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APR 05 '05 15=49 FR IBM \ r C < 



IN THE UN1TEI 




TENT AND TRADEMARK OFFICE 



9149453281 TO 917032991475 



P. 02/25 



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



Date: April 4, 2005 
Docket: YO987-074BZ 
Group Art Unit: 1751 
Examiner: M. Kopec 



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

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



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

1. I received a B. S. degree in Mechanical Engineering from National Taiwan 
University (1960), and M. S. and Ph.D. degrees in Material Science (1963, 1966) 
respectively from California Institute of Technology. 

2. I refer to Attachments A to Z and AA herein which were submitted in a separate 
paper designated as "FIRST SUPPLEMENTAL AMENDMENT' in response to the 
Office Action dated July 28, 2004. I also refer to Attachments AB to AG which were 
submitted in a separate paper designated as "THIRD SUPPLEMENTAL AMENDMENT" 
in response to the Office Action dated July 28, 2004. 

3. I have worked as a research staff member and manger in the physics of 
superconducting, amorphous and structured materials at the Thomas J. Watson 
Research Center of the International Business Machines Corporation in Yorktown 
Heights, New York from 1973 to the present. 

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



AFFIDAVIT UNDER 37 C.F.R. 1.132 



Sir: 



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5. My resume and list of publications is in Attachment 1 included with this affidavit. 

6. This affidavit is in addition to my affidavit dated December 1 5, 1 998. I have 
reviewed the above-identified patent application (Bednorz-Mueller application) and 
acknowledge that it represents the work of Bednorz and Mueller, which is generally 
recognized as the first discovery of superconductivity in a material having a T c > 26°K 
and that subsequent developments in this field have been based on this work. 

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

8. Once a person of skill in the art knows of a specific type of composition 
described in the Bednorz-Mueller application which is superconducting at greater than 
or equal to 26°K, such a person of skill in the art, using the techniques described in the 
Bednorz-Mueller application, which includes all principles of ceramic fabrication known 
at the time the application was initially filed, can make the compositions encompassed 
by the claims of the Bednorz-Mueller application, without undue experimentation or 
without requiring ingenuity beyond that expected of a person of skill in the art of the 
fabrication of ceramic materials. This is why the work of Bednorz and Mueller was 
reproduced so quickly after their discovery and why so much additional work was done 
in this field within a short period after their discovery. Bednorz and Mueller's discovery 
was first reported in Z. Phys. B 64 page 189-193 (1996). 

9. The techniques for placing a superconductive composition into a 
superconducting state have been known since the discovery of superconductivity in 
1911 by Kamerlingh-Onnes. 



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1 0. Prior to 1 986 a person having a bachelor's degree in an engineering discipline, 
applied science, chemistry, physics or a related discipline could have been trained 
within one year to reliably test a material for the presence of superconductivity and to 
flow a superconductive current in a superconductive composition. 

1 1 Prior to 1986 a person of ordinary skill in the art of fabricating a composition 
according to the teaching of the Bednorz-Mueller application would have: a) a Ph.D. 
degree in solid state chemistry, applied physics, material science, metallurgy, physics or 
a related discipline and have done thesis research including work in the fabrication of 
ceramic materials; or b) have a Ph.D. degree in these same fields having done 
experimental thesis research plus one to two years post Ph.D. work in the fabrication of 
ceramic materials; or c) have a master's degree in these same fields and have had five 
years of materials experience at least some of which is in the fabrication of ceramic 
materials. Such a person is referred to herein as a person of ordinary skill in the 
ceramic fabrication art. 

12. The general principles of ceramic science referred to by Bednorz and Mueller in 
their patent application and known to a person of ordinary skill in the ceramic fabrication 
art can be found in many books and articles published before their discovery, priority 
date (date of filing of their European Patent Office patent application EPO 0276343A1, 
January 23, 1987) and initial US Application filing date (May 22, 1987). An exemplary 
list of books describing the general principles of ceramic fabrication are: 

a) Introduction to Ceramics, Kingery et al.. Second Edition, John 

Wiley & Sons, 1976, in particular pages 5-20, 269-319, 381-447 and i(; 
448-51 3, a copy of which is in Attachment B. 

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



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c) Ceramic Processing Before Firing, Onoda et al., John Wiley & 
Sons, 1 978, the entire book, a copy of which is in Attachment D. 

d) Structure, Properties and Preparation of Perovskite-Type 
Compounds, F. S. Galasso , Pergamon Press, 1969, in particular pages 
159-186, a copy of which is in Attachment E. 

These references were previously submitted with the Affidavit of Thomas Shaw 
submitted December 15, 1998. 

