate with a 
perovskite or perovskite- like crystal structure normally minimizes the formation 
of the pyrochlore phase and improves the properties of the perovskite 
dielectric. However, the materials used thus far for the deposition surface have 
several problems. For example, they typically involve new cations such ... 

... layer each comprise the same metal. The metal should be conductive in its 
metallic state and should remain conductive when partially or fully oxidized, 
and when in a perovskite. Generally, the perovskite-seed layer has a perovskite 
or perovskite- like crystal structure and lattice parameters which are similar to 
the perovskite dielectric layer formed thereon. At a given deposition 
temperature, the crystal quality and other properties of the perovskite 
dielectric will generally be enhanced by depositing it on ... 

DETDESC: 

TABLE 

ruthenate seed layer perovskites or perovskite- 

* * like materials (e.g. 

FOCUS - 14 OF 107 PATENTS 

5,585,300 

<=2> GET 1st DRAWING SHEET OF 5 

Dec. 17, 1996 

Method of making conductive amorphous-nitride barrier layer 
for high-dielectric-constant material electrodes 

INVENTOR: Summerfelt, Scott R., Dallas, Texas 



C7 



DETDESC : 



TABLE 

* * Conductive perovskite like 

FOCUS - 15 OF 107 PATENTS 

5,583,096 

<=2> GET 1st DRAWING SHEET OF 8 

Dec. 10, 1996 

Superconductive compounds and process for producing said 

compounds 

INVENTOR: Cavazos, Ramon G., Paseo de la Reforma 403, Primer Piso, Mexico D F 
06500 

DETDESC : 

... A. Muller in their article entitled "Possible High Tc Superconductivity 
in Ba-La-Cu-0 System". (Zeitschrift fur Physik B-Condensed Matter 64,189-193 
(1986), reported: "... perovskite- like-mixed valent copper compound. Upon 
cooling, the samples show a linear decrease in resistivity, then an 
approximately logarithmic increase, interpreted as a beginning of localization. 
Finally, an abrupt decrease by ... 

FOCUS - 16 OF 107 PATENTS 

5,563,331 

<=2> GET 1st DRAWING SHEET OF 3 

Oct. 8, 1996 

Magnetoresistive sensor utilizing a sensor material with a 
perovskite- like crystal structure 

INVENTOR: Von Helmolt, Rittmar, Erlangen, Federal Republic of Germany 
Wecker, Joachim, Roettenbach, Federal Republic of Germany 

ABST: 

A magnetoresistive sensor may be constructed with material having a 
perovskite- like crystal structure and an increased magnetoresistive effect. The 
material is based on the composition (Al) [ 1-x] (A2) [x]MnO[z] , with Al (trivalent) 
selected from Y, La, or a lanthanide, A2 (bivalent) from an alkaline- ... 

SUM: 

BACKGROUND OF THE INVENTION 

The present invention relates to a magnetoresistive sensor with a layer made 
of a sensor material that possesses a perovskite- like crystal structure and 
exhibits an increased magnetoresistive effect. 

The general structure and operation of magnetoresistive sensors with thin 
films made of ferromagnetic transition metals are explained further in, for 
example, the book "Sensors", Vol. ... 

... x]Se (cf. "Journal of Applied Physics," Vol. 38, No. 3, Mar. 1, 1967, pp. 
959-964). A corresponding effect is also evident in NdO . 5Pb0 . 5Mn03 crystals; 
these crystals have a perovskite- like structure (cf. "Physics B," Vol. 155, 
1989, pp. 362-365). However, the change in electrical resistance as a function 
of magnetic induction observed in these material systems is confined to low . . . 

... occur only to a reduced extent, in a sensor material that is the subject 
of a German patent application No. P 43 10 318.9 (not previously disclosed). 

c 6 



This material possesses ^(perovskite- like crystal struc'^i and exhibits an 
increased magnetoresistxve effect. A composition based on (Al) [ 1-x] (A2) [x]MnO[x 
]is to be selected for the material, such that the trivalent constituent Al at 
least contains . . . 

. . . sensor according to an embodiment of the present invention includes at 
least two layers, a first layer and a second layer. Each of the first and second 
layers is made of a sensor material that possesses a perovskite- like crystal 
structure and exhibits an increased magnetoresistive effect. The sensor material 
of each of the first and second layers has a composition based on 
(Al)[l-x](A2)[x]MnO[z] , where Al is a trivalent ... 

DETDESC : 

... indicated can also contain minimal impurities with less than 0.5 atomic 
percent of each impurity element. Exemplary embodiments for corresponding 
materials are therefore LaO. 67BaO .33Mn03, or PrO . 5SrO . 5Mn03 , or 
Nd0.33Ca0.67MnO3, or (DyO . 67MgO . 33) (MnO . 8CuO . 2)02 . 9 . All these materials have 

Pat. No. 5563331, * 

FOCUS 

a perovskite- like crystal structure and are characterized by an increased 
magnetoresistive effect M[r ]of, in particular, more than 10%, and preferably 
more than 50%. The effect is thus considerably greater than in known Cu/Co 
multilayer systems. 



... 1557-1559). According to the present invention, corresponding layers of 
the sensor material are advantageously deposited onto substrates whose 
respective crystalline unit cell has dimensions matched to the unit cell of the 
sensor material. Substrate materials that also have a perovskite- like crystal 
structure are therefore particularly suitable. Corresponding exemplary 
embodiments are SrTi03, MgO, LaA103, NdGa03, MgA1204, or Y-stabilized Zr02 
(abbreviated YSZ) . In addition, however, Si substrates that are coated with a 
special intermediate . . . 

... [»1] a layer system comprising at least two layers, including: 

a first layer; and 

a second layer; 

wherein each of said first and second layers comprises a sensor material that 
possesses a perovskite- like crystal structure and exhibits an increased 
magnetoresistive effect, such that the sensor material of each of said first and 
second layers has a composition based on (Al) [ 1-x] (A2) [x]MnO[z] , wherein Al is a 



. . . [*4] similar to said first layer and layers similar to said second 
layer. 

[*5] 5. A magnetoresistive sensor according to claim 2; wherein the layer 
system is deposited on a substrate made of a material that has a 
perovskite- like crystal structure. 

[*6] 6. A magnetoresistive sensor according to claim 1, wherein the first 
layer and the second layer have different thicknesses. 

[*7] 7. A magnetoresistive sensor according to claim 6, wherein the layer 
system includes . . . 

... [*7] similar to said first layer and layers similar to said second 
layer . 

[*8] 8. A magnetoresistive sensor according to claim 6, wherein the layer 
system is deposited on a substrate made of a material that has a 
perovskite- like crystal structure. 

c9 



[*9] 9. A ntagnetoresxstxve sensor according to clann 1, wherein the layer 
system includes more than two layers which alternate between layers similar to 
said first layer and layers similar to said second layer. 

[*10] 10. A raagnetoresistive sensor according to claim 9, wherein the layer 
system is deposited on a substrate made of a material that has a 

Pat. No. 5563331, *10 

FOCUS 

perovskite-like crystal structure. 

[*11] 11. A raagnetoresistive sensor according to claim 1, wherein the layer 
system is deposited on a substrate made of a material that has a 
perovskite-like crystal structure. 

[*12] 12. A magnetoresistive sensor according to claim 1, wherein 0.25 </= 
x </= 0.75. 1 

f*13] 13. A magnetoresistive sensor according to claim 1, wherein z = 3. 

FOCUS - 17 OF 107 PATENTS 



5,554,585 



<=2> GET 1st DRAWING SHEET OF 1 



Sep. 10, 1996 



Method of forming a superconductor microstrip transmission 

line 



INVENTOR: Simon, Randy W., Long Beach, California 
Piatt, Christine E., El Segundo, California 
Lee, Alfred E., Torrance, California 
Lee, Gregory S., West Los Angeles, California 

REF-CITED: 

. . . 61(l):28-35 (1973). 
Geballe, "Paths to Higher .Temperature Superconductors," Science, vol. 259, Mar. 
12, 1993, pp. 1550-1551. 

Geller, S., et al., "Crystallographic Studies of Perovskite-like Compounds. II. 
Rare Earth Aluminates," Acta. Cryst., 9:1019-1025 (1956). 

Geller, S., "Crystallographic Studies of Perovskite-like Compounds. IV. Rare 
Earth Scandates, Vanadites, Galliates, Orthochroraites Acta Cryst., 10:243-248 
(1957). 

Gulyaev,, Yu V., et al., "YBa2Cu30[7 - x ]Films with a High-temperature ... 

FOCUS - 18 OF 107 PATENTS 

5,552,373 

<=2> GET 1st DRAWING SHEET OF 2 



Sep. 3, 1996 

Josephson junction device comprising high critical 
temperature crystalline copper superconductive layers 

INVENTOR: Agostinelli, John A., Rochester, New York 
Mir, Jose M., Webster, New York 
Lubberts, Gerrit, Penfield, New York 
Chen, Samuel, Penfield, New York 



DETDESC : 

. . . can take any convenient form capable of permitting deposition of USCO" 
thereon as a thin film. 



In a specifically preferred form of the invention SUB" is chosen from 



materials that themsel ^Jexhibit a perovskite or perov: ^le- like crystal 
structure. Strontium titanate is an example of a perovskite crystal structure 
which is specifically preferred for use as a substrate. Lanthanum aluminate 
(LaA103), lanthanum gallium oxide (LaGa03) and potassium tantalate are ... 

FOCUS - 19 OF 107 PATENTS 

5,527,567 

<=2> GET 1st DRAWING SHEET OF 6 

Jun. 18, 1996 

Metalorganic chemical vapor deposition of layered structure 

oxides 

INVENTOR: Desu, Seshu B . , Blacksburg, Virginia 
Tao, Wei, Blacksburg, Virginia 
Peng, Chien H., Blacksburg, Virginia 
Li, Tingkai, Blacksburg, Virginia 
Zhu, Yongfei, Blacksburg, Virginia 

SUM: 

... 1961), 695; G. A. Sraolenski, V. A. Isupov and A. I. Agranovskaya, Fiz 
Tverdogo Tela, 3, (1961), 895). These compounds have a pseudo-tetragonal 
symmetry and the structure is comprised of stacking of perovskite- like units 
between (Bi202)<2 + > layers along the pseudo-tetragonal c-axis. A large number 
of these compounds do not contain any volatile components in their sublattice 
that exhibits spontaneous polarization. The tendency for ... 

PAGE 22 

FOCUS - 20 OF 107 PATENTS 
5,523,283 
<=2> GET 1st DRAWING SHEET OF 1 
Jun. 4, 1996 

L[a]A103 Substrate for copper oxide superconductors 

INVENTOR: Simon, Randy W., Long Beach, California 
Piatt, Christine E., El Segundo, California 
Lee, Alfred E., Torrance, California 
Lee, Gregory S., West Los Angeles, California 

REF-CITED: 

. . . 61(l):28-35 (1973). 
Gaballe, "Paths to Higher Temperature Superconductors," Science, vol. 259, Mar. 
12, 1993, pp. 1550-1551. 

Geller, S., et al., "Crystal lographic Studies of Perovskite- like Compounds. II. 
Rare Earth Aluminates," Acta. Cryst., 9:1019-1025 (1956). 

Geller, S., "Crystallographic Studies of Perovskite- like Compounds. IV. Rare 
Earth Scandates, Vanadites, Galliates, Orthochromites , " Acta Cryst., 10:243-428 
(1957). 

Gulysev, Yu V., et al., M YBa2CU30 [ 7-x ] Films with a High-temperature ... 

FOCUS - 21 OF 107 PATENTS 

5,523,282 

<=2> GET 1st DRAWING SHEET OF 1 

Jun. 4, 1996 

High-frequency substrate material for thin-film layered 
perovskite superconductors 

INVENTOR: Simon, Randy W., Long Beach, California 



Piatt, Christine E . , E^Pkgundo, California 
Lee, Alfred E., Torrance, California 
Lee, Gregory S., West Los Angeles, California 

REF-CITED: 

. .. A et al., "The Flux Shuttle-A Josephson Junction Shift Register 
Employing Single Flux Quanta, Proceedings of the IEEE, 61(l):28-35 (1973) 
Geller, S Crystal lographic Studies of Perovskite- like Compounds. Rare Earth 
Q957) teS ' Vanadites * Galliates, Orthochromites , " Acta Cryst . , 10:243-251 

Gurvitch M et al., "Preparation and Substrate Reactions of Superconducting 
i-Ha-Cu-0 Films, . 

... in the f| Coprecipitation of Carbonate and Hydroxide Compounds of Lanthanum 
and Aluminum, Russian Journal of Inorganic Chemistry, vol. 22, No 11 did 
1622-1625, 1977. ' pp ' 

S. Geller et al., "Crystallographic Studies of Perovskite- like Compounds. II. 
Kare Earth Alurainates, Acta Cryst., vol. 9, pp. 1019-1025, 1956. 

J * J K ^ ner et al '» ,,Elect rolytes for the High Temperature Fuel Ceil; Experimental 
and Theoretical ... r 

FOCUS - 22 OF 107 PATENTS 
5,519,234 
<=2> GET 1st DRAWING SHEET OF 30 
May 21, 1996 

Ferroelectric dielectric memory cell can switch at least 
giga cycles and has low fatigue - has high dielectric 
constant and low leakage current 

INVENTOR: Paz de Araujo, Carlos A., Colorado Springs, Colorado 
Cuchiaro, Joseph D. , Colorado Springs, Colorado 
Scott, Michael C, Colorado Springs, Colorado 
McMillan, Larry D. , Colorado Springs, Colorado 

ABST: 

. . . s2 > . . . Sk xk < + ak > Bl yl < + bl> B2 y2 < + b2 > . . Bl yl < + 
bl> Q z < - 2> , where Al, A2 . . . Aj represent A-site elements in a 
perovskite- like structure, SI, S2 . . . Sk represent superlattice generator 
elements, Bl, B2 . . . Bl represent B-site elements in a perovskite- like 
structure, Q represents an anion, the superscripts indicate the valences of the 
respective elements, the subscripts indicate the number of atoms of the element 
in the unit cell, and at least wl and yl are non-zero. Some of these materials 
are extremely low . . . 

