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IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



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



Date: May 15, 2008 



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 
United States Patent and Trademark Office 
P.O. Box 1450 
Alexandria, VA 22313-1450 



BRIEF ATTACHMENTS AM TO AW 



Respectfully submitted, 



/Daniel P Morris/ 

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



APPEAL BRIEF 
PART IX 



CFR 37 §41 .37(c) (1) (ix) 



SECTION 1 



VOLUME 5 



Part 2 



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

Yorktown Heights, New York 10598 



BRIEF ATTACHMENT AM 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



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



Group Art Unit: 1751 
Examiner: M. Kopec 



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



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



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



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



SIXTH SUPPLEMENTAL AMENDMENT 



Sir: 



Serial No.: 08/479,810 



Page 1 of 5 



Docket: YO987-074BZ 



'ft 



IECEIPT 

IN THE UNITED STATES PATENJ^AND TRADEMARK OFFICE 

In re Patent Application of / ^\ Date: April 14, 2005 



Applicants: Bednorz et al. I m 1 * BH& SI Docket: YO987-074BZ 

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

Filed: June 7. 1995 XtiR^' Examiner: M. Kopec 

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

Commissioner for Patents _ 
P.O. Box 1450 r £ , 

Alexandria, VA 22313-1450 r-f 35 o 

AFFIDAVIT UNDER 37 C.F.R. 1.132 °r 

Sir: 3 -i 

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

— i vr> 

\ -< 

1. I received a B. S. degree In Metallurgy from the University of Liverpool, Liverpool, 
England and a M. S. and a Ph.D. degree in Material Science (1981) from the University 
of California, Berkeley. 

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

3. I have worked as a postdoctoral researcher in the Material Science Department 
of Cornell University form 1981-1982. I have worked at Rockwell International Science 
Center in Thousand Oaks, California from 1 982-1 984 as a ceramic scientist. I have 
worked as a research staff member in Ceramics Science at the Thomas J. Watson 
Research Center of the International Business Machines Corporation in Yorktown 
Heights, New York from 1 984 to the present. 



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Page 1 of 21 



Docket: YO987-074BZ 





IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



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



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



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

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



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

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

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

3. I have worked as a postdoctoral researcher in the Material Science Department 
of Cornell University form 1981-1982. I have worked at Rockwell International Science 
Center in Thousand Oaks, California from 1982-1984 as a ceramic scientist. I have 
worked as a research staff member in Ceramics Science at the Thomas J. Watson 
Research Center of the International Business Machines Corporation in Yorktown 
Heights, New York from 1 984 to the present. 



AFFIDAVIT UNDER 37 C.F.R. 1.132 



Sir: 



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

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

6. This affidavit is in addition to my affidavit dated December 15, 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 1 986 a person of ordinary skill in the art of fabricating a composition 
according to the teaching of the Bednorz-Mueller application would have: a) a Ph.D. 
degree in solid state chemistry, applied physics, material science, metallurgy, physics or 
a related discipline and have done thesis research including work in the fabrication of 
ceramic materials; or b) have a Ph.D. degree in these same fields having done 
experimental thesis research plus one to two years post Ph.D. work in the fabrication of 
ceramic materials; or c) have a master's degree in these same fields and have had five 
years of materials experience at least some of which is in the fabrication of ceramic 
materials. Such a person is referred to herein as a person of ordinary skill in the 
ceramic fabrication art. 

12. The general principles of ceramic science referred to by Bednorz and Mueller in 
their patent application and known to a person of ordinary skill in the ceramic fabrication 
art can be found in many books and articles published before their discovery, priority 
date (date of filing of their European Patent Office patent application EPO 0275343A1 , 
January 23, 1987) and initial US Application filing date (May 22, 1987). An exemplary 
list of books describing the general principles of ceramic fabrication are: 

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

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



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c) Ceramic Processing Before Firing, Onoda et al. f John Wiley & 
Sons, 1978, the entire book, a copy of which is in Attachment D. 

d) Structure, Properties and Preparation of Perovskite-Type 
Compounds, F. S. Galasso , Pergamon Press, 1969, in particular pages 
1 59-1 86, a copy of which is in Attachment E. 

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

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

a) Oxygen Defect K2MF4 - Type Oxides: The Compounds 
La2.xSr x Cu04-x/2 + *, Nguyen et al., Journal of Solid State Chemistry 39, 
1 20-1 27 (1 981 ). See Attachment F. 

b) The Oxygen Defect Perovskite BaLajCus-Om, 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 BaTi0 3 + 
(1-x) Ba(Ln 05 B 05 ) 0 3 , V.S. Chincholkar et al., Therm. Anal. 6th, Vol. 2., p. 
251-6,1980. See Attachment I. 