1 3. An exemplary list of articles applying the general principles of ceramic fabrication 
to the types of materials described in Applicants' specification are: 

a) Oxygen Defect K 2 NiF 4 - Type Oxides: The Compounds 
Laz.xSrxCuO^-, Nguyen et al., Journal of Solid State Chemistry 39, 
120-127 (1981). See Attachment F. 

b) The Oxygen Defect Perovskite BaLa 4 Cu5.0 13 .4, A Metallic (This is 
referred to in the Bednorz-Mueller application at page 21, lines 1-2) 
Conductor, C. Michel etal., Mat. Res. Bull., Vol. 20, pp. 667-671, 1985. 
See Attachment G. 

c) Oxygen Intercalation in Mixed Valence Copper Oxides Related to 
the Perovskite, C. Michel et al., Revue de Chemie Minerale, 21 , p. 407, 
1984. (This is referred to in the Bednorz-Mueller application at page 27, 
lines 1-2). See Attachment H. 

d) Thermal Behaviour of Compositions in the Systems x BaTiOj + 
(1-x) Ba(Lno.s B os ) 0 3 , V.S. Chincholkar et al., Therm. Anal. 6th, Vol. 2., p. 
251-6,1980. See Attachment I. 



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s 



14. The Bednorz-Mueller application in the paragraph bridging pages 6 and 7 states 
in regard to the high T c materials: 

These compositions can carry supercurrents (i.e., electrical currents in a 
substantially zero resistance state of the composition) at temperatures 
greater than 26°K. In general, the compositions are characterized as 
mixed transition metal oxide systems where the transition metal oxide can 
exhibit multivalent behavior. These compositions have a layer-type 
crystalline structure, often perovskite-like, and can contain a rare earth or 
rare earth-like element. A rare earth-like element (sometimes termed a 
near rare earth element is one whose properties make it essentially a rare 
earth element. An example is a group IIIB element of the periodic table, 
such as La. Substitutions can be found in the rare earth (or rare 
earth-like) site or in the transition metal sites of the compositions. For 
example, the rare earth site can also include alkaline earth elements 
selected from group IIA of the periodic table, or a combination of rare 
earth or rare earth-like elements and alkaline earth elements. Examples 
of suitable alkaline earths include Ca, Sr, and Ba. The transition metal 
site can include a transition metal exhibiting mixed valent behavior, and 
can include more than one transition metal. A particularly good example 
of a suitable transition metal is copper. As will be apparent later, Cu- 
oxide based systems provide unique and excellent properties as high T c 
superconductors. An example of a superconductive composition having 
high T c is the composition represented by the formula RE-TM-O, where 
RE is a rare earth or rare earth-like element, TM is a nonmagnetic 
transition metal, and 0 is oxygen. Examples of transition metal elements 
include Cu, Ni, Cr etc. In particular, transition metals that can exhibit 
multi-valent states are very suitable. The rare earth elements are typically 
elements 58-71 of the periodic table, including Ce, Nd, etc. 



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15. In the passage quoted in paragraph 14 the general formula is RE-TM-0 "where 
RE is a rare earth or rare earth-like element, TM is a nonmagnetic transition metal, and 
0 is oxygen." This paragraph states "Substitutions can be found in the rare earth (or 
rare earth-like) site or in the transition metal sites of the compositions. For example, the 
rare earth site can also include alkaline earth elements selected from group IIA of the 
periodic table, or a combination of rare earth or rare earth-like elements and alkaline 
earth elements." Thus applicants teach that RE can be something other than an rare 
earth. For example, it can be an alkaline earth, but is not limited to a alkaline earth 
element. It can be an element that has the same effect as an alkaline earth or 
rare-earth element, that is a rare earth like element. Also, this passage teaches that : 
TM can be substituted with another element, for example, but not limited to, a rare 
earth, alkaline earth or some other element that acts in place of the transition metal. 

1 6. The following table is compiled from the Table 1 of the Article by Rao (See 
Attachment AB) and the Table of high T e materials from the "CRC Handbook of 
Chemistry and Physics" 2000-2001 Edition (See Attachment AC). An asterisk in 
column 5 indicated that the composition of column 2 does not come within the scope of 
the claims allowed in the Office Action of July 28, 2004. 

17. I have reviewed the Office Action dated July 28, 2004, which states at page 6 
"The present specification is deemed to be enabled only for compositions comprising a 
transition metal oxide containing at least a) an alkaline earth element and b) a 
rare-earth element of Group IIIB element." I disagree for the reasons given herein. 



1 8. Composite Table 



1 


2 


3 


4 


5 


6 


7 


# 


MATERIAL 


RAO 

ARTICLE 


HANDBOOK 
OF CHEM & 
PHYSICS 




ALKALINE 

EARTH 

ELEMENT 


RARE 

EARTH 

ELEME 

.NT 


1 


L^CuO^kj 




V 


* 


N 


Y 


2 


La2. x Sr x (Ba x )Cu04 




V 




Y 


Y 


3 


La2Cai.xSrxCu 2 06 


>/ 


V 




Y 


Y 



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A 
H 


Y ri£t2V^U3V^7 








Y 


Y 


c 
J 


Yr>a2V^U4V/s 








Y 


Y 


D 


V T3«a Pn,Oir 

X 2j3a4^U7v^l5 




V 




Y 


Y 


7 






V 


* 


Y 


N 


J? 
O 








* 


Y 


N 


Q 


0 12^-w 3*2 U3 1 0 






* 


Y 


N 




X5l2Or2(L/Ill.xV^vxj2V-/U2W10 








Y 


Y 


1 1 
1 1 


nri tirt pun 




V . 