SUM: 

... 676 (1962) and Chapter 8 pages 241-292 and pages 624 & 625 of Appendix F 
of the Lines and Glass reference cited ^above. As outlined in section 15.3 of the 
Sraolenskii book, the layered perovskite- like materials can be classified under 
three general types: 

(I) compounds having the formula A m - 1 Bi2M ra 0 3m + 3 , where A = Bi<3 + > 
, Ba<2 + > , Sr< ... 

... strontium titanates Sr2Ti04, Sr3Ti207 and Sr4Ti3010; and 

(III) compounds having the formula AmMm0 3m+2 , including compounds 
such as Sr2Nb207, La2Ti207, Sr5TiNb4017, and Sr6Ti2Nb4O20 . 

Sraolenskii pointed out that the perovskite- like layers may have different 
thicknesses, depending on the value of ra, and that the perovskite AM03 is in 
principal the limiting example of any type of layered perovskite- like structure 

u 1 " ~ infinit y- Sraolenskii also noted that if the layer with minimum 
thickness (m - 1) is denoted by P and the bismuth-oxygen layer is denoted by B, 
then the type I compounds may be described as ... BP m BP ra ... Further 



C(2_ 



Smolenskii noted that : is a fractional number then \ ^^lattice contains 
perovskite-like layers of various thicknesses, and that all the known type I 
compounds are f erroelectrics . Similarly, Smolenskii noted that the type two 
compounds could be represented as . . . SP m SP ra . . . where P is the 
perovskite-like layer of thickness m and S is the strontium-oxygen connecting 
layer, and that since the type I and type II compounds have similar 
perovskite-like layers, the existence of "hybrid compounds such as . . . BP m 
SP n BP m SP ra . . . 'should not be ruled out", though none had been obtained at 
that time. 

Pat. No. 5519234, * 

FOCUS 

Up to now, these layered ferroelectric . . . 

... s2 > . . . Sk xk < + sk> Bl yl < + bl> B2 y2 < + b2 > . . . Bl yl < + bl> 
Q z < - 2> , where Al, A2 . . . Aj represent A-site elements in a 
perovskite-like structure, SI, S2 . . . Sk represent super lattice generator 
elements, Bl, B2 . . . Bl represent B-site elements in a perovskite-like 
structure, Q represents an anion, the superscripts indicate the valences of the 
respective elements, the subscripts indicate the average number of atoms of the 
element in the unit cell, and at least wl and yl are non-zero. Preferably, the 
A- . . . 

. . . layered superlattice material comprises a material having a localized 
structure, within a grain or other larger or smaller unit, which localized 
structure contains predominately repeatable units containing one or more 
perovskite-like layers and one or more intermediate non-perovskite- like layers 
spontaneously linked in an interdependent manner. 

In another aspect the invention provides a non-volatile ferroelectric memory 
comprising: a ferroelectric memory cell including a layered superlattice ... 

DETDESC: 

... curves as shown in FIG. 5C, which show fatigue of less than 30X, which is 
much less than for any ferroelectric material on which endurance tests had been 
performed in the prior art. It was realized that the SrBi4Ti4015 was one of the 
layered perovskite-like materials catalogued by Smolenskii, and thought that 
perhaps the natural layered structure of these materials might be the source of 
the low- fatigue property. Other devices were fabricated having the structure 
shown in FIG. 2C, i.e. a ... 

... flexible than the lattice of a ferroelectric material. Turning to FIG. 
13, a layered superlattice material 92 is illustrated. Smolenskii recognized 
that what we call the layered superlattice materials spontaneously form into 
layers 94 with a perovskite-like structure which alternate with layers 96 having 
a simpler structure. Depending on the material, the perovskite-like layers 94 
may include one or a plurality of linked layers of perovskite-like octahedrons 
90. As an example, FIG. 14 shows a unit cell of the material ABi2B2< + 5> 09, 
which is the formula for strontium bismuth tantalate (SrBi2Ta209) and other 
layered superlattice materials, such as tantalum, niobium, and tungsten, having 
a element with a valence of + 5 in the B-site. In this structure, each 
perovskite-like layer 94 includes two layers of octahedrons 90 which are 
separated by layers 96 of a material that does not have a perovskite-like 
structure. In this material the primitive unit cell consists of two perovskite 
layers 94 and two non-perovskite layers 96, since the structure shifts between 
the layers 98A and 98B. In FIG. ... 

... 015, which is the formula for strontium bismuth titanate ( SrBi4Ti4015 ) 
and other layered superlattice materials having an element, such as titanium, 
hafnium, and zirconium, having a valence of + 4 in the B-sites. In this material 
each the perovskite-like layer 94 has four layers of octahedrons 90. 

As the understanding of what Smolenskii called a layered perovskite-like 
structure increased, the inventors have realized that these materials are more 
than a substance which spontaneously forms in layers. This is seen most easily 
by an example. Strontium bismuth tantalate (SrBi2Ta209) can be considered to 

Pat. No. 5519234, * 

C|3 



FOCUS 



be . . . 

...in the following definition: (B) a material having a localized structure, 
within a grain or other larger or smaller unit, which localized structure 
contains predominately repeatable units containing one or more perovskite- like 
layers and one or more intermediate non-perovskite- like layers spontaneously 
linked in an interdependent manner. 

It has been discovered that the layered superlattice materials catalogued by 
Smolenskii et al. are all likely candidates for fatigue free switching 
f erroelectrics and dielectric materials that are resistant to . . . 

. . . x2 < + s2 > . . . Sk xk < + sk> Bl yl < + bl> B2 y2 < + b2 > . . Bl vl 

< + bl> Q z < - 2> , y 

where Al, A2 . . . Aj represent A-site elements in the perovskite- like 
structure, which may be elements such as strontium, calcium, barium, bismuth, 
lead, and others SI, S2 . . . Sk represent superlattice generator elements, 
which usually is bismuth, but can also be materials such as yttrium, scandium, 
lanthanum, antimony, chromium, thallium, and other elements with a valence of + 
3, Bl, B2 . . . Bl represent B-site elements in the perovskite- like structure, 
which may be elements such as titanium, tantalum, hafnium, tungsten, niobium, 
zirconium, and other elements, and Q represents an anion, which generally is 
oxygen but may also be other elements, such as fluorine, ... 

... [*2] s2 > . . . Sk xk < + sk> Bl yl < + bl> B2 y2 < + b2 > . . . Bl yl 

< + bl> Q z < - 2> , where Al, A2 . . . Aj represent A-site elements in a 
perovskite- like structure, SI, S2 . . . Sk represent superlattice generator 
elements, Bl, B2 . . . Bl represent B-site elements in a perovskite- like 
structure, Q represents an anion, the superscripts indicate the valences of the 
respective elements, the subscripts indicate the average number of atoms of the 
element in the unit cell, and at least wl and yl are non-zero. 

[*3] 3. A ... 

FOCUS - 23 OF 107 PATENTS 

5,504,041 

<=2> GET 1st DRAWING SHEET OF 5 

Apr. 2, 1996 

Conductive exotic-nitride barrier layer for 
high-dielectric-constant materials 

INVENTOR: Summerfelt, Scott R . , Dallas, Texas 

DETDESC : 

TABLE 

* * Conductive perovskite like materials 

FOCUS - 24 OF 107 PATENTS 

5,489,548 

<=2> GET 1st DRAWING SHEET OF 3 

Feb. 6, 1996 

Method of forming high-dielectric-constant material 
electrodes comprising sidewall spacers 

INVENTOR: Nishioka, Yasushiro, Tsukuba, Texas, Japan 
Summerfelt, Scott R., Dallas, Texas 



Park, Kyung-Ho, Tsukube ^Papan 
Bhattacharya, Pijush, Midnapur, India 



DETDESC: 

TABLE 

* * Conductive perovskite like 

FOCUS - 25 OF 107 PATENTS 

5,478,610 

<=2> GET 1st DRAWING SHEET OF 5 

Dec. 26, 1995 

Metalorganic chemical vapor deposition of layered structure 

oxides 

INVENTOR: Desu, Seshu B., Blacksburg, Virginia 
Tao, W., Blacksburg, Virginia 

SUM: 

... 34, (1961), 695; G. A. Sraolenski, V. A. Isupov and A. I. Agranovskaya , 
Fiz Tverdogo Tela, 3, (1961), 895). These compounds have pseudo-tetragonal 
symmetry and the structure is comprised of stacking of perovskite- like units 
between (Bi202)<2 + > layers along the pseudo- tetragonal c-axis. A large number 
of these compounds do not contain any volatile components in their sublattice 
that exhibits spontaneous polarization. The tendency for ... 

FOCUS - 26 OF 107 PATENTS 

5,468,679 

<=2> GET 1st DRAWING SHEET OF 27 

Nov. 21, 1995 

Process for fabricating materials for ferroelectric, high 
dielectric constant, and integrated circuit applications 

INVENTOR: Paz de Araujo, Carlos A., Colorado Springs, Colorado 
Scott, Michael C, Colorado Springs, Colorado 
Cuchiaro, Joseph D. , Colorado Springs, Colorado 
McMillan, Larry D., Colorado Springs, Colorado 

SUM: 

... 676 (1962) and Chapter 8 pages 241-292 and pages 624 & 625 of Appendix F 
of the Lines and Glass reference cited above. 

As outlined in section 15.3 of the Smolenskii book, the layered 
perovskite- like materials can be classified under three general types: 

(I) compounds having the formula A ra-1 Bi2M m 0 3m + 3 , where A = Bi<3 + > 
Ba<2 + > , Sr< . . . 

... s2> . , . Sk xk < + sk> Bl yl < + bl> B2 y2 < + b2> . . . Bl yl < + bl> Q 
z < - 2> , 

where Al, A2 . . . Aj represent A-site elements in a perovskite- like 
structure, SI, S2 . . . Sk represent superlattice generator elements, Bl, B2 . . 
. Bl represent B-site elements in a perovskite- like structure, Q represents an 
anion, the superscripts indicate the valences of the respective elements, the 
subscripts indicate the average number of atoms of the element in the unit cell, 
and at least wl and yl are non-zero. Preferably, the A- ... 

DETDESC : 

... compatible with, or can be designed to be compatible with, the other 



or 



materials commonly use integrated circuits, such as ^Ricon and gallium 

arsenide. 

The class of materials are those disclosed by Smolenskii as having a layered 
perovskite- like structure, as discussed in the Background of the Invention It 
has been realized that these materials are more than a substance which 
spontaneously forms in layers. This is seen most easily by an example. Strontium 
bismuth tantalate (SrBi2Ta209) can ... 

... in the following definition: (B) a material having a localized structure, 
within a grain or other larger or smaller unit, which localized structure 
contains predominately repeatable units containing one or more perovskite-like 
layers and one or more intermediate non-perovskite- like layers spontaneously 
linked in an interdependent manner. 

It is well-known that compounds having the perovskite structure may be 
described in terms of the general formula ABQ3, where A and B are cations and Q 
is an anion. In the ... 

Pat. No. 5468679, * 

FOCUS 

... flexible than the lattice of a ferroelectric material. Turning to FIG . 
13, a layered superlattice material 92 is illustrated. Smolenskii recognized 
that what we call the layered superlattice materials spontaneously form into 
layers 94 with a perovskite-like structure which alternate with layers 96 having 
a simpler structure. Depending on the material, the perovskite-like layers 94 
may include one or a plurality of linked layers of perovskite-like octahedrons 
90. As an example, FIG. 14 shows a unit cell of the material ABi2B2< + 5> 09 , 
which is the formula for strontium bismuth tantalate (SrBi2Ta209) and other 
layered superlattice materials, such as tantalum, niobium, and tungsten, having 
a element with a valence of + 5 in the B-site. In this structure, each 
perovskite-like layer 94 includes two layers of octahedrons 90 which are 
separated by layers 96 of a material that does not have a perovskite-like 
structure. In this material the primitive unit cell consists of two perovskite 
layers 94 and two non-perovskite layers 96, since the structure shifts between 
the layers 98A and 98B. In FIG. ... 

... 015, which is the formula for strontium bismuth titanate (SrBi4Ti4015 ) 
and other layered superlattice materials having an element, such as titanium, 
hafnium, and zirconium, having a valence of + 4 in the B-sites. In this material 
each the perovskite-like layer 94 has four layers of octahedrons 90. 

It has been discovered that the layered superlattice materials catalogued by 
Smolenskii et al. are all likely candidates for fatigue free switching 
f erroelectrics and dielectric materials that are resistant to ... 

. . . x2 < + s2> . . . Sk xk < + sk> Bl yl < + bl> B2 y2 < + b2> . . . Bl vl 
<bl> Q z < - 2> , 

where Al, A2 . . . Aj represent A-site elements in the perovskite-like 
structure, which may be elements such as strontium, calcium, barium, bismuth, 
lead, and others SI, S2 . . . Sk represent superlattice generator elements, 
which usually is bismuth, but can also be materials such as yttrium, scandium, 
lanthanum, antimony, chromium, thallium, and other elements with a valence of + 
3, Bl, B2 . . . Bl represent B-site elements in the perovskite-like structure, 
which may be elements such as titanium, tantalum, hafnium, tungsten, niobium, 
zirconium, and other elements, and Q represents an anion, which generally is 
oxygen but may also be other elements, such as fluorine, ... 

FOCUS - 27 OF 107 PATENTS 

5,447,908 

<=2> GET 1st DRAWING SHEET OF 1 

Sep. 5, 1995 

Superconducting thin film and a method for preparing the 



same 



INVENTOR: Itozaki, Hideo, Hyogo, Japan 
Tanaka, Saburo, Hyogo, Japan 
Fujita, Nobuhiko, Hyogo, Japan 
Yazu, Shuji, Hyogo, Japan 
Jodai, Tetsuji, Hyogo, Japan 



SUM: 



;^c S ^ rUC ^ U ! e *u The ter !" ° f q uasi -perovskite type means a structure which can 
ILZ "t X ?* T f t0 SUCh 3 Cr * Stal structure that is similar to 



e or 



u 1 . i - j -j" i ' Bi o uj. li^ Luie Liiti l is similar to 

Ferovskite-type oxides and includes an orthorhombical ly distorted perovskit 
a distorted oxygendef icient perovskite or the like. perovskit 

con^stinr;a?n?r^ n f **** "J" be ™° ther of superconductor 

consisting mainly of a compound oxide represented by the formula: 

THETA 4( PHI 1-q ,Ca q ) m Cu ... 

FOCUS - 28 OF 107 PATENTS 

5,447,906 

Sep. 5, 1995 

Thin film high TC oxide superconductors and vapor deposition 
methods for making the same 

INVENTOR: Chaudhari, Praveen, Briarcliff Manor, New York 

Gambino, Richard J., Yorktown Heights, New York 

Koch, Roger H., Amawalk, New York 

Lacey, James A., Mahopac, New York 

Laibowitz, Robert B . , Peekskill, New York 

Viggiano, Joseph M., Wappingers Falls, New York 

SUM: 

. . . areas . 

It is another object of the present invention to provide continuous, smooth 
copper oxide superconductive films exhibiting superconductivity at temperatures 
xn excess of 40o K. and methods for making these films, where the films exhibit 
perovskite- like structure. 

It is another object of this invention to provide transition metal oxide 
superconductive films including a rare earth element, or rare earth- like 
element, where the films exhibit superconductivity at temperatures greater than 

... earth-like element, B is an alkaline earth element, and y is sufficient 
to satisfy valence demands of the composition. 

It is another object of the present invention to provide smooth, continuous 
copper oxide superconducting films having a perovskite- like crystal structure 
and exhibiting superconductivity at temperatures in excess of 40o K. , and to 
provide methods for making these films 
SUMMARY OF THE INVENTION 

The films of this invention are oxide superconductors exhibiting 
superconductivity at temperatures in excess of 

... addition to being continuous, smooth, and of excellent compositional 
uniformity. The Cu oxide films are therefore considered to be unique examples of 
this class of films, as are the processes for making them. 

Typically, the films are characterized by a perovskite- like crystalline 
Re^ue^d 6 * SUCh ^ th ° Se described in raore de tail by C. Michel and B . Rayeau in 



c /? 



Chimie Minerale, 21 W- 407 (1984). These films are Wmed by a 

FOCUS - 29 OF 107 PATENTS 

5,439,878 

<=2> GET 1st DRAWING SHEET OF 21 

Aug. 8, 1995 

Method for preparing copper oxide superconductor containing 

carbonate radicals 

INVENTOR: Kinoshita, Kyoichi, Hoya, Japan 
Yamada, Tomoaki, Higashitnurayama , Japan 

SUM: 

... novel superconducting material. 
Description of the Prior Art 

Several types of copper oxide superconductors have been discovered since 
hxgh-To superconductivity was detected in the La-Ba-Cu-0 system. 
Superconductivity would arise from the layered perovskite- like structure havin 
Cu06 octahedra, or Cu05 pyramids, or Cu02 square planes as a building unit. Th 
layered perovskite- like structure and a sufficient carrier concentration of th 
material are essential factors for making the material superconducting as 
indicated by Osamura & Zhang (Japan. J . Appl .Phys . 26 , L2094-L2096, 1987). 

FOCUS - 30 OF 107 PATENTS 

5,439,876 

<=2> GET 1st DRAWING SHEET OF 5 

Aug. 8, 1995 

Method of making artificial layered high T c superconductors 

INVENTOR: Graf, Volker, Wollerau, Switzerland 
Mueller, Carl A., Hedingen, Switzerland 

DETDESC: 

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 

One material particularly suited as a substrate in the epitaxial growth of 
high T c superconductor material is strontium titanate, SrTi03, which forms 
crystals like perovskite (FIG. 1). Each titanium ion 1 is octahedrally 
surrounded by six oxygen ions 2, the bigger strontium ions 3 being disposed in 
the spaces in between. At room temperature, ... 

FOCUS - 31 OF 107 PATENTS 

5,426,092 

<=2> GET 1st DRAWING SHEET OF 14 

Jun. 20, 1995 

Continuous or serai-continuous laser ablation method for 
depositing fluorinated superconducting thin film having 
basal plane alignment of the unit cells deposited on 
non- lattice-matched substrates 

INVENTOR: Ovshinsky, Stanford R., Bloomfield Hills, Michigan 
Young, Rosa, Troy, Michigan 

SUM: 

... growth of a crystalline superconducting material in a manner as if 
mimicking the orientation of a substrate having an identical lattice structure 

C/3 



without the presence oi^ch a substrate lattice struct!^ Simply stated, an 

epitaxial- like perovskite superconducting material grown on a 
non- lattice-matched substrate would nonetheless be characterized by a lattice 
structure identical to the lattice structure which would be present if the 
material was grown on a perovskite substrate. Thus, 11 ... 

FOCUS - 32 OF 107 PATENTS 

5,424,282 

<=2> GET 1st DRAWING SHEET OF 5 

Jun. 13, 1995 

Process for raanuf acturing a composite oxide superconducting 

wire 

INVENTOR: Yamamoto, Susumu, Hyogo, Japan 

Murai, Teruyuki, Hyogo, Japan 

Kawabe, Nozomu, Hyogo, Japan 

Awazu, Tomoyuki, Hyogo, Japan 

Yazu, Shuji, Hyogo, Japan 

Jodai, Tetsuji, Hyogo, Japan 

DETDESC: 

. . . term of "quasiperovskite type structure" means any oxide that can be 
considered to have such a crystal structure-that is similar to perovskite-type 
oxides and may include an orthorhombically distorted perovskite or a distorted 
oxygen-deficient perovskite or the like. 

In practice, the element ct is preferably selected from Ba, Sr and/or Ca and 

the element beta is preferably selected from Y, La and/or lanthanid such as Sc, 
Ce, Gd, Ho, Er, Tin, Y b, ... 

FOCUS - 33 OF 107 PATENTS 

5,423,285 

<=2> GET 1st DRAWING SHEET OF 27 

Jun. 13, 1995 

Process for fabricating materials for ferroelectric, high 
dielectric constant, and integrated circuit applications 

INVENTOR: Paz de Araujo, Carlos A., Colorado Springs, Colorado 
Cuchiaro, Joseph D., Colorado Springs, Colorado 
Scott, Michael C, Colorado Springs, Colorado 
McMillan, Larry D., Colorado Springs, Colorado 

SUM: 

... 676 (1962) and Chapter 8 pages 241-292 and pages 624& 625 of Appendix F 
of the Lines and Glass reference cited above. 

As outlined in section 15.3 of the Smolenskii book, the layered 
perovskite- like materials can be classified under three general types: 

(I) compounds having the formula A m-1 Bi2M m 0 3m + .3 , where A = Bi<3 + > 
Ba<2 + > , Sr< . . . 

. . . s2> . . . Sk xk < + sk> Bl yl < + bl> B2 y2 < + b2> . . . Bl yl < + bl> Q 
z < - 2> , where Al, A2 . . . Aj represent A-site elements in a perovskite- like 
structure, SI, S2 . . . Sk represent superlattice generator elements, Bl, B2 
♦ Bl represent B-site elements in a perovskite- like structure, Q represents an 
anion, the superscripts indicate the valences of the respective elements, the 
subscripts indicate the average number of atoms of the element in the unit cell, 
and at least wl and yl are non-zero. Preferably, the A- . . . 

DETDESC : 



. . . compatible with can be designed to be corapat with, the other 

materials commonly used in integrated circuits, such as silicon and gallium 
arsenide . 



The class of materials are those disclosed by Smolenskii as having a layered 
perovskite-like structure, as discussed in the Background of the Invention. It 
has been realized that these materials are more than a substance which 
spontaneously forms in layers. This is seen most easily by an example. Strontium 
bismuth tantalate (SrBi2Ta209) can ... 

... in the following definition: (B) a material having a localized structure, 
within a grain or other larger or smaller unit, which localized structure 
contains predominately repeatable units containing one or more perovskite-like 
layers and one or more intermediate non-perovskite- like layers spontaneously 
linked in an interdependent manner. 

It is well-known that compounds having the perovskite structure may be 
described in terms of the general formula ABQ3, where A and B are cations and Q 
is an anion. In the . . . 

... flexible than the lattice of a ferroelectric material. Turning to FIG. 
13, a layered superlattice material 92 is illustrated. Smolenskii recognized 

Pat. No. 5423285, * 

FOCUS 

that what we call the layered superlattice materials spontaneously form into 
layers 94 with a perovskite-like structure which alternate with layers 96 having 
a simpler structure. Depending on the material, the perovskite-like layers 94 
may include one or a plurality of linked layers of perovskite-like octahedrons 
90. As an example, FIG . 14 shows a unit cell of the material ABi2B2< + 5> 09, 
which is the formula for strontium bismuth tantalate (SrBi2Ta209) and other 
layered superlattice materials, such as tantalum, niobium, and tungsten, having 
a element with a valence of + 5 in the B-site. In this structure, each 
perovskite-like layer 94 includes two layers of octahedrons 90 which are 
separated by layers 96 of a material that does not have a perovskite-like 
structure. In this material the primitive unit cell consists of two perovskite 
layers 94 and two non-perovskite layers 96, since the structure shifts between 
the layers 98A and 98B. in FIG. ... 

... 015, which is the formula for strontium bismuth titanate (SrBi4Ti4015) 
and other layered superlattice materials having an element, such as titanium, 
hafnium, and zirconium, having a valence of + 4 in the B-sites. In this material 
each the perovskite-like layer 94 has four layers of octahedrons 90. 

It has been discovered that the layered superlattice materials catalogued by 
Smolenskii et al. are all likely candidates for fatigue free switching 
ferroelectrics and dielectric materials that are resistant to ... 

... Sk xk < + sk> Bl yl < + bl> B2 y2 < + b2> . . . Bl yl < + bl> Q z < - 2> 
,tra (1) 

where Al, A2 . . . Aj represent A-site elements in the perovskite-like 
structure, which may be elements such as strontium, calcium, barium, bismuth, 
lead, and others SI, S2 . . . Sk represent superlattice generator elements, 
which usually is bismuth, but can also be materials such as yttrium, scandium, 
lanthanum, antimony, chromium, thallium, and other elements with a valence of + 
3, Bl, B2 . . . Bl represent B-site elements in the perovskite-like structure, 
which may be elements such as titanium, tantalum, hafnium, tungsten, niobium, 
zirconium, and other elements, and Q represents an anion, which generally is 
oxygen but may also be other elements, such as fluorine, ... 

FOCUS - 34 OF 107 PATENTS 

5,409,890 

Apr. 25, 1995 

Process for producing an elongated sintered article 



0,2.0 




INVENTOR: Yaraamoto, Susurau, Hyogo, Japan 
Kawabe, Nozomu, Hyogo, Japan 
Awazu, Toraoyuki, Hyogo, Japan 
Murai, Teruyuki, Hyogo, Japan 

SUM: 

... term quasi-perovskite type means a structure which can be considered to 
have such a crystal structure that is similar to perovskite- type oxides and 
includes an orthorhombically distorted perovskite or a distorted 
oxygen-deficient perovskite or the like. 

The sintering operation of the powder mixture is carried out at temperature 
which is higher than 600o C. but is not higher than the lowest melting point of 
any component in the naterial powder to be sintered. If the sintering 
temperature exceeds the . . . 

FOCUS - 35 OF 107 PATENTS 
5,401,715 
<=2> GET 1st DRAWING SHEET OF 1 
Mar. 28, 1995 

Semiconductor substrate having a superconducting thin film 

INVENTOR: Itozaki, Hideo, Hyogo, Japan 
Harada, Keizo, Hyogo, Japan 
Fujiraori, Naoji, Hyogo, Japan 
Yazu, Shuji, Hyogo, Japan 
Jodai, Tetsuji, Hyogo, Japan 

DETDESC : 

. . . term quasi-perovskite type means a structure which can be considered to 
have such a crystal structure that is similar to perovskite- type oxides and 
includes an orthorhombically distorted perovskite or a distorted 
oxygen-deficient perovskite or the like. 

An atomic ratio of the lanthanide element ,r Ln M :Ba:Cu is preferably 1:2:3 as 
is defined by the formula but the atomic ratio is not restricted strictly to 
this ratio. In fact, the other compound oxides having ... 

FOCUS - 36 OF 107 PATENTS 

5,389,603 

<=2> GET 1st DRAWING SHEET OF 5 

Feb. 14, 1995 

Oxide superconductors, and devices and systems comprising 
such a superconductor 

INVENTOR: Batlogg, Bertram J., New Providence, New Jersey 
Cava, Robert J., Bridgewater, New Jersey 

DETDESC: 

... microscopy indicate a basically orthorhorabic crystal structure, but there 
are also indications that, at least for some of the inventive compounds, the 
structure may be weakly monoclinic. Both of these possibilities are intended to 
be included in the term "perovskite- like" or analogous terms. Diffraction 
studies have also revealed the presence of a variety of long period long range 
ordered super lattices (typically in the ab plane). 

FIG. 2 shows the field (225 Oe)-cooled ... 

We claim: 



c 2-/ 



1. An articl ^Bmprising a superconductive el ^Kt comprising at least 
one superconductive material having a perovskite- like crystal structure and 
nominal formula (Pb2A2 Cu')BCu208 + delta with (A selected from the group 
consisting of Sr, Ba, Sr and Ba, Sr and Ca, and Sr, Ba and Ca; Cu 1 is selected 
from the group consisting of ... 