4c 


Y 


N 




1 l2UaJDEl2v-'U2^8 






* 


Y 


N 




1 l2^a2JP«2v^ u 3^lO 


V 






Y 


N ' 


14 


Tl^BaLa^CuOs 


V 






Y 


Y 


15 


TlfSrLa^CuOs 


V 






Y 


Y 


16 


fTlo.sPbo.s)Sr 2 CuOs 


V 






Y 


N 


17 


TlCaBa^CujO? 


>/ 


< 




Y 


N 


18 


(Tin <Pbn ^CaS^C^O? 


V 




* 


Y 


N 


19 


TISisYa <Can.*;CU707 


V 






Y 


Y 


20 


TlCaoBaoCiuOR 


V 


>/ 


* 


Y 


N 


21 


^ X l0'5 A ^O0'5^»3*2^ c *2 v ^ u 3 v ^9 


V 




* 


Y 


N 




TIR^T ni P*> ^ClloOo 








Y 


Y 


23 


Pk Qr.T rPsu criuOe 

jr U2 dr2J^no- s ^ «o* 5^ u 3 








Y 


Y ., 


OA 


PK fQr T raVPiufYt 




V 




Y 


Y : 


2S 


nPK Pn^isfT n Pa^PibO? 

^x U/or2V 1 -L'Al,\^ a)\s U2V-/7 








Y 


Y . 


26 


/Ph PnVSr EtAfPu Ce^ClbO* 








Y 


Y .. 


27 








* 


N 


Y 


• 28 










Y 


Y 


29 


Sri „Nd.CuQ> 

Ol i-xi.^« vixv^ 








Y 


Y 


30 


fa, Q r PuO^ 








Y 


N 


31 


JO ao 6^0-4*5 1\J} 








Y 




X) 


XVU2^5^60 






* 


N 




J J 


M/TOo.PiuPU 
INQx3a2^U3V^7 




V 




Y 


Y 


34 


oITLD aOlv^UVJ7 




V 




Y 


Y - 


3^ 


JjUDdjI V^U3V/7 




V 




Y 


Y 


36 


BaSrCu 3 0 7 






* 


Y 


N 


37 


DyBaSrCu 3 0 7 




V 




Y 


Y 


38 


HuBaSrCu 3 0 7 




V 




Y 


Y 


39 


ErBaSrCu 3 0 7 (Multiphase) 








Y 


Y 


40 


TmBaSrCu 3 0 7 (Multiphase) 








Y 


Y . 



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41 


\HRaSrCuiOi 




V 




Y 


Y 


42 


HgBa 2 CuQ 2 






* 


Y 


N 


43 


HgBa 2 CaCu 2 0 6 
(annealed in 0 2 ) 






* 


Y 


XT 

N 


44 


HaBa 2 Ca 2 Cu 3 O s 






* 


Y 


N 


45 


HsBa 2 Ca 3 CmOio 






* 


Y 


N 



19. The first composition, La 2 Cu 0^ , has the form RE 2 CuOa which is explicitly 
taught by Bednorz and Mueller. The S indicates that there is a nonstoichiometric 
amount of oxygen. 



20. The Bednorz-Mueller application teaches at page 1 1 , line 19 to page 12, line 7: 

An example of a superconductive compound having a layer-type structure 
in accordance with the present invention is an oxide of the general 
composition RE2TMO4 where RE stands for the rare earths (lanthanides) 
or rare earth-like elements and TM stands for a transition metal. In these j 
compounds the RE portion can be partially substituted by one or more 
members of the alkaline earth group of elements. In these particular 
compounds, the oxygen content is at a deficit. For example, one such 
compound that meets this general description is lanthanum copper oxide 
La 2 Cu0 4 ... 

21. The Bednorz-Mueller application at page 15, last paragraph states "Despite their 
metallic character, the Ba-La-Cu-0 type materials are essentially ceramics, as are other 
compounds of the RE 2 TM0 4 type, and their manufacture generally follows known 
principles of ceramic fabrication." 



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22. Compound number 27 of the composite table contains Nd and Ce, both rare 
earth elements. All of the other compounds of the composite table, except for number 
32, have 0 and one of the alkaline earth elements which as stated above is explicitly 
taught by applicants. Compound 31 is a Bi0 3 compound in which TM is substituted by 
another element, here Bi, as explicitly taught by Applicants in the paragraph quoted 
above. 

23. The rare earth elements are Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, 
Er, Tm, Yb, and Lu. See the Handbook of Chemistry and Physics 59th edition 
1978-1979 page B262 in Appendix A. The transition elements are identified in the 
periodic table from the inside front cover of the Handbook of Chemistry and Physics in 
Appendix A. 

24. The basic theory of superconductivity has been known many years before 
Applicants' discovery. For example, see the book "Theory of Superconductivity", M. 
von Laue, Academic Press, Inc., 1952 (See Attachment AD). 

25. In the composite table, compound numbers 7 to 10 and 31 are Bismuth (Bi) 
compounds. Compound number 12 to 22 are Thallium (Tl) compounds. Compound 
numbers 23 to 26 are lead (Pb) compounds. Compounds 42 to 45 are Mercury (Hg) 
compounds. Those compounds that do not come within the scope of an allowed claims 
(the compounds which are not marked with an asterisk in column 3 of the composite 
table) are primarily the Bi, Tl, Pb and Hg compounds. These compounds are made 
according to the principles of ceramic science known prior to applicant's filing date. For 
example, Attachments J, K, L, and M contain the following articles: 

Attachment J - Phys. Rev. B. Vol. 38, No. 16, p. 6531 (1988) is directed to 
Thallium compounds. 