... [*1] parallel to the ab- plane; and wherein the composition is selected 
such that the superconductive material has a transition temperature of at least 
about 30K. 

[*2] 2. An article comprising a superconductive element comprising at least 
one superconductive material having a perovskite- like crystal structure and 
nominal formula (X2A2Cu') BCu208 + delta , where X is selected from the group 
consisting of Pb, Pb and Bi, Pb and Tl, and Pb, Bi and Tl, with X being at least 
50 atomic % of ... 

FOCUS - 37 OF 107 PATENTS 
5,362,710 
<=2> GET 1st DRAWING SHEET OF 2 
Nov. 8, 1994 

Process for preparing high Tc superconducting material 

INVENTOR: Fujita, Nobuhiko, Hyogo, Japan 
Kobayashi, Tadakazu, Hyogo, Japan 
Itozaki, Hideo, Hyogo, Japan 
Tanaka, Saburo, Hyogo, Japan 
Yazu, Shuji, Hyogo, Japan 
Jodai, Tetsuji, Hyogo, Japan 

SUM: 

. . . quasi-perovskite type oxide means a structure which can be considered to 
have such a crystal structure that is similar to perovskite-type oxides and 
includes an orthorhombically distorted perovskite or a distorted 
oxygen-deficient perovskite or the like. 

The present invention also provides a process for producing the 
abovementioned superconducting material, characterized by sintering a mixture of 
the following powders: 

an oxide, carbonate, nitrate or sulfate of one element "A" selected from . . . 

FOCUS - 38 OF 107 PATENTS 

5,356,674 

<=2> GET 1st DRAWING SHEET OF 2 

Oct. 18, 1994 

Process for applying ceramic coatings using a plasma jet 
carrying a free form non-metallic element 

INVENTOR: Henne, Rudolf, Boeblingen, Federal Republic of Germany 
Weber, Winfried, Leinf elden-Echterdingen , Federal Republic of Germany 
Schiller, Guenter, Gerlingen, Federal Republic of Germany 
Schnurnberger , Werner, Stuttgart, Federal Republic of Germany 
Kabs, Michael, Hanau, Federal Republic of Germany 

SUM: 

... materials are oxidized materials, for example, spinels and perovskites on 
a nickel or cobalt or nickel-cobalt basis. It is, however, also conceivable to 
apply all possible kinds of spinels and perovskites in accordance with the 
inventive process. This also applies to spinel- like and perovskite- like 
compounds and to non oxidized compounds, for example, nitrides, halides, 
carbides, etc., with nitrogen or halogens or also non-metallic compounds, 



methane or acetylene t\ ^^being carried along as non-me; ^^ic element by the 

FOCUS - 39 OF 107 PATENTS 



5,354,733 
<=2> GET 1st DRAWING SHEET OF 21 
Oct. 11, 1994 

Copper oxide superconductor containing carbonate radicals 

INVENTOR: Kinoshita, Kyoichi, Hoya, Japan 
Yamada, Tomoaki, Higashimurayama , Japan 

SUM: 

... 2. Description of the Prior Art 

Several types of copper oxide superconductors have been discovered since 
high-T c superconductivity was detected in the La-Ba-Cu-0 system. 
Superconductivity would arise from the layered perovskite- like structure having 
Cu06 octahedra, or Cu05 pyramids, or Cu02 square planes as a building unit. The 
layered perovskite- like structure and a sufficient carrier concentration of the 
material are essential factors for making the material superconducting as 
indicated by Osamura & Zhang (Japan. J.Appl .Phys .26, L2094-L2096, 1987). ... 

FOCUS - 40 OF 107 PATENTS 

5,340,796 

<=2> GET 1st DRAWING SHEET OF 5 

Aug. 23, 1994 

Oxide superconductor comprising Cu, Bi, Ca and Sr 

INVENTOR: Cava, Robert J., Bridgewater, New Jersey 
Sunshine, Steven A., Berkeley Heights, New Jersey 

ABST: 

Novel superconductive oxides are disclosed. The oxides all have layered 
perovskite- like crystal structure and manifest superconductivity above about 
77K. An exemplary material has composition Bi2 . 2Sr2CaO . 8Cu208 . Other materials 
are described by the nominal formula X2+xMn-xCun- ... 

SUM: 

. . . high temperature superconductors has been reported since publication of 
the above seminal papers. Most of the work deals with YBa2Cu30 x (the so-called 
1-2-3 compound) and related compounds. 

In all of these compounds the superconducting phase is perovskite- like, 
typically having orthorhorabic crystal structure, and the compounds that exhibit 
high (i.e., T c > 77K) temperature superconductivity generally contain one or 
more rare earth elements. 

The discovery of high T c superconductivity in some . . . 

... likely to be stable high T c superconductors, with T c s likely to be 
above 100K. 

The novel phases all have a crystal structure that is closely related to that 
of the above described 80K compound and thus are perovskite- like . They differ 
from each other essentially only in the number of crystal planes between the two 
Bi-0 double planes that bound the unit cell in the c-direction, or by the size 
of the supercell. The composition of the ... 

DETDESC : 

... in added layers of M and Cu between the Bi-0 double layers and are 
expected to result in one or more phases of stable high T c superconductive 



material . 



All of the inventive phases have layered perovskite- like crystal structure, 
and the existence of relatively weak bonding between at least some layers maybe 
the cause of the observed relatively high ductility of the inventive materials. 
It will be appreciated that by "perovskite- like" we mean not only the 
prototypical, truly cubic structure, but very significantly distortions 
therefrom . 

Material specification in accordance with the invention depends upon the 
nature of the intended use. For power transmission, or any other currentcarrying 

PAGE 

Pat. No. 5340796, * 

FOCUS 

What is claimed is: 

1. An article comprising material perovskite- like structure and of 
nominal composition X2+xM4-x Cu3010 +0.5 +/- delta , where [x = p/q < 
0.4, and p and q are positive integers] 0 </= x < 0.4, X is Bi and Pb, ... 

FOCUS - 41 OF 107 PATENTS 

5,338,721 

<=2> GET 1st DRAWING SHEET OF 5 

Aug. 16, 1994 

Process for manufacturing a superconducting composite 

INVENTOR: Yamamoto, Susumu, Hyogo, Japan 

Murai, Teruyuki, Hyogo, Japan 

Kawabe, Nozomu, Hyogo, Japan 

Awazu, Tomoyuki, Hyogo, Japan 

Yazu, Shuji, Hyogo, Japan 

Jodai, Tetsuji, Hyogo, Japan 

DETDESC : 

. . . quasi-perovskite type structure" means any oxide that can be considered 
to have such a crystal structure that is similar to perovskite- type oxides and 
may include an orthorhombically distorted perovskite or a distorted 
oxygen-deficient perovskite or the like. 

In practice, the element alpha is preferably selected from Ba, Sr and/or Ca 
and the element beta is preferably selected from Y, La and/or lanthanid such as 
Sc, Ce, Gd, Ho, Er, Tra, Yb, Lu and the ... 

FOCUS - 42 OF 107 PATENTS 

5,332,722 

<=2> GET 1st DRAWING SHEET OF 3 

Jul. 26, 1994 

Nonvolatile memory element composed of combined 
superconductor ring and MOSFET 

INVENTOR: Fujihira, Mitsuka, Yokohama, Japan 

DETDESC: 

. . . term quasi-perovskite type means a structure which can be considered to 
have such a crystal structure that is similar to perovskite-type oxides and 
includes an orthorhombically distorted perovskite or a distorted 
oxygen-deficient perovskite or the like. 

Another superconducting compound oxide which can be used by the present 
invention is represented by the general formula: 



(M,Sr)2CuO 4- delta 



in which M stands for Y or La and . . . 

FOCUS - 43 OF 107 PATENTS 

5,328,892 

Jul. 12, 1994 

Oxide superconductor composition and a process for the 
production thereof 

INVENTOR: Manako, Takashi, Tokyo, Japan 
Shimakawa, Yuichi, Tokyo, Japan 
Kubo, Yoshirai, Tokyo, Japan 

SUM: 

... following formulae: 
TISr 3 - x Y x Cu207(IA) 
wherein 0.1 </= x </= 1, and 
TISr 4 - x Y x Cu309(IB) 

wherein 0.1 </= x </= 2. Unit cells of the layered perovskite- like crystal 
structures of these compositions of the formulae (IA) and (IB) may be shown 
respectively as follows: 

T10/Sr0/Cu02/Sr or Y/Cu02/Sr0( IX) 

T10/Sr0/Cu02/Sr or Y/ ... 

FOCUS - 44 OF 107 PATENTS 

5,296,458 

<=2> GET 1st DRAWING SHEET OF 4 

Mar. 22, 1994 

Epitaxy of high T c superconducting films on (001) silicon 

surface 

INVENTOR: Himpsel, Franz J., Mt. Kisco, New York 
SUM: 

... first showed superconducting behavior in mixed copper- ox ides , typically 
including rare earth and/or rare earth- like elements and alkaline earth 
elements, for example La, Ba, Sr, . . ^ , and having a perovskite- like 
structure. Materials including the so called " 1-2-3 phase in the Y-Ba-Cu-0 
system have been found to exhibit a superconducting transition temperature in 
excess of 77K. 

R B 

FOCUS - 45 OF 107 PATENTS 

5,286,712 

<=2> GET 1st DRAWING SHEET OF 2 

Feb. 15, 1994 

High TC superconducting film 

INVENTOR: Fujita, Nobuhiko, Hyogo, Japan 
Kobayashi, Tadakazu , Hyogo, Japan 



Itozaki, Hideo, Hyogo, japan 
Tanaka, Saburo, Hyogo, Japan 
Yazu, Shuji, Hyogo, Japan 
Jodai, Tetsuji, Hyogo, Japan 

SUM: 

. . . quasi-perovskite type oxide means a structure which can be considered to 
have such a crystal structure that is similar to perovskite-type oxides and 
includes an orthorhombically distorted perovskite or a distorted 
oxygen-deficient perovskite or the like. 

The present invention also provides a process for producing the 
abovementioned superconducting material, characterized by sintering a mixture of 
the following powders: 

an oxide, carbonate, nitrate or sulfate of one element "A" selected from . . . 

FOCUS - 46 OF 107 PATENTS 

5,283,465 

<=2> GET 1st DRAWING SHEET OF 5 

Feb. 1, 1994 

Superconducting lead on integrated circuit 

INVENTOR: Yamazaki, Shunpei, Tokyo, Japan 

DETDESC: 

... subjected to supplemental annealing at 500o-600o C. for 1-2 hours as 
illustrated in FIG. 1(B). The supplemental annealing allows the superconducting 
ceramic material to form a modulated perovskite- like structure and, as a result, 
a high critical temperature is realized. On the substrate, there are provided 
superconducting leads 10 and 10 1 for interconnection among devices and contacts 
formed in or on the semiconductor substrate and a ... 

FOCUS - 47 OF 107 PATENTS 

5,278,140 

<=2> GET 1st DRAWING SHEET OF 5 

Jan. 11, 1994 

Method for forming grain boundary junction devices using 
high T c superconductors 

INVENTOR: Chaudhari, Praveen, Briarcliff Manor, New York 
Chi, Cheng-Chung J., Yorktown Heights, New York 
Dimos, Duane B., Montclair, New Jersey^ 

Mannhart, Jochen D., Metzingen, New York, Federal Republic of Germany 
Tsuei, Chang C, Chappaqua, New York 

SUM: 

... first showed superconducting behavior in mixed copper-oxides, typically 
including rare earth and/or rare earth- like elements and alkaline earth 
elements, for example La, Ba, Sr, . . . , and ^having a perovskite- like 
structure. Materials including the so called "1-2-3 phase in the Y-Ba-Cu-0 
system have been found to exhibit a superconducting transition temperature in 
excess of 77K. R . B. ... 

FOCUS - 48 OF 107 PATENTS 
5,252,547 
<=2> GET 1st DRAWING SHEET OF 1 
Oct. 12, 1993 




Method of foi^^g an inorganic protective lay^^on an oxide 

superconducting film 

INVENTOR: Itozaki, Hideo, Hyogo, Japan 
Tanaka, Saburo, Hyogo, Japan 
Fujita, Nobuhiko, Hyogo, Japan 
Yazu, Shuji, Hyogo, Japan 
Jodai, Tetsuji, Hyogo, Japan 

SUM: 

... term of quasi-perovskite type means a structure which can be considered 
to have such a crystal structure that is similar to Perovskite-type oxides and 
includes an orthorhombically distorted pexovskite or a distorted 
oxygen-deficient perovskite or the like. 

The superconducting thin film may be also another type of superconductor 
consisting mainly of a compound oxide represented by the formula: 

THETA 4( PHI 1 - q ,Ca q ) id Cu ... 

FOCUS - 49 OF 107 PATENTS 

5,249,525 

<=2> GET 1st DRAWING SHEET OF 11 

Oct. 5, 1993 

Spark-discharge lithography plates containing image-support 

pigments 

INVENTOR: Lewis, Thomas E . , E . Hampstead, New Hampshire 
Nowak, Michael T., Gardner, Massachusetts 

DETDESC : 

... A perspective view of the first layer, labeled n Layer 0", appears in FIG 
6E. As shown in these figures, the spinel structure contains a number of 
octahedral sites for metal ions. Like perovskite structures spinels may also be 
defective, an example being gamma-Fe203. A spinel structure may also be 
intergrown with other structures . 

In spinel compounds useful as image-support pigments, the 

FOCUS - 50 OF 107 PATENTS 

5,244,874 

Sep. 14, 1993 

Process for producing an elongated superconductor 

INVENTOR: Yamamoto, Susumu, Hyogo, Japan 
Kawabe, Nozorau, Hyogo, Japan 
Awazu, Tomoyuki, Hyogo, Japan 

DETDESC : 

... term quasi-perovskite type means a structure which can be considered to 
have such a crystal structure that is similar to perovskite-type oxides and 
includes an orthorhombically distorted perovskite or a distorted 
oxygen-deficient perovskite or the like. 

Another superconducting compound oxide which can be prepared by the present 
invention is represented by the general formula: 

(M, Sr)2CuO 4 - delta 

in which M stands for Y or La and 

FOCUS - 51 OF 107 PATENTS 



C 2.7 



5,241,191 



<=2> GET 1st DRAWING SHEET OF 1 
Aug. 31, 1993 

Cubic perovskite crystal structure, a process of preparing 
the crystal structure, and articles constructed from the 

crystal structure 

INVENTOR: Agostinelli, John A., Rochester, New York 
Chen, Samuel, Penfield, New York 

DETDESC : 

. 1, PA-2, PA-3, PA-4 and PA-5, cited above and here incorporated by 
reference, can be employed. Highly compatible substrates are materials that 
themselves exhibit a perovskite or perovskite- like crystal structure. Strontium 
titanate is an example of a perovskite crystal structure which is specifically 
preferred for use as a substrate. Lanthanum alurainate (LaA103), lanthanum 
gallium oxide (LaGa03) and potassium tantalate are . , . 

FOCUS - 52 OF 107 PATENTS 

5,236,894 

Aug. 17, 1993 

Process for producing a superconducting thin film at 
relatively low temperature 

INVENTOR: Tanaka, Saburo, Itami, Japan 
Itozaki, Hideo, Itami, Japan 
Higaki, Kenjiro, Itami, Japan 
Yazu, Shuji, Itami, Japan 
Jodai, Tetsuji, Itami, Japan 

SUM: 

... crystal structure. The term quasi-perovskite type means a structure which 
can be considered to be similar to perovskite-type oxides and includes an 
orthorhombically distorted perovskite or a distorted oxygen-deficient 
perovskite or the like. 

Still another example of the above-mentioned compound oxide is compound 
oxides represented by the general formula: 

THETA 4( PHI 1 - q , Ca q ) m Cu n 0 p + ... 

FOCUS - 53 OF 107 PATENTS 

5,221,660 

<=2> GET 1st DRAWING SHEET OF 1 

Jun. 22, 1993 

Semiconductor substrate having a superconducting thin film 

INVENTOR: Itozaki, Hideo, Hyogo, Japan 
Harada, Keizo, Hyogo, Japan 
Fujimori, Naoji, Hyogo, Japan 
Yazu, Shuji, Hyogo, Japan 
Jodai, Tetsuji, Hyogo, Japan 

DETDESC : 

• - . term quasi-perovskite type means a structure which can be considered to 
have such a crystal structure that is similar to perovskite-type oxides and 
includes an orthorhombically distorted perovskite or a distorted 
oxygen-deficient perovskite or the like. 



C 2^8 



An atomic ratio of lanthanide element "Ln" : Ba :Cu preferably 1:2:3 as 

is defined by the formula but the atomic ratio is not restricted strictly to 
this ratio. In fact, the other compound oxides having ... 

FOCUS - 54 OF 107 PATENTS 

5,212,148 

<=2> GET 1st DRAWING SHEET OF 1 

May 18, 1993 

Method for manufacturing oxide superconducting films by 

laser evaporation 

INVENTOR: Roas , Bernhard, Erlangen, Federal Republic of Germany 
Endres, Gerhard, Forchheira, Federal Republic of Germany 
Schultz, Ludwig, Bubenreuth, Federal Republic of Germany 

SUM: 

... yet exactly established. This initial product is then converted, by 
applying a heat and oxygen treatment, into the material with the desired 
superconducting phase. 

The superconductive metal-oxide phases, to be obtained in this manner, can 
have perovskite-like crystal structures and, in the case of YBa2Cu30 7 - x , 
whereby 0 < x < 0.5, have an orthorhomic structure (compare, for example, 
Europhysics Letters' 1 , Vol. 3, No. 12, Jun. 15, 1987, pages ... 

FOCUS - 55 OF 107 PATENTS 

5,183,799 

<=2> GET 1st DRAWING SHEET OF 16 

Feb. 2, 1993 

Superconducting materials including La-Sr-Nb-0, Y-Ba-Nb-0, 
La-Sr-Nb-Cu-O, and Y-Ba-Nb-Cu-0 

INVENTOR: Ogushi, Tetsuya, Kagoshima, Japan 
Hakuraku, Yoshinori, Kagoshima, Japan 
Ogata, Hisanao, Ibraki, Japan 

ABST: 

... V, Nb, Ta, T, Zr or Hf; 0 < x < 1; 0 < z < 1; i = 1, 3/2 or 2; 0 < y </= 
4; Gis F, CI or N; delta is oxygen defect, and having a perovskite-like crystal 
structure, show superconductivity at a temperature higher than the liquid 
nitrogen temperature. 

SUM: 

BACKGROUND OF THE INVENTION 

This invention relates to a superconducting material having a 
perovskite-like crystal structure and a superconducting part using the same, 
particularly to a superconducting material suitable for having a high 
superconducting transition temperature (Tc), and a process for producing the 
same . 

Heretofore, . . . 

DETDESC : 

DESCRIPTION OF THE PREFERRED EMBODIMENTS 

The superconducting materials of this invention have a perovskite-like 
crystal structure and represented by the formulae: 



(L x A 1 - x ) i MO ^1) 



(LxAl-x)iMl-zCuz... 

... by laminating this superconducting material with other films of 
electrical insulating material. It is preferable to laminate a plurality of 
film-like layers alternately, respectively. Further, it is preferable to use as 
an insulating material a perovskite- like ceramic of the same series. 

Further, in the above-mentioned formulae (1) and (2), a total of valence 
number (p) of L, A and M, or L, A, M and Cu, and the valence number y of ... 

... OMITTED p SYMBOL OMITTED = SYMBOL OMITTED y SYMBOL OMITTED +/- 0.5 

Pat. No. 5183799, * 

FOCUS 

Further, it is preferable to include M of the valence of two. 

More in detail, the material represented by the formula (1) has a 
perovskite-like crystal structure and has as the L element at least one element 
selected from the group consisting of scandium (Sc), yitriura (Y), and lanthanide 
elements of atomic numbers 57 to 71 (La to Lu) belonging to the group . . . 

... Ta) belonging to the group Vb of the periodic table and titanium (Ti), 
zirconium (Zr) and hafnium (Hf) belonging to the group IVb of the periodic 
table, these element being able to include Cu. 

The oxide superconducting material having the perovskite-like crystal 
structure of this invention has as a fundamental constitution an octahedron 
having the M element which is an atom belonging to the group Vb or IVb as its 
center and 6 oxygen atoms. Since this material has defect of oxygen, that is, 
one or ... 

... a mutual action of strong attraction necessary for forming a hole pair or 
electron pair showing a superconducting phenomenon at a temperature of 150K or 
higher . 

The oxide superconducting material of this invention has the perovskite* like 
crystal structure as shown in FIGS. 1 and 2. These drawings show unit lattices 
of the materials represented by the formulae: 

(L x A 1 - x ) i MO y( 1) 

and ( ... 

... formula (4) with at least one element selected from those of the group 
IVb and Vb, the total amount of the elements of the group IVb and Vb can exceed 
the amount of Cu. 

It is also possible to produce an oxide superconducting powder having a 
perovskite-like crystal structure containing M element mainly by mixing a powder 
of oxide material represented by (L x A 1 - x ) i CuO y , wherein x is 0 < x < 



... Cu:M = 1:1, carrying out substitution reaction between Cu and M element 
in vacuum, and finally pulverizing the final reaction product. 

It is further possible to produce an oxide superconducting powder having a 
perovskite-like crystal structure and containing M element mainly by depositing 
in vacuum a film of pure metal of M element selected from the elements of groups 
IVb and Vb on outer surface of oxide ceramic . . . 

... 1, 3/2 or 2; y is 0 < y </= 4, containing the M element mainly (M being 



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A* rk * \\- k A A A A A A A A A A A A A A A A A A A - A A A A A A A A A 0 3460 * ******* A A A A A A A A A A A A A A A A A A-***-, 1 " **** 

LEVEL 1 - 1 OF 2 PATENTS 
5,134,042 
<=2> GET 1st DRAWING SHEET OF 6 
Jul. 28, 1992 

Solid compositions for fuel cells, sensors and catalysts 

INVENTOR: Madou, Marc J., Palo Alto, California 
Otagawa, Takaaki, Fremont, California 
Sher, Arden, Foster City, California 

... [*12] selected from lanthanum, cerium, neodyraium, praseodymium, or 
scandium, B is independently selected from strontium, calcium, barium or 
magnesium, Q is independently selected from nickel, cobalt, iron or manganese, 
and y is between about 0,0001 and 1, wherein the perovskite or perovskite- type 
structure has an average size and distribution of between about 50 and 200 
Angstroms in diameter; and the composite layer of between about 25 and 1000 
microns in thickness; 



said composite havin 




Itiple interfaces between: 




PAGE 



LEVEL 1 - 2 OF 2 PATENTS 
4,948,680 
<=2> GET 1st DRAWING SHEET OF 26 
Aug. 14, 1990 
Solid compositions for fuel cell electrolytes 



INVENTOR: Madou, Marc J., Palo Alto, California 
Otagawa, Takaaki, Fremont, California 
Sher, Arden, Foster City, California 

... [*25] 1.5 and d is between 0.001 and less than or equal to 3, 

wherein either the first electrode material (C) or second electrode material 
(A 1 ) comprises 

Al-xBxQ0 3 

having a perovskite or perovskite-type structure as an electrode catalyst i 
combination with 

A 1 - x B x Z 

as a polycrystalline solid electrolyte wherein 

A is independently selected from lanthanum, cerium, neodymium, praseodymium 
or scandium, 



2 PAGES 
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JOB 53252 

11/24/97 



100G6J 




Perovskites and High T c 
Superconductors 



by 

Francis S. Galasso 

United Technologies Research Laboratories 
East Hartford, Connecticut 
USA 



GORDON AND BREACH SCIENCE PUBLISHERS 
New York • Philadelphia • London • Paris • Montreux 
Tokyo • Melbourne 



© 1990 by OPA (Amsterdam) B.V. All rights reserved. Published under 
license by Gordon and Breach Science Publishers S.A. 



Gordon and Breach Science Publishers 



Post Office Box 786 
Cooper Station 
New York, New York 10276 
United States of America 



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Japan 



Post Office Box 197 
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Private Bag 8 
Camberwell, Victoria 3124 
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United Kingdom 

58, rue Lhomond 
75005 Paris 
France 

Portions of this material were published previously in "Structure, 
Properties and Preparation of Perovskite-Type Compounds" by 
Francis S. Galasso, copyright © 1968 by Pergamon Press, Oxford. 

Library of Congress Cataloging-in-Publication Data 

Galasso, Francis S. 

Perovskites and high T c superconductors / by Francis S. Galasso. 



ISBN 2-88124-391-6 

1. High temperature superconductors. 2. Perovskite. I. Title 
QC611.98.H54G35 1990 



No part of this book may be reproduced or utilized in any form or by 
any means, electronic or mechanical, including photocopying and 
recording, or by any information storage or retrieval system, without 
permission in writing from the publishers. Printed in the United States 
of America, 



p. cm. 



537.6'23--dc20 



89-38877 
CIP 



C) 



F. Galasso 



<:hese compounds as 
ibed. In addition, a 
cs oxides with the 

dc bubble research, 
high dielectric con- 
c memory work and 
:n conducted for the 
of interest in devices 
o been investigated 



Chapter II 

Structure of Perovskite-type 
Compounds 



e more interest in 
n that the greatest 
the discovery of the 
k is devoted to this 



Most of the compounds with the general formula AB0 3 have the 
perovskite structure. The atomic arrangement in this structure was first 
found for the mineral perovskite, CaTi0 3 . It was thought that the unit 
cell of CaTi0 3 could be represented by calcium ions at the corners of a 
cube with titanium ions at the body center and oxygen ions at the center 
of the faces (Fig. 2.1). This simple cubic structure has retained the name 
perovskite, even though CaTi0 3 was later determined to be orthor- 
hombic by Megaw.* 1 ' Through the years it has been found that very few 
perovskite-type oxides have the simple cubic structure at room temper- 
ature, but many assume this ideal structure at higher temperatures. 

In the perovskite structure, the A cation is coordinated with twelve 
oxygen ions and the B cation with six. Thus, the A cation is normally 
found to be somewhat larger than the B cation. In order to have contact 
between the A, B, and O ions, R A + R G should equal X /2(R B + R G ), 
where R A , R B and R 0 are the ionic radii. Goldschmidt* 2 ' has shown that 
the cubic perovskite structure is stable only if a tolerance factor, t 
defined by R A + R G = f \/2(R B + R 0 X has an approximate range of 
0.8 < t < 0.9, and a somewhat larger range for distorted perovskite 
structures. It should be noted that conflicting reports in the literature 
make it difficult to assign the correct unit cell dimensions for these 
distorted perovskite structures. 

The ternary perovskite-type oxides described in this chapter will be 
divided into A l+ B 5 + 0 3 , A 2 + B 4 + 0 3 , A 3 + B 3+ 0 3 types and 
oxygen- and cation-deficient phases. The oxygen- and cation-deficient 
phases will be regardecTas those which contain considerable vacancies 
and not those phases which are only slightly non-stoichiometric. Many 
of these contain B ions of one element in two valence states and should 



COPPER OXIDE 
SUPERCONDUCTORS 



Charles P. Poole, Jr. 
Timir Datta 
Horacio A, Farach 

with help from 

M. M. Rigney 
C. R. Sanders 

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




WILEY 

A Wiley-Interscience Publication 
JOHN WILEY & SONS 

New York • Chichester • Brisbane • Toronto • Singapore 

Fl 



Copyright © 1988 by John Wiley & Sons, Inc. 