Attachment K - Jap. Joun. of Appl. Phys., Vol. 27, No. 2, p. L209-L210 
(1 988) is directed to Bismuth (Bi) compounds. 



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Attachment L - Letter to Nature, Vol. 38, No. 2, p. 226 (18 March 1993) is 
directed to Mercury (Hg) compounds. 

Attachment M - Nature, Vol. 336, p. 211 (17 November 1988) is directed 
to Lead (Pb) based compounds. 

26. The article of Attachment J (directed to Tl compounds) states at page 6531 , left 
column: 

The samples were prepared by thoroughly mixing suitable amounts of 
Tl 2 0 3 , CaO, Ba0 2 , and CuO, and forming a pellet of this mixture under 
pressure. The pellet was then wrapped in gold foil, sealed in quartz tube 
containing slightly less than 1 atm of oxygen, and baked for approximately 
3 h at * 880-C. 

This is according to the general principles of ceramic science known prior to 
applicant's priority date. 

27. The article of Attachment K (directed to Bi compounds) states at page L209: 

The Bi-Sr-Ca-Cu-0 oxide samples were prepared from powder reagents 
of Bi 2 0 3 , SrC0 3 . CaC0 3 and CuO. The appropriate amounts of powders 
were mixed, calcined at 800-870'C for 5 h, thoroughly reground and then 
cold-pressed into disk-shape pellets (20 mm in diameter and 2 mm in 
thickness) at a pressure of 2 ton.cm 2 . Most of the pellets were sintered at 
about 870*C in air or in an oxygen atmosphere and then furnace-cooled to 
room temperature. 

This is according to the general principles of ceramic science known prior to 
applicant's priority date. 



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28. The article of Attachment L (directed to Hg compounds) states at page 226: 

The samples were prepared by solid state reaction between stoichiometric 
mixtures of Ba 2 Cu0 3 .* and yellow HgO (98% purity, Aldrich). The 
precursor BaaCuOw was obtained by the same type of reaction between 
Ba0 2 (95% purity, Aldrich) and CuO (NormalPur, Prolabo) at 930'C in 
oxygen, according to the procedure described by De Leeuw et al. 6 . The 
powders were ground in an agate mortar and placed in silica tubes. Al) 
these operations were carried out in a dry box. After evacuation, the 
tubes were sealed, placed in steel containers, as described in ref. 3, and 
heated for 5 h to reach -800*0. The samples were then cooled in the 
furnace, reaching room temperature after ~10 h. 

This is according to the general principles of ceramic science known prior to 
applicant's priority date. 

29. The article of Attachment M (directed to Pb compounds) states at page 21 1 , 
column: 

The preparative conditions for the new materials are considerably more 
stringent than for the previously known copper-based superconductors. 
Direct synthesis of members of this family by reaction of the component 
metal oxides or carbonates in air or oxygen at temperatures below 900/C 
is not possible because of the stability of the oxidized SrPbOs-based 
perovskite. Successful synthesis is accomplished by the reaction of PbO 
with pre-reacted (Sr, Ca, Ln) oxide precursors. The precursors are 
prepared from oxides and carbonates in the appropriate metal ratios, 
calcined for 16 hours (in dense Al 2 0 3 crucibles) at 920-980'C in air with 
one intermediate grinding. 



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This is according to the principles of ceramic science known prior to applicant's 
priority date. . 

30. A person of ordinary skill in the art of the fabrication of ceramic materials would 
be motivated by the teaching of the Bednorz-Mueller application to investigate 
compositions for high superconductivity other than the compositions specifically 
fabricated by Bednorz and Mueller. 

31 . In Attachment U, there is a list of perovskite materials from pages 191 to 207 in 
the book "Structure, Properties and Preparation of Perovskite-Type Compounds" by F. 
S. Galasso, published in 1969, which is Attachment E hereto. This list contains about 
300 compounds. Thus, what the term "Perovskite-type" means and how to make these 
compounds was well known to a person of ordinary skill in the art in 1969, more than 17 
years before the Applicants' priority date (January 23, 1987). 

This is clear evidence that a person of skill in the art of fabrication of ceramic 
materials knows (prior to Applicants' priority date) how to make the types of materials in 
Table 1 of the Rao Article and the Table from the Handbook of Chemistry and Physics 
as listed in the composite table above in paragraph 17. 

f 

32. The standard reference "Landholt-B6rnstein", Volumn 4, "Magnetic and Other 
Properties of Oxides and Related Compounds Part A" (1970) lists at page 148 to 206 
Perovskite and Perovskite-related structures. (See Attachment N). Section 3.2 starting 
at page 190 is entitled "Descriptions of perovskite-related structures". The German title 
is "Perowskit-anliche Strukturen". The German word "anliche" can be translated in 
English as "like". The Langenscheidt's German-English, English-German Dictionary 