All rights reserved. Published simultaneously in Canada- 
Reproduction or translation of any part of this work 
beyond that permitted by Section 107 or 108 of the 
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 Department, John Wiley & Sons. Inc. 

Library of Congress Cataloging in Publication Data: 

Poole. Charles P. 
Copper oxide superconductors / Charles P. Poole, Jr.. Timir Datta 
and Horacio A. Farach: with help from M. M. Rigncy and C. R. S; 
p. cm. 

"A Wilcy-Intcrscicncc publication." 
Bibliography: p. 
Includes index. 

I. Copper oxide superconductors. I. Datta. Timir. II. Farach. 
Horacio A. 111. Title. 

QC6IJ.98.C64P66 1988 
539.6'23-dc 19 88-18569 CIP 
ISBN 0-471-62342-3 

Printed in the United States of America 

10 9876S4321 




78 CRYSTALLOGRAPHIC STRUCTURES 



tetragonal phase, and the metal-to-insulator transition occurs at the tetragonal- 
to-orthorhombic phase boundary* = 0.35 (Matt7, Sleil). 



D. PEROVSKITE TYPE SUPERCONDUCTING STRUCTURES 

In their first report on high-temperature superconductors Bednorz and Miiller 
referred to their samples as "metallic, oxygen deficient . . . perovskite like 
mixed valent copper compounds." Subsequent work has confirmed that the new 
superconductors do indeed have these characteristics. In this section we will 
comment on their perovskite-like aspects. 

I. Atom Sizes 

In the oxide superconductors Cu replaces the Ti' + ions (0.68 A ) of perovskite 
and in most cases retains the CuO, layering with two oxygens per copper in the 
layer. Other catton.c replacements tend to be Bi. Ca, La. Sr, Tl. and Y for the 
larger Ba, forming "layers" containing only one oxygen or none per cation We 
see from the following list of ionic radii 



Cu- 1 * 


0.72 A 




0.74 A 




0.94 A 


Tl- 1 " 


0.95 A 




0.96 A 


Ca : * 


0.99 A 


Sr : * 


1.12 A 


La ; " 


1.14 A 


Ba : ~ 


1.34 A 




1.32 A 



(VI-4) 



that there are four s.ze groups, with all other cations significantly smaller then 
the Ba of perovsk.te. The common feature of CuO, layers that are planar or close 
to planar establishes a fairly uniform lattice size in the a.b plane. The parame- 

T«Q / e pTr dS LaSrCU ° { " = b - = 3 77 A >' YBaCu0 <* = 3-83 A.b = 
3.89 A), B.SrCaCuO (a = b = 3.82 A), and TIBaCaCuO (« = b = 3.86 A) 

are all between the ideal fee oxygen lattice value of 3.73 A and the perovskite 
one of 4.01 A . 

Table VI-2 gives the ionic radii of the positively charged ions of various ele- 
ments of the periodic table. These radii are useful for esnmatiny changes in lat- 
tice constant when tome substitutions are made in existing structures They also 
prov.de some msight ,nto which types of substitutions will be most favorable. 



F3 





ion occurs at the tetragonal- 
SJeil ). 



STRUCTURES 

ictors Bednorz and Muiler 
icient . . . perovskite like 
has confirmed that the new 
cs. In this section we will 



ns (0.68 A) of perovskite, 
oxygens per copper in the 
La, Sr, Tl, and Y for the 
-*n or none per cation. We 



(VI-4) 



gnificantfy smaller (hen 
i that are planar or close 
plane. The parame- 
<CuO(a = 3.83 A,* = 
MO(a = b = 3.86 A) 
5 A and the perovskite 

ged ions of various ele- 
"mating changes in lat- 
g structures. They also 
•II be most favorable. 



TABLE VI-2. Ionic Radii in Angstroms of Selected Elements tor Various Positive 


Charge Stales" 








Z 


Element 


+ 1 +2 +3 


+4 +5 


+6 






Alkali 






3 


Li 


0.68 






11 


Na 


0.97 






19 


K 


1.33 






37 


Rb 


1.47 






cc 




1.67 










Alkaline earths 






4 


Be 


0.44 0.35 






12 


Mg 


0.82 0.66 






20 


Ca 


1.18 0.99 






38 


Sr 


1.12 






S6 


Oil 


1 .53 1 .34 










Group III 






5 


B 


0.35 0.23 






13 


Al 


0.51 






31 


Ga 


0.81 0.62 






4Q 


i n 


0.81 






81 


Tl 


1 .47 0.95 










Group /V 






6 


C 




0.16 




14 


»>1 


0.65 


0.42 




32 


Ge 


0.73 


0.53 




50 


Sn 


0.93 


0.71 




82 


Pb 


1.20 


0.84 








Group V 






IS 


P 


0.44 


0.35 




33 


As 


0.5H 


0.46 




5) 


Sb 


0.89 ().76 


0.62 




83 


Bi 


0.98 0.96 


0.74 








ChalcagvniiU's 






16 


S 




0.37 


0.30 


34 


Se 


0.66 


0.50 


0.42 


52 


Te 


0.82 


0.70 


0.56 






First transition series (3d n } 






21 


Sc 


0.81 






22 


Ti 


0.96 0.94 0.76 


0.68 




23 


• V 


0.88 0.74 


0.63 0.59 




24 


Cr 


0.8! 0.89 0.63 




0.52 


25 


Mn 


0.80 0.66 


0.60 






i 

s 

I 

S 1 
ED; 

2.1 

a ; 
5 ' 



79 



COPPER OXIDE 
SUPERCONDUCTORS 



Charles P. Poole, Jr. 
Timir Datta 
Horacio A. Farach 

with help from 

M. M. Rigney 
C. R. Sanders 

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




WILEY 

A Wiley-Interscience Publication 
JOHN WILEY & SONS 

New York • Chichester • Brisbane • Toronto • Singapore 




Copyright © 1988 by John Wiley & Sons, Inc. 

AH rights reserved. Published simultaneously in Canada. 

Reproduction or translation of any part of this work 
beyond that permitted by Section 107 or 108 of the 
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 Department, John Wiley & Sons. Inc. 

Library of Congress Cataloging in Publication Data: 

Poole, Charles P. 
Copper oxide superconductors / Charles P. Poole, Jr.. Timir Datta. 
and Horacio A. Farach: with help from M. M. Rigney and C. R. Sanders, 
p. cm. 

"A Wilcy-Intcrscicnce publication." 
Bibliography: p. 
Includes index. 

I. Copper oxide superconductors. 1. Datta. Timir. II. Farach, 
Horacio A. 111. Title. 

QC611.98.C64P66 1988 
539.6'23-dc 19 88-I8S69 CIP 
ISBN 0-471-62342-3 

Printed in the United States of America 

10 987654321 



T 
ti- 
ll 
st 
t< 
^ 
ti 
v 
v 
d 



X2- 



VI 



CRYSTALLOGRAPHIC STRUCTURES 



A. INTRODUCTION 



To properly understand the mechanisms that bring about the superconducting 
state in particular materials it is necessary to know the structures of the com- 
pounds that exhibit this phenomenon. Single-crystal structure studies have been 
carried out to determine the dimensions of the unit cell, the locations of the 
atoms in this cell, electronic charge distributions, and the possible presence of 
atomic irregularities. Neutron powder diffraction has also provided much of the 
detailed structure information found in this chapter (e.g., Antso, Beech, Cappo, 
Coxzz, Davil , Dayzz, Greed, John4. Jorge, Jorgl, Paulz, Torar, Vakni, Yamag, 
Yanz2). More routine X-ray powder pattern measurements which can identify a 
known structure and provide the unit cell dimensions are useful for checking the 
quality of samples, as was explained in Section VI. 

The numerical values of quantities such as lattice parameters and bond 
lengths show some variation in the literature, and many of our quoted values will 
be typical ones. Much of the quantitative structural information is organized in 
the tables. 

In the beginning of this chapter we will introduce the perovskite structure and 
indicate how it is related to the oxide superconductors. Then we will describe the 
21 structure of LaSrCuO and the 123 structure of YBaCuO, we will show how 
each is generated from a perovskite prototype, and we will clarify its layering 
scheme. The chapter will end with descriptions of the structures of the newer 
high-transition-temperature bismuth and thallium compounds. 



72 




CTURES 



ie superconducting 
ictures of the com- 
e studies have been 
he locations of the 
ossible presence of 
^videdmuch of the 
tso, Beech, Cappo, 
*r, Vakni, Yamag, 
hich can identify a 
ui for checking the 

meters and bond 
quoted values will 
on is organized in 

kite structure and 
e will describe the 
we will show how 
'arify its layering 
ares of the newer 



PEROVSKITES 



73 



B. PEROVSKITES 



Much has been written about the oxide superconductor compounds being 
perovskite types, so we will begin with a description of the perovskite structure. 
This will permit us to develop some of the notation to be used in describing the 
structures of the superconductors themselves. 

1. Cubic Form 

Above 200°C barium titanate crystallizes in the perovskite structure, which is 
cubic, so the three lattice parameters are all equal (i.e., a = b = c). The unit cell 
contains one formula unit BaTi0 3 and the atoms are located in the following 
special j^ositions (Wyck2, p. 390): 



Ba 
Ti 
O 



i i i 



(la) 
(lb) 0,0,0 

(3c) 0,0,i; 0,^0:^,0,0 



(VI-1) 



where w ' have employed the crystallographic notation (la) for an a-type lattice 
site which contains one atom, (3c) for a c-type lattice site which contains three 
atoms, ; nd so on. Each atomic position is given by three coordinates, such as 
0,0,f for the oxygen located atx = 0,jy = 0, z = 0.5a. This arrangement corre- 
sponds to placing a titanium atom on each apex, a barium atom in the body 
center, and an oxygen atom on the center of each edge of the cube, as illustrated 
on Fig. VI-1 . We see from the figure that the barium atoms are 12-fold coordi- 
nated and the titaniums have sixfold (octahedral) coordination. The lattice con- 
stant or length of the unit cell is a = 4.0118 A at 201 °C. The crystallographic 
space group is Pm3m, O l h . 

An alternate way to represent this structure, which is commonly used in solid- 
state texts and in crystallography monographs (e.g., Wyck2), is to locate the 




Fig. VI-1. Perovskite cubic unit cell showing titanium on the apices and oxygen in the 
edge-centered positions. Barium, which is in the body center, is not shown. 



74 CRYSTALLOGRAPHIC STRUCTURES 

origin at the barium site; this places titanium in the center and the oxygens on 
the centers of the cube faces. The representation (Eq. VI-1) given above is more 
convenient for comparison with the structures of the oxide superconductors. 

The compound LaBaCu 2 O s was found to have a cubic perovskite subcell with 
the lattice parameter a = 3.917 A (Sishe). 

2. Tetragonal Form 

Atroom temperature barium titanate is tetragonal with the unit cell dimensions 
a = 3.9947 A and c = 4.0336 A , which is close to cubic. For this lower symme- 
try the oxygens are assigned to two different sites, a single site along the side 
edges and a twofold one at the top and bottom. The atomic positions (Wyck2 
p. 401) 



Ba £,i,0.488 

Ti 0,0,0 

O(l) 0,0,0.511 

0(2) 0^,-0.026; £,0,-0.026 



(VI-2) 



are shown in Fig. Vl-2. The distortions from the ideal structure of F|g. VM are 
exaggerated on this sketch. We will see later that a similar distortion occurs in 
the YBaCuO structure. The cubic and tetragonal atom arrangements (VM) and 
(VI-2) are compared in Table VM, and we see from this table that the deviation 
from cubic symmetry is actually quite small. 

3. Orthorhombic Form 

When barium titanate is cooled below 5°C it undergoes a transition with a fur- 
ther lowering of the symmetry to the orthorhombic space group Amm2, C 2v , and 



TABLE VM. Comparison of Atom Positions of BaTi0 3 in Its Cubic, Tetragonal and 
Orthorhombic Forms" 



Group Atom 



Ti0 2 



BaO 



TiO, 



l o 

( Ba 
I O 



Cubic and Tetragonal 

x y 



o 

o 
i 

2 

0 

2 

0 
0 

i 

2 



2 

0 



2 

0 

2 

0 



2 
I 

2 

0 

0 
0 



Cubic Tetragonal Orthorhombic 



1 

0.974 
0.974 
0.511 
0.488 
0 

-0.026 
-0.026 



I 

1 

I 
■ 

2 
I 

2 

0 
0 
0 



-The x andy coordinates are the same for both positions. The orthorhombic form z coordinates are 
also given ( Wyck2. pp. 390, 40 J , 405). 




ter and the oxygens on 
-1) given above is more 
de superconductors, 
perovskite subcell with 



te unit cell dimensions 
For this lower symme- 
>Ie site along the side 
nic positions (Wyck2, 



(VI-2) 



cture of Fig. VI ] are 
r distortion occ urs in 
ingements(VM)and 
ble that the deviation 



Transition with a fur- 
iup Amm2, C 2v , and 



ubic, Tetragonal and 

I Orthorhombic 
z 

I 
I 



2 

0 
0 
0 

c form z coordinates < 



PEROVSKITES 



75 




Fig. VI-2* Perovskite tetragonal unit cell showing the puckering of the Ti-O layers. 



an enlargement of the unit cell to accommodate two formula units (BaTiOj) 2 . 
The enlarged cell is rotated by 45° relative to the higher-temperature ones, as 
shown on Fig. VI-3, and therefore its a and b lattice parameter?; are larger by 
the factor V2. The three lattice constants are a — 5.669 — 4.009\/2~ A, b = 
5.682 = 4.018Vy A, and c = 3.990 A. There are no longer any special sites, 
and the atomic positions are (Wyck2, p. 405): 



Ba (2a) 0,±,i; ±M 

Ti (2b) 0 f M + i,0; £,w,0 with u = 0.510 
O(l) (2a) 0,t/ + £,£;|.">i with u — 0.490 
0(2) (4e) w,v-hi,0; -w,v+£,0; w + i t v,0; -w + |,v,0 
with u = 0.253, v = 0.237 



(Vi-3) 



where u — 0 for Ba. 