1 970, at page 446 translates the English "like" as the German "anliche". (See 
Attachment O). Pages 126 to 147 of Attachment N describes "crystallographic and 
magnetic properties of perovskite and perovskite-related compounds", see title of 
Section 3 at page 126. Section 3.2.3.1 starting at page 192 of "Landholt-Bornstein" _ 
Vol. 4 (See Attachment N) is entitled "Bismuth Compounds". Thus Bismuth 



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perovskite-like compounds and how to make them were well known more than 16 years 
prior to Applicants' priority date. Thus the "Landholt B6rnstein" book published in 1970, 
more than 16 years before Applicants' priority date (January 23, 1987), shows that the 
term "perovskite-like" or "perovskite related" is understood by persons of skill in the art 
prior to Applicants' priority date. Moreover, the "Landholt-Bornstein" book cites 
references for each compound listed. Thus a person of ordinary skill in the art of 
ceramic fabrication knows how to make each of these compounds. Pages 376-380 of 
Attachment N has figures showing the crystal structure of compounds containing Bi and 
Pb. 

33. The standard reference "Landholt-Bornstein, Volume 3, Ferro- and 
Antiferroelectric Substances" (1 969) provides at pages 571-584 an index to 
substances. (See Attachment P). This list contains numerous Bi and Pb containing 
compounds. See, for example pages 578 and 582-584. Thus a person of ordinary skill 
in the art of ceramic fabrication would be motivated by Applicants' application to 
fabricate Bi and/or Pb containing compounds that come within the scope of the 
Applicants' claims. 

34. The standard reference "Landholt-Bornstein Volume 3 Ferro- and 
Antiferroelectric Substances" (1969) (See Attachment P) at page 37, section 1 is 
entitled "Perovskite-type oxides." This standard reference was published more than 17 
years before Applicants' priority date (January 23, 1 987). The properties of 
perovskite-type oxides are listed from pages 37 to 88. Thus the term perovskite-type 
was well known and understood by persons of skill in the art of ceramic fabrication prior 
to Applicants' priority date and more than 17 years before Applicants' priority date 
persons of ordinary skill in the art knew how to make Bi, Pb and many other perovskite, 
perovskite-like, perovskite-related and perovskite-type compounds. 



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35. At page 14, line 10-15 of the Bednorz-Mueller application, Applicants' state 
"samples in the Ba-La-Cu-0 system, when subjected to x-ray analysis, revealed three 
individual crystallographic phases V.12. a first layer-type perovskite-like phase, related 
to the K 2 NiF 4 structure ..." Applicants' priority document EP0275343A1 filed July 27, 
1988, is entitled "New Superconductive Compounds of the KaNiF4 Structural Type 
Having a High Transition Temperature, and Method for Fabricating Same." See (See 
Attachment AE). The book "Structure and Properties of Inorganic Solids" by Francis S. 
Galasso, Pergamon Press (1969) at page 190 lists examples of Tallium (Tl) compounds 
in the K2NiF 4 structure. (See Attachment Q). Thus based on Applicants' teachings prior 
to Applicants' priority date, a person of ordinary skill in the art of ceramic fabrication 
would be motivated to fabricate Thallium based compounds to test for high Tc 
superconductivity. 

36. The book "Crystal Structures" Volume 4, by Ralph W. G. Wyckoff, lnterscience 
Publishers, 1960 states at page 96 "This structure, like these of Bi 4 Ti 2 0i 2 (IX, F 12 ) and 
Ba Bu TU O* (XI, 1 3) is built up of alternating Bi 2 0 2 and perovskite-like layers." Thus 
layer of perovskite-like Bismuth compounds was well known in the art in 1960 more 
than 26 years before Applicants' priority date. (See Attachment R). 

37. The book "Modern Oxide Materials Preparation, Properties and Device 
Applications" edited by Cockayne and Jones, Academic Press (1972) states (See 
Attachment S) at page 155 under the heading "Layer Structure Oxides and Complex 
Compounds": 

"A large number of layer structure compounds of general formula (Bi 2 0 2 ) 2+ 
(A».iB,0 3 *fi) 2 - have been reported (Smolenskii et at. 1961; Subbarao, 
1 962), where A = Ca, Sr, Ba, Pb, etc., B = Ti, Nb, Ta and x = 2, 3, 4, or 5. 
The structure had been previously investigated by Aurivillius (1949) who 
described them in terms of Alternate (Bi 2 0 2 ) 2 * layers and perovskite layers 
of oxygen octahedra. Few have been found to be ferroelectric and 
include SrBi 2 Ta 2 0 9 (T c = 583°K), PbBi 2 Ta 2 0 8 (T c = 703°K), BiBi 3 Ti 2 TiOi 2 or 



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BuTi 3 0, 2 (T c = 948°K), Ba 2 Bi 4 Ti 5 0ie (T e = 598°K) and Pb 2 BuTi 5 0i 8 (T c = 
583°K). Only bismuth titanate BUTi 3 0 12 has been investigated in detail in 
the single crystal form and is finding applications in optical stores 
(Cummins, 1967) because of its unique ferroelectric-optical switching 
properties. The ceramics of other members have some interest because 
of their dielectric properties. More complex compounds and solid 
solutions are realizable in these layer structure oxides but none have 
significant practical application." 