One should note that in Eq. (VI-3) Ba and O(l) are in the same (2a) type of 
site with different values of the parameter u. Figure VI-3 shows the coordinates 
of the atoms in the orthorhombic cell drawn using the approximation for 
0.490 and 0.510 and = \ for 0.253 and 0.237. 

A comparison of Eqs. VM to VI-3 indicates that the transformation from 
cubic to tetragonal involves only shifts in the z coordinates of atoms, while the 
orthorhombic phrase differs from the cubic one only through shifts in atom posi- 
tions within xy planes (see Taole VI- 1). 



4. Atom Arrangements 

The ionic radii of Ba 2+ (1.34 A) and O 2- (1.32 A) are almost the same, and 
together they form a face-centered cubic (fee) close-packed lattice with the 
smaller Ti 4+ ions (0.68 A) located in octahedral holes. The octahedral holes of a 
close-packed oxygen lattice have a radius of 0.545 A , and if these holes were 
empty the lattice parameter would be a = 3.73. as shown on Fig. VI-4a . If each 



IC 



76 CRYSTALLOGRAPHIC STRUCTURES 



Barium 



2=1/2 
Layer 



2 = 0 
Layer 




Oxygen 



Titanium (copper) 



Kg* VI-3. Atom positions of perovskite when (the monomolecular tetragonal unit cell is 
expanded to the bimolecular orthorhombic cell with new axes at 45° with respect to the 
old ones. v 



titanium were to move the surrounding oxygens apart to its ionic radius when 

!T : ™ P r n i the h °' e ' " Sh ° Wn ° n Fifi - VlAb - the lattice Parameter « would be 
4.00 A.. The observed cubic (« = 4.012 A) and tetragonal (a = 3 995 A c = 
4 034 A) lattice parameters are close to these values, indicating a pushing apart 
of the oxygens. The tetragonal distortion illustrated on Fig. VI-2 and the 
orthorhombic distortion of Eq. (VI-3) constitute attempts to achieve this 
through an enlarged but distorted octahedral site. This same mechanism is oper- 
ative in the oxide superconductors. 



C. BARIUM-LEAD-BISMUTH OXIDE 

In 1983 Mattheiss and Hamann referred to the 1975 "discovery by Sleight et al 
of high temperature superconductivity" of the compound BaPb, ^O, in the 
composuion range 0.05 < l£ 0.3 with T t up to 13 K (Matt7. Sleig). Many 
consider this system, which disproportionates 2 Bi<+ - Bi 3+ + Bi 5+ in going 
from the metallic to the semiconducting state, as a predecessor to the LaSrCuO 
system. 



3:7 



82 CRYSTALLOGRAPHIC STRUCTURES 



TABLE VI-3. Atom Positions of Regular and Alternate LajCuO, Structure, Both of 
Which Correspond to Space Group IMmmm, 



Regular Structure 



Alternate Structure 



Complex Jdeafr Atom Site 



Atom Site jr. 



Cu0 2 
OLa 

LaO 
0 2 Cu 
LaO 

OLa 

Cu0 2 



( 0(1) 
1 CKD 
(.Cu 

0 833 fe) 



fO(2) 
(La 
(QW 
\ W) 

0.333 U ? 
CO(2) 



= 0.667 



z = 0.167 



foci) 

(La 
fCKl) 
0(1) 

Lea 



4c 
4c 
2a 
4e 
4e 



4e 
4e 
4c 
4c 
2a 
4e 
4e 



4e 
4e 
4c 
4c 
2a 



2 

0 
0 
i 

2 



0 
I 

2 
1 

2 

0 
0 



2 

0 
I 

2 

0 



2 

0 
I 

2 

0 



1 
1 
1 

0.862 
0.818 



0.682 
0.638 



0.362 



i 0.318 



0.182 
0.138 

0 

0 

0 



0(1) 
Oil) 
Cu 
La 

<X2) 
Oil) 

La 

O(l) 

0(1) 

Cu 

La 

0(2) 
0(2) 

La 
O(l) 
O(l) 
Cu 



4c 
4c 
2a 
4e 

4d 
4d 

4e 
4c 
4c 
2a 
4e 

4d 
4d 

4e 
4c 
4c 
2a 



2 

0 



0 
0 

i 

2 

I 

2 

0 



2 
1 
2 

0 



0 
1 

2 

0 

I 

2 



0 

I 

2 

0 
I 

2 

0 



1 

2 

0 

I 

2 



1 
1 
1 

0.862 



0.638 



0.362 



0.138 
0 
0 
0 



•Superconducting compounds crystallize in the regular structure 
2 values in column 2 are for the prototype perovskitc. 



(Oguch; see also Onoda). The ideal 



constants for tetragonal LaSrCuO superconductors with various values of jc, 
and 6 in the formula (La^SrJj.yCuO^. 



2. Alternate Tetragonal Form 

In the previous section we discussed the tetragonal structure which is adopted by 
LaSrCuO superconductors. It has a variant (Hutir, Oguch) called the Nd 2 CuO« 
structure in which the oxygens 0(2) are in special sites (4d) instead of the general 
(4e) sites in the same space group, corresponding to 

0(2) <4d) 0,i,i;i ? 0.4;i f O,i;O f U (VI-7) 

The remaining atoms are in the positions given by Eq. (VI-6) and listed in Table 
VI-3, and the unit cell is sketched on the right-hand side of Fig. VI-5. This struc- 
ture tends to be unstable relative to its K 2 NiF< counterpart, and is not known to 
superconduct. 



If 



-Vive's. 



78 CRYSTALLOGRAPHIC STRUCTURES 

,e,ra 8 on„ phase, and * «M«7 ^"r" " *' le " 28 °° a " 

tcorthorhombic phase boundarj' * - »-35 <Matt7, 

D. PEROVSKITE-TYPE SUPERCONDUCTING STRUCTURES 

,„ ,„«„- firs, report - j^-g-. ^T^tl 

referred to the,. s»»P>« » s H fT*^- °"X.rk to confirmed that the «r. 
comment on their perovskite-like aspects. 



1. Atom Sizes . . 

and in most cases retains the CO, * ™° U and Y for the 

see from the following list of ionic radii 



Cu J+ 
Bi J+ 



0.72 A 
0.74 A 



Bi 3+ 
Ca 2+ 



0.94 A 
0.95 A 
0.96 A 
0.99 A 



(VI-4) 



Sr 2+ 
La ,+ 



1.12 A 
1.14 A 



Ba 2+ 
O 2 " 



1.34 A 
1.32 A 



th at there are four s, Z e group, ,Uh ^^fJJJ^S 

the Ba of perovskite. The common feature of CuO laye * that P 

to planar VstabHshes a fairly uniform lattice size m ^J^™ P A , b = 

terUf the compounds LaSrCuOt* = b = b = 3.86 A) 

3.89 A), BiSrCaCuO (« = b = 3.82 A , and TlBaCaCuO (a b 

are all between the ideal fee oxygen lattice value of 3.73 A and pe 

° ne Tabt' VW gives the ionic radii of the positively charged ions of various £ 
J25 the pedodic table. These radii are u*fu. 



x? 



rs at the tetragonal- 



TURES 

"ednorz and Miiller 
. . perovskite like 
firmed that the new 
his section we will 



3 A ) of perovskite, 
s per copper in the 
■, Tl, and Y for the 
one per cation. We 



(VI-4) 



antly smaller then 
are planar or close 
ane. The parame- 
{a =3.83 A t b = 
i = b = 3.86 A) 
;nd the perovskite 

»ns of various ele- 
ng changes in lat- 
lctures. They also 
most favorable. 



TABLE VI-2. Ionic Radii in Angstroms of Selected Elements (or Various Positive 
Charge Slates" 



z 


Element 


+ 1 


+2 +3 


+4 








Alkali 




3 


Li 


0.68 






11 


Na 


0.97 






19 


K 


1.33 






3? 


Rb 


1.47 






55 


Cs 


1.67 












Alkaline earths 




4 


Be 


0.44 


0.35 




12 


Mg 


0.82 


0.66 




20 


a 


1.18 


0.99 




38 


Sr 




1.12 




56 


Ba 










*< 




www 

Group HI 




5 


B 


0.35 


0.23 




13 


ai; 




0.51 




31 


Ga 
In 


0.81 


0.62 




49 




n fit 




81 


Tl 


1.47 


0.95 










fwFfh IJfl MY 




6 


C 






0.16 


1 A 

J4 


OH 






0.42 


32 


Go 




0.73 


0.53 


50 


Sn 




0.93 


0.71 


82 


Pb 




1.20 


f\ OA 

0.84 








Group V 




15 


P 




0.44 




33 


As 




0.56 




51 


Sb 


0.89 


0.70 




83 


Bi 


0.98 


0.% 










Chalcogenides 




16 


S 






0.37 


34 


Se 


0.66 




0.50 


52 


Te 


0.82 




0.70 






First transition series (3d n ) 




21 


Sc 




0.81 




22 


Ti 


0.96 


0.94 0.76 


0.68 


23 


V 




0.88 0.74 


0.63 


24 


Cr 


0.81 


0.89 0.63 




25 


Mn 




0.80 0.66 


0.60 



+5 



+6 



0.35 
0.46 
0.62 
0.74 



0.30 
0.42 
0.56 



0.59 



0.52 
79 



7ZIV 



TABLE VI-2, (continued) 



z 


Element 


+ 1 


+2 +3 


zo 


re 




0.74 0.64 


27 


Co 




0.72 0.63 


28 


Ni 




0.69 


29 


Cu 


0.96 


0.72 


30 


Zn 


0.88 


0.74 






Second transition series (4d n ) 


39 


Y 




0.94 


40 


Zr 


1.09 




41 


Nb 


1.00 




42 


Mo 


0.93 




*i j 


Tc 






44 


Ru 






45 


Rh 




0.68 


46 


Pd 




0.80 


47 


Ag 


1.26 


0.89 


48 


Gd 


1.14 


0.97 






Third transition series (5d n ) 


72 


Hf 






73 


Ta 






74 


W 






75 


Re 






76 


Os 






77 


lr 






78 


Pt 




0.80 


79 


Au 


1.37 


0.85 


80 


Hg 


1.27 


1.10 








Rare earths (4f n ) 



+4 



+5 



+6 



57 
58 
59 
60 
61 
62 
63 
64 
65 
66 
67 
68 
69 
70 
71 



La 

Ce 

Pr 

Nd 

Pm 

Sm 

Eu 

Gd 

Tb 

Dy 

Ho 

Er 

Tm 

Yb 

Lu 



1.39 
1.27 



1.14 
1.07 
1.06 
1.04 
1.06 
1.00 
0.98 
0.62 
0.93 
0.92 
0.91 
0.89 
0.87 
0.86 
0.85 



0.79 
0.74 
0.70 

0.67 

0.65 



0.78 

0.70 
0.72 
0.88 
0.68 
0.65 



0.94 
0.92 



0.81 



0.69 



0.62 



0.68 



0.62 
0.69 



•Three anion radii arc 
Physics). 

80 



1.32 for 0 2 ~. 1.33 for F~, and 1.84 for S 2 ' (Handbook of Chemistry and 




+5 +6 



0.69 



0.62 



0.68 



0.62 
0.69 



yf Chemistry and 



PEROVSKITE-TYPE SUPERCONDUCTING STRUCTURES 81 

2* Unit Cell Stacking 

Three and four fundamental fee unit cells stack vertically to form the supercon- 
ducting unit cells of YBaCuO and LaSrCuO, respectively, with some oxygens 
removed in the process. This causes the vertical height or c parameter of the unit 
cell to be less than that expected for the stacking of perovskite cells: 



YBaCuO: c * 11.7 A, 3c fcc = 11.19 A, 3^ = 12.03 A^ 
LaSrCuO: c * 13.18 A, 4c fcc = 14.92 A, Ac^ = 16.04 A 



(VI-5) 



Similar stackings occur in the BiSrCaCuO and TIBaCaCuO compounds. 



E. LANTHANUM-COPPER OXIDE 

The structure of LaSrCuO, (La^MJiCuO^, called the 21 structure, where M 
is usually Sr or Ba, is tetragonal in some cases and orthorhombic in others. We 
will describe the tetragonal case first and then the orthorhombic distortion of it. 
The structures will be described in terms of the prototype compound La 2 Cu€> 4 
corresponding to jc = 8 = 0 in the above expression, keeping in mind that in th« 
superconducting compounds themselves some of the La atoms are replaced by, a 
divalent cation such as Sr or Ba. Since lanthanum has a charge of +3 and oxy- 
gen is - 2, it follows that all of the copper is divalent ( + 2) when x = 0, and some 
becomes trivalent for x > 0. 

The compound La 2 Cu0 4 itself is considered to be nonsuperconducting, but 
some investigators claim that it or portions of it do exhibit superconductivity, 
perhaps of a f ilimentary type (Beill, Coopl, Dvora, Granl, Pickl, Shahe, Skelt, 
Skell, Skel2). 



1. Tetragonal Form 

The tetragonal LaSrCuO superconductors crystallize in what is called the 
K 2 NiF< structure with space group H/www, D\l and two formula units per unit 
cell (e.g., Burns, Colli, Hirot, Mossz, Onoda; Wyck3, p. 68). The copper atoms 
and one of the oxygen types O(l) are in special positions and the remaining at- 
oms are all in general positions, with a single undetermined parameter associ- 
ated with the z coordinate. The positions are 



La (4e) 0,0,w; 0\0,-«; + + f 

Cu (2a) 0,0,0; 

O(l) (4c) 0,£,0; £,0,0; ±,0,4; 0*hl 

0(2) (4e) 0,0,v; 0,0,-v; £,i,v+ J; i,i.-v+± 



(VI-6) 



w ith u = 0.362 and v = 0.182. Typical lattice dimensions area = b = 3.77 A, 
c = 13.18 A. Table VI-3 gives more details on the atom positions and Fig. VI- 
5a provides a sketch of this 21 structure. Table Vl-4 lists the measured lattice 






82 CRYSTALLOGRAPHY STRUCTURES 

TABLE VI-3. Atom Positions of Regular and Alternate La 2 CuO< Structure, Both <f 
Which Correspond to Space Group /4/mmm, D 4h a 



Regular Structure 



Complex Ideal z At om Site x 

4c 0 



Cu0 2 
OLa 

LaO 

0 2 Cu 

LaO 

OLa 
Cu0 2 



rod) 

1 O(l) 
0.833 [£ 2) 



ro(D 
0(1) 
Uu 

0 333 [Sa 



i - 0.167 



2a 
4e 
4e 



4e 
4e 
4c 
4c 
2a 
4e 
4e 



2 

0 

JL 

2 



y 
o 

2 

0 

i 

2 



2 

0 

2 

0 
1 

2 

0 



Alternate Structure 
Atom Site x y 



O(l) 
CKD 
Cu 



0(2) 


4e 


0 


0 


0.182 


La 


4e 


I 

2 


1 

2 


0.138 


0(1) 


4c 


I 

- 2 


0 


0 


O(l) 


4c 


0 


1 

2 


0 


Cu 


2a 


0 


0 


0 



0.862 La 
0.818 

0(2) 
0(2) 

0.682 

0.638 La 
\ O(l) 
1 CXI) 
j; Cu 

0.362 La 

0.318 

J 0(2) 
0(2) 



O(l) 
O(l) 
Cu 



4c 
4c 
2a 
4e 

4d 
4d 

4e 
4c 
4c 
2a 
4e 

4d 
Ad 

4e 
4c 
4c 
2a 



0 

0 
i 

2 
I 
2 

0 



2 
0 



2 
0 

0 



2 

0 
1 

2 

0 



1 
1 
1 

0.862 



0 0.638 



2 
1 
2 
1 

0.362 



0.138 
0 
0 
0 



-Superconducting compounds crystallize in the regular structure (Oguch; see also Onoda). The ideal 
z values in column 2 are for the prototype perovskite. 



constants for tetragonal LaSrCuO superconductors with various values of *, 
and 6 in the formula (Lai-xSr^CuO^. 



2. Alternate Tetragonal Form 

In the previous section we discussed the tetragonal structure which fa ; adopted I by 
LaSrCuO superconductors. It has a variant (Hutir, Oguch) called the Nd 2 Cu04 
structure in which the oxygens 0(2) are in special sites <4d) instead of the general 
(4e) sites in the same space group, corresponding to 

o(2) (4d) o,U; i.o.4; i.o.3; o.M ( VI * 7) 

The remaining atoms are in the positions given by Eq. (VI-6) and lis* d i Table 
Vl-3. and the unit cell is sketched on the right-hand side of Fig VI-5. This ^struc 
ture tends to be unstable relative to its K 2 NiF< counterpart, and is not known 
superconduct. 



PEROVSKITE TYPE SUPERCONDUCTING STRUCTURES 83 



ructure, Both of 



ate Structure 



X 


y 


2 


2 


0 


1 


0 


2 


1 


0 


0 


1 


1 

2 


1 
2 


0.862 


0 


t 

2 


3 
4 


1 

2 


0 


2 
4 


0 


0 


0.638 


0 


1 

2 


i 

2 


1 

2 


0 


1 
2 


1 

2 


1 

2 


1 


0 


0 


0.362 


1 

2 


0 


i 

4 


0 


1 

2 


1 
4 


1 

2 


i 

2 


0.138 


i 
2 


0 


0 


0 


1 

2 


0 


0 


0 


0 




ilso Onoda). The ideal 



Fig. VI-5. Lanthanum copper oxide tetragonal unit cell. The regular cell (a) associated 
with the superconducting compounds is shown on the left and the alternative one {b) is on 
the right (Oguch; see also Ohbal). The oxygens denoted! by <8> have different positions in 
the two cells. 



>us values of x, y\ 



■rich is adopted by 
lied the Nd 2 CuO, 
ead of the general 



(VI-7) 

nd listed in Table 
. VI S. This struc- 
id is not known to 



3. Orthorhombic Form 

The 21 orthorhombic LaSrCuO structure (Longo) is related to its tetragonal ana- 
logue given by Eq. (VI-6) in the same way that the orthorhombic perovskite 
structure (Vl-3) is related to its tetragonal (VI-2) and cubic (VI I) forms. This 
means that the orthorhombic basis directions are at 45° relative to the tetragonal 
ones, and the number of formula units in the cell is doubled. The situation is 
similar to that described by Fig. VI-3, with a = 5.363 A = 3.792V? A, b = 
5.409 A = 3.825V2~A, c = 13.17 A. Writing the a and b lattice parameters 
times ^compensates for the new choice of axes and shows that the orthorhom- 
bic values are close to the tetragonal a = 3.81 A given earlier. There is also very 
little change in c. Table VI-5 lists the measured lattice constants for several 
orthorhombic compounds. The anisotropy factors ANIS 



ANIS = 



100 \b ~a\ 



0.5 {b + a) 

listed in column 6 give the percentage deviation from tetragonality. 



(VI-8) 




84 CRYSTALLOGRAPHIC STRUCTURES 



TABLE VR Selected Lattice Parameters for (R l x M,) 2 CuO^ Type Superconductors 
with Tetragonal Structure" ^ 



Lattice Parameters* 



R-M 



a = 6(A) 



• (A) 



Ref. 



Y-Ba 
La-Ba 



La-Sr 



0.4 

0.0S 

0.075 

0.075 

0.1 

0.05 

0.05' 

0.063 

0.075 

0.075 

0.075 

0.075 

0.087 

0.1 

0.1 

o.i a? 

0.125 
0.132 
0.15 



3.828 

3.782 

3.7817 

3.787 

3.791 

3.7839 

3.78 

3.7784 

3.7793 
3.7771 

3.776 

3.772 

3.7739 

3.7739 

3.777 

3.7708 

3.7685 

3.7666 

3.7657 



12.68 

13.168 

13.2487 

13.31 

13.35 

13.211 

13.25 

13.216 

13.2 

13.226 

13.234 

13.247 

13.232 

13.23 

13.2309 

13.242 

13.247 

13.255 

13.259 



Allge 

Skelt 

Yuzzz 

Fujit 

Fujtt 

Taral 

Hidak 

Taral 

Decro 

Taral 

Shelt 

Brunz 

Taral 

Taral 

Przys 

Taral 

Taral 

Taral 

Taral 



•The table is sorted by cations and then by increasing*, the dopant parameter (prepared 

Sea and b lattice parameters were converted from measured values of « 0 , *o of Fig. VI 
the expression a = b = b 0 />f2. 



by M. M. 
-3 through 



1 



t 
t 
t 

F 
b 



Copper atoms and one of the oxygen types O(l) are in special pos,t.ons; the 
remaining two atoms La and 0(2) are in general positions with a single undeter- 
mined parameter associated with the z coordinate. The space group is Fmmm, 
D», and the positions of the atoms are as follows: 



La (8i) o,o,«; o.|,i+«;i,oi+«;U.«; 

o,o,-«; o,i,i-w, £.o,*-«; 

Cu (4a) 0,0,0; O.i.i; i.O.i; 5.5.O 
O(l) (8e) U.0; M.fc iMi , 

4.M: U.0; f.i.o, J.J.i 

0(2) (8i) 0,0,v; . . . (same as La with v replacing «) 



(VI-9) 



where the parameters u = 0.362 and v = 0.182 have the same values a the 
tetragonal case presented above. Since u and v are the same and the lattice ■ « 
stants are so close to the tetragonal values, the sketch of the tetragonal unit ceU 
in Fig Vl-Sa applies here also. Another work (Hirot, see also Onoda) assigned 



>erconductors 



Ref. 

Allge 

Skelt 

Yuzzz 

Fujit 

Fujit 

Taral 

Hidak 

Taral 

Decro 

Taral 

Shelt 

Brunz 

Taral 

Taral 

Przys 

Taral 

Taral 

Taral 

Taral 

;pared by M. M. 
ig. VI-3 through 



positions; the 
ngle undeter- 
jp is Fmmnii 



(Vl-9) 



u) 



lues as in the 
le lattice con- 
onal unit cell 
>da) assigned 



PEROVSKITE-TYPE SUPERCONDUCTING STRUCTURES 



85 



TABLE VI-5. Selected Lattice Parameters for (R,. x M x ) 2 Cu04_ A Type Superconductors 
with the Orthorhombic Structure 0 









Lattice Parameters 








R-M 


X 


a (A) 


MA) 


c(A) 


ANIS 


Ref. 


La-Ba 


0.02 


3.786 


3.811 


13.17 


0.66 


Fujit 




0.075 


3.786* 


3.808* 


13.257 


0.58 


Shelt 




0.075 


3.798* 


3.803* 


13.234 


0.13 


Onoda 


La-Ba 


0.1 


3.786* 


3.824* 


13.264 


1.00 


Hirot 


U-Ca 


0.075 


3.772* 


3.808* 


13.168 


0.95 


Shelt 



•ANIS is the anisotropy factor 100|5 — a\/0.$(b + a) (prepared by M. M. Rigney). 

*The a and b lattice parameters were converted from the measured values of a 0 . *o of Fig. VI-3 

through the expressions a = a<>/>/2, b — b 0 /y/2. 



(Lao.^Bao.i^O* to the space group Pccm, D\ h with a = 5.354 = 3.786V2 A , b = 
5.408 = 3.824V2 A , and c = 13.264 A. 



4. Phase Transition 

The compounds (La|. jr M jr ) 2 Cu04 with M = Sr and Ba are orthorhombic at low 
temperatures and low M contents, and tetragonal otherwise, and superconduc- 
tivity has been found on both sides of this transition (Baris, Bedn3, Birge, 
Dayzz, Dvora, Fujit, Greel, Kangz, Koyam, Mihal, Paulz; see also Heldz). The 
prototype compound La 2 Cu0 4 itself also exhibits the tetragonal-to-orthorhom- 
bic transition. The phase diagram of Fig. VI-6 shows the tetragonal, orthorhom- 



400 



200 - 



1 1 


1 1 




Tetragonal 


~ Onho- 




N rhombic £V 


bH 


\, (SDW) 


X (Super- 

\ Conducting) _ 







0.05 



0.10 



0.15 



Fig, VI-6- Phase diagram showing data points along the tetragonal-to-orthorhombic 
transition line for (Lai_ jr Ba jr ) 2 Cu0 4 -5 (O, Fujit) and (La,.,SrJ 2 Cu0 4 K Moret). The 
spin-density wave (SDW) and superconducting • regions are indicated. These two com- 
pounds have about the same superconducting region. 



if 



M 

I 

Si- 

•35 i 

r- 

SO : 

S 
< 



16 



86 CRYSTALLOGRAPHIC STRUCTURES 



bic, superconducting, and spin-density wave (SDW) regions for the barium 
compound (Fujit), and data points for the strontium compound (Moret, 
More8). An alternate phase diagram has been proposed (Aharl). Alkaline metal 
contents much larger than those shown on the figure (e.g., x ~ 0.5) can be non- 
superconducting. The SDW region occurs below the minimum concentration for 
the onset of superconductivity. Another work (Geise) showed that LaSr<0.04) 
undergoes a structural phase transition between 180 and 300 K. 

5. Generation of LaSrCuO Structures 

The LaSrCuO tetragonal structures may be visualized as being derived from four 
LaCuOj perovskite unit cells of the type illustrated in Fig. VI-1 stacked one 
above the other along the z or c axis. To generate La 2 Cu0 4 in the K 2 NiF 4 struc- 
ture the layers of Cu0 2 atoms on the z = \ and z = 5 levels of this four-cell 
stacking are removed, La and O are interchanged on two other layers, and the 
middle layer Cu atom is shifted from the edge to the center point of the 

unit cell. Then the cell is compressed vertically from 14.9 to 13.2 A (Table VI-4) 
** to take up the space formerly occupied by the removed Cu0 2 layers. Finally, the 
lanthanums along the c axis and the oxygens along the side edges are shifted 
vertically to accommodate the new atom arrangement. 

To generate La 2 Cu0 4 with the Nd 2 Cu0 4 arrangement from this same four-cell 
stacking all of the oxygens on the vertical edges are removed, and two lan- 
thanums are moved to edge sites. Copper is handled the same way as before, so 
in both cases the generated structure lacks two Cu0 2 layers. 

6. Layering Scheme of LaSrCuO 

When we described the LaSrCuO structures we left out what is perhaps their 
most important characteristic, namely, their layered aspect. Lanthanum copper 
oxide may be looked upon as consisting of Cu-O layers of square-planar coordi- 
nated copper ions with lanthanum and 0(2)-type oxygen ions populating the 
spaces between the layers. These Cu-O layers are stacked equally spaced, per- 
pendicular to the c axis, as shown in Fig. VI-7, and their oxygens are aligned 
along the c axis, as indicated by the vertical dotted line on the left side of the 
figure. The copper ions, on the other hand, are not aligned vertically, but rather 
alternate between (000) and (Hi) sites in adjacent layers, as illustrated in Figs. 
VI-5 and Vl-7. 

The copper is actually octahedrally coordinated with oxygen, but the Cu-O 
distance of 1.9 A in the Cu0 2 planes is much less than the vertical distance of 
2.4 A between copper and the oxygens above and below, as shown in Fig. VI-8. 
When the structure is distorted orthorhombically the Cu-O spacings in both the 
planes and the c direction remain quite close to their tetragonal counterparts. 

The copper ions and the OUHype oxygens in the planes are both in special 
sites in the tetragonal and orthorhombic forms, in accordance with Eqs. (VI-6) 
and (VI-9), and as a result the plane is perfectly flat in both cases. When the 




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