Thus the term layered oxides was well known and understood prior to Applicants' 
priority date. Moreover, layered Bi and Pb compounds were well known in 1972 more 
than 15 years before Applicants' priority date. 

38. The standard reference "Landholt-B6rnstein, Volume 3, Ferro and 
Antiferroelectric Substances" (1969) at pages 107 to 1 14 (See Attachment T) list 
"layer-structure oxides" and their properties. Thus the term "layered compounds" was 
well known in the art of ceramic fabrication in 1 969 more than 16 years prior to 
Applicants' priority date and how to make layered compounds was well known prior to 
applicants priority date. 

39. Layer perovskite type Bi and Pb compounds closely related to the Bi and Pb high 
T c compounds in the composite table above in paragraph 17 have been known for 
some time. For example, the following is a list of four articles which were published 
about 35 years prior to Applicants' first publication date: 

( 1 ) Attachment V - "Mixed bismuth oxides with layer lattices", B. 
Aurivillius, Arkiv Kemi 1, 463, (1950). 

(2) Attachment W - "Mixed bismuth oxides with layered lattices ", B. 
Aurivillius, Arkiv Kemi 1, 499, (1950). 



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(3) Attachment X - "Mixed bismuth oxides with layered lattices ", B. 
Aurivillius, Arkiv Kemi 2, 519, (1951). 

(4) Attachment Y - "The structure of Bi 2 NbO s F and isomorphous 
compounds", B. Aurivillius, Arkiv Kemi 5, 39, (1952). 

These articles will be referred to as Aurivillius 1, 2, 3 and 4, respectively. 

40. Attachment V (Aurivillius 1), at page 463, the first page, has the subtitle "I. The 
structure type of CaNb 2 Bi 2 0 9 . Attachment V states at page 463: 

X-ray analysis ... seemed to show that the structure was built up of Bi 2 OV 
layers parallel to the basal plane and sheets of composition Bi 2 Ti 3 0 2 io'. 
The atomic arrangement within the Bi 2 Ti 3 OV sheets seemed to be the 
same as in structure of the perovskite type and the structure could then 
be described as consisting of Bi 2 OY layers between which double 
perovskite layers are inserted. 

41 . Attachment V (Aurivillius 1) at page 464 has a section entitled "PbBi 2 Nb 2 0 9 
Phase". And at page 471 has a section entitled "Bi 3 NbTi0 9 ". And at page 475 has a 
table of compounds having the "CaBi 2 Nb 2 0 9 structure" listing the following compounds 
Bi 3 NbTi0 9 , Bi 3 TaTi0 9 , CaBi 2 Nb 2 0 9l SrBi 2 Nb 2 0 9 , SrBi 2 Ta 2 0 9l BaBi 2 Nb 2 0 9 , PbBi 2 Nb 2 0 9 . 
NaBi 5 Nb40i8, KBi 5 Nb<0 18 . Thus Bi and Pb layered perovskite compounds were well 
known in the art about 35 years prior to Applicants' priority date. 

42. Attachment W (Aurivillius 2) at page 499, the first page, has the subtitle "II 
Structure of Bi^CV'. And at page 510, Fig. 4 shows a crystal structure in which "A 
denotes a perovskite layer Bi 2 Ti 3 OV, C Bi 2 OV layers and B unit cells of the 
hypothetical perovskite structure BiTi0 3 . 



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43. Attachment X (Aurivillius 3) has at page 519, the first page, the subtitle "in 
Structure of BaBLTuOis". And in the first paragraph on page 519 states referring to the. 
articles of Attachments V (Aurivillius 1), and W (Aurivillius 2) "X ray studies on the 
compounds CaBi 2 Nb 2 0 9 [the article of Attachment V] and Bi 4 Ti 3 0i 2 [the article of 
Attachment W] have shown that the comparatively complicated chemical formulae of 
these compounds can be explained by simple layer structures being built up from 
Bi 2 OV layers and perovskite layers. The unit cells are pictured schematically in Figs. 
1a and 1c." And Fig. 4 at page 526 shows "One half of a unit cell of BaB'uTuOis. A 
denotes the perovskite region and B the Me 2 0 4 layer" where Me represents a metal 
atom. 

44. Attachment Y (Aurivillius 4) is direct to structures having the Bi 3 N, 0 O 3 F structure. 

45. Attachment AA is a list of Hg containing solid state compounds from the 1 989 
Powder Diffraction File Index. Applicants do not have available to them an index from 
prior to Applicants' priority date. The Powder Diffraction File list is a compilation of all 
known solid state compounds with reference to articles directed to the properties of 
these compositions and the methods of fabrication. From Attachment AA it can be 
seen, for example, that there are numerous examples of Hg based compounds. 
Similarly, there are examples of other compounds in the Powder Diffraction File. A 
person of ordinary skill in the art is aware of the Powder Diffraction File and can from 
this file find a reference providing details on how to fabricate these compounds. Thus 
persons of ordinary skill in the art would be motivated by Applicants' teaching to look to 
the Powder Diffraction File for examples of previously fabricated composition expected 
to have properties similar to those described in Applicants' teaching. 



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46. It is generally recognized that it is not difficult to fabricate transition metal oxides 
and in particular copper metal oxides that are superconductive after the discovery by 
Applicants of composition, such as transition metal oxides, that are high T c 
superconductors. This is noted in the book "Copper Oxide Superconductors" by 
Charles P. Poole, Jr., Timir Datta and Horacio A. Farach. John Wiley & Sons (1998), 
referred to herein as Poole 1988: Chapter 5 of Poole 1988 (See Attachment AF) in the 
book entitled "Preparation and Characterization of Samples" states at page 59 "[c]opper 
oxide superconductors with a purity sufficient to exhibit zero resistivity or to 
demonstrate levitation (Early) are not difficult to synthesize. We believe that this is at 
least partially responsible for the explosive worldwide growth in these materials". Poole 
1988 further states at page 61 n [i]n this section three methods of preparation will be 
described, namely, the solid state, the coprecipitation, and the sol-gel techniques 
(Hatfi). The widely used solid-state technique permits off-the-shelf chemicals to be 
directly calcined into superconductors, and it requires tittle familiarity with the subtle ( 
physicochemical process involved in the transformation of a mixture of compounds into 
a superconductor." Poole 1 988 further states at pages 61-62 "[i]n the solid state 
reaction technique one starts with oxygen-rich compounds of the desired components . 
such as oxides, nitrates or carbonates of Ba, Bi, La, Sr, Ti, Y or other elements. ... 
These compounds are mixed in the desired atomic ratios and ground to a fine powder 
to facilitate the calcination process. Then these room-temperature-stabile salts are 
reacted by calcination for an extended period (~20hr) at elevated temperatures 
(~900°C). This process may be repeated several times, with pulverizing and mixing of 
the partially calcined material at each step." This is generally the same as the specific 
examples provided by Applicants and as generally described at pages 8, line 19, to 
page 9, line 5, of the Bednorz-Mueller application which states "[t]he methods by which 
these superconductive compositions can be made can use known principals of ceramic 
fabrication, including the mixing of powders containing the rare earth or rare earth-like, 
alkaline earth, and transition metal elements, coprecipitation of these materials, and 
heating steps in oxygen or air. A particularly suitable superconducting material in 
accordance with this invention is one containing copper as the transition metal." 



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Consequently, it is my opinion that Applicants have fully enabled high T c materials 
oxides and their claims. 

47. Charles Poole et al. published another book in 1 995 entitled "Superconductivity- 
Academic Press which has a Chapter 7 on "Perovskite and Cuprate Crystallographic 
Structures". (See Attachment Z). This book will be referred to as Poole 1995. 



At page 179 of Poole 1995 states: 



V. PEROVSKITE-TYPE SUPERCONDUCTING STRUCTURES 

In their first report on high-termperature superconductors Bednorz and 

Miieller (1986) referred to their samples as "metallic, oxygen-deficient .. 

perovskite-like mixed-valence copper compounds." Subsequent work h 

confirmed that the new superconductors do indeed possess these 

characteristics. 



I agree with this statement. 



48. The book "The New Superconductors", by Frank J. Owens and Charles P. 
Poole, Plenum Press, 1996, referred to herein as Poole 1996 in Chapter 8 entitled 
"New High Temperature Superconductors" starting a page 97 (See Attachment AG) 
shows in Section 8.3 starting at page 98 entitled "Layered Structure of the Cuprates" 
schematic diagrams of the layered structure of the cuprate superconductors. Poole 
1996 states in the first sentence of Section 8.3 at page 98 "All cuprate superconductors 
have the layered structure shown in Fig. 8.1." This is consistent with the teaching of 
Bednorz and Mueller that 'These compositions have a layer-type Crystalline Structure 
often Perovskite-like" as noted in paragraph 14 above. Poole 1996 further states in the 
first sentence of Section 8.3 at page 98 "The flow of supercurrent takes place in 
conduction layers and bonding layers support and hold together the conduction layers". 
The caption of Fig. 8.1 states "Layering scheme of the cuprate superconductors". Fig. 
8.3 shows details of the conduction layers for difference sequence of copper oxide 



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planes and Fig. 8.4 presents details of the bonding layers for several of the cuprates 
which include binding layers for lanthanum superconductor La^CuCX neodymium 
superconductor Nd 2 CuO<, yttrium superconductor YBazOhOa,*, bismuth 
superconductor Bi 2 Sr 2 Can-i Cu n 0 2 „-4, thallium superconductor TI 2 Ba 2 Can.iCun0 2 „~,, and 
mercury superconductor HgBa 2 Ca„.iCu«0 2n . 2 . Fig. 8.5 at pages 102 and 103 show a 
schematic atomic structure showing the layering scheme for thallium superconductors. 
Fig. 8.10 at page 109 shows a schematic crystal structure showing the layering scheme 
for LajCuOA. Fig. 8.11 at page 110 shows a schematic crystal structure showing the 
layering scheme for HgBa 2 Ca 2 Cu 3 CW The layering shown in Poole 1 996 for high T c 
superconductors is consistent with the layering as taught by Bednorz and Mueller in 
their patent application. 



49. Thus Poole 1 988 states that the high T c superconducting materials "are not 
difficult to synthesize" and Poole 1995 states that "the new superconductors do indeed 
possess [the] characteristics" that Applicants' specification describes these new 
superconductors to have. Poole 1996 provide details showing that high T c 
superconductors are layered or layer-like as taught by Bednorz and Mueller. Therefore; 
as of Applicants' priority date persons of ordinary skill in the art of ceramic fabrication 
were enabled to practice Applicants' invention to the full scope that it is presently 
claimed, including in the claims that are not allowed from the teaching in the 
Bednorz-Mueller application without undue experimentation that is by following the 
teaching of Bednorz and Mueller in combination with what vvas known to persons of 
ordinary skill in the art of ceramic fabrication. The experiments to make high T c 
superconductors not specifically identified in the Bednorz-Mueller application were 
made by principles of ceramic fabrication prior to the date of their first publication. It is 
within the skill of a person of ordinary skill in the art of ceramic fabrication to make 
compositions according to the teaching of the Bednorz-Mueller application to determine 
whether or not they are high T e superconductors without undue experimentation. 



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50. I have personally made many samples of high Tc superconductors following the 
teaching of Bednorz and Mueller as found in their patent applications. In making these 
materials it was not necessary to use starting materials in stoichiometric proportions to 
produce a high T c superconductor with insignificant secondary phases or multi-phase 
compositions, having a superconducting portion and a non-superconducting portion, 
where the composite was a high Tc superconductor. Consequently, following the 
teaching of Bednorz and Mueller and principles of ceramic science known prior to their 
discovery, I made, and persons of skill in the ceramic arts were able to make, high T c 
superconductors without exerting extreme care in preparing the composition. Thus I 
made and persons of skill in the ceramic arts were able to make high T c 
superconductors following the teaching of Bednorz and Mueller, without 
experimentation beyond what was well known to a person of ordinary skill in the 
ceramic arts prior to the discovery by Bednorz and Mueller. 



51 . I hereby swear that all statements made herein of my knowledge are true and 
that all statements made on information and belief are believed to be true; and further, 
that these statements were made with the knowledge that willful false statements and 
the like so made are punishable by fine or imprisonment, or both, under Section 1001 
of Title 18 of the United States Code and that such willful false statements made 
jeopardize the validity of the application or patent issued thereon. 



Date: 4j£±LSu^?£- 



By: 



C T- 



Chang C. Tsuei 



Sworn to befer i 




Notary Public 



, 2005. 



DANIEL R MORRIS 
NOTARY PUBLIC. State of New York 
No. *33S6676 
Qualified in Wesichesier County 
Commission Exoires March 16, Vt^** 



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Attachment 1 



PPR 05 '05 15 ; 5>^rnWv 9149453281 TO 917032991475 P. 24/25 

Chang C. Tsuei 




#1B'M Thomas J. Watson Research Center 
P.O. Box 218 
Yorktown Heights, NY 10598 
Phone: (914) 945-2799 
Fax: (914) 945-2141 

Education: . 

ph D 1 966 Materials Science - California Institute of Technology 

M S 1 963 Materials Science - California Institute of Technology 

B.S.' 1960 Mechanical Engineering - National Taiwan University 

Professional Positions: 

IBM Thomas J. Watson Research Center 

1 993 - Present Research Staff Member, Superconductivity 

1 983 - 1 993 Manager, Physics of Structured Materials 

1 979 _ 1 983 Manager, Physics of Amorphous Materials 
1 974 _ 1 975 Acting Manager, Superconductivity 

1 973 - 1 979 Research Staff Member 

Universite Paris-Sud . 
1 996 - 1 997 Invited Professor in Solid State Physics 

Harvard University . 

1 980 (summer) Visiting Scholar in Applied Physics 

Stanford University . 

09/1982 -04/1983 Visiting Scholar in Applied Physics 
California Institute of Technology ,. . 

1 972 - 1 973 Senior Research Associate in Applied Physics 

1 969 _ 1 972 Senior Research Fellow in Materials Science 

1 966 - 1969 Research Fellow in Materials Science 

Honors: . . 

2000 Dynamic Achiever Award from the Organization of Chinese Americans 
2000 IBM Corporate Award 

1 998 Bodo von Borries Lectureship sponsored by the Bodo von Borries Stiftung of Germany. 
1998 Co-recipient of the Oliver £. Buckley Condensed Matter Physics Prize of the American 

Physical Society . 
1996-1997 Appointment as Invited Professor at the Universite Pans-Sud 
1996 Elected to Academia Sinica m . 

1996 Academic Achievement Award from the Chinese American Academic and Professional 

Society - 
1 995 IBM Outstanding Innovation Award for contributions to the work on half integer nux 

quantization observed with a scanning SQUID microscope 
1 992 Max Planck Research Prize from the Max Planck Society and the Alexander von 

Humbolt Foundation of Germany 
1 990 IBM Outstanding Technical Achievement Award for contributions to the understanding 

of electrical properties of grain boundaries in high-T c superconductors 
1984 IBM Invention Achievement Award 



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if 

Chang C.Tsuei- page 2 

1 980 Invention Achievement Award 
Professional Societies Honors: 

2001 Fellow of the American Association for the Advancement of Science 
1 996 Academician of Academia Sinica 
1 974 Fellow of American Physical Society 

Publications: available upon request 



** TOTAL PAGE. 25 **