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14. The Bednorz-Mueller application in the paragraph bridging pages 6 and 7 states 
in regard to the high 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 MB 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 MA 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 eartrHike element, TM is a nonmagnetic 
transition metal, and 0 is oxygen. Examples of transition metal elements 
include Cu, Ni, Crete. In particular, transition metals that can exhibit 
multi-valent states are very suitable. The rare earth elements are typically 
elements 58-71 of the periodic table, including Ce, Nd, etc. 



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Docket: YO987-074BZ 




15. In the passage quoted in paragraph 14 the general 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 HA of the 
periodic table, or a combination of rare earth or rare earth-like elements and alkaline 
earth elements." Thus applicants teach that RE can be something other than an rare 
earth. For example, it can be an alkaline earth, but is not limited to a alkaline earth 
element. It can be an element that has the same effect as an alkaline earth or 
rare-earth element, that is a rare earth like element. Also, this passage teaches that 
TM can be substituted with another element, for example, but not limited to, a rare 
earth, alkaline earth or some other element that acts in place of the transition metal. 

16. The following table is compiled from the Table 1 of the Article by Rao (See 
Attachment AB) and the Table of high T c 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. 



18. Composite Table 



1 


2 


3 


4 


5 


6 


7 


# 


MATERIAL 


RAO 

ARTICLE 


HANDBOOK 
OF CHEM & 
PHYSICS 




ALKALINE 

EARTH 

ELEMENT 


RARE 
EARTH 
ELEME 
NT 


1 


La 2 Cu0 4 *5 




V 


* 


N 


Y 


2 


La 2 . x Sr x (Ba x )Cu0 4 


V 


V 




Y 


Y 


3 


La 2 Ca,. x Sr x Cu206 




V 




Y 


Y 



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Docket: YO987-074BZ 



4 


YBa 2 Cu 3 0 7 


V 


V 




Y 


Y 


5 


YBa 2 Cu40 8 


V 


V 




Y 


Y 


6 


Y 2 Ba4Cu 7 Oi5 


V 


V 




Y 


Y 


7 


Bi 2 Sr 2 Cu0 6 


V 


V 


* 


Y 


N 


8 


Bi 2 CaSr 2 Cu 2 0 8 


V 


V 


* 


Y 


N 


9 


Bi 2 Ca 2 Sr 2 Cu 3 Oio 


V 


V 


* 


Y 


N 


10 


Bi 2 Sr 2 (Lni . x Cex) 2 Cu 2 0 io 


V 


V 




Y 


Y 


11 


Tl 2 Ba 2 Cu0 6 


V 


V 


* 


Y 


N 


12 


Tl 2 CaBa 2 Cu 2 0 8 


V 




* 


Y 


N 


13 


Tl 2 Ca 2 Ba 2 Cu 3 Oi 0 


- V 




* 


Y 


N 


14 


Tl(BaLa)Cu0 5 


V 


V 




Y 


Y 


15 


Tl(SrLa)Cu0 5 


V 


V 




Y 


Y 


16 


(Tl 0 .5Pbo.5)Sr 2 Cu0 5 


V 


V 




Y 


N 


17 


TlCaBa 2 Cu 2 0 7 


V 


V 


* 


Y 


N 


18 


(Tl 0 .5Pbo.5)CaSr 2 Cu 2 0 7 


V 




* 


Y 


N 


19 


TlSr 2 Yo. 5 Cao.5Cu 2 07 


V 


V 




Y 


Y 


20 


TlCa 2 Ba 2 Cu 3 0 8 


V 


V 


* 


Y 


N 


21 


(Tl 0 .5Pbo.5)Sr 2 Ca 2 Cu 3 0 9 


V 


V 


* 


Y 


N 


22 


TlBa 2 (Ln,. x Ce x ) 2 Cu 2 0 9 


V 


V 




Y 


Y 


23 


Pb 2 Sr 2 Lno5Cao.sCu 3 0 8 


V 


V 




Y 


Y 


24 


Pb 2 (Sr,La) 2 Cu 2 0 6 


V 


V 




Y 


Y 


25 


(Pb,Cu)Sr 2 (Ln,Ca)Cu 2 0 7 


V 


V 




Y 


Y 


26 


(Pb,Cu)(Sr,Eu)(Eu,Ce)Cu 2 O x 








Y 


Y 


27 


Nd 2 . x CexCu0 4 


V 




* 


N 


Y 


28 


Ca,. x Nd x Cu0 2 


V 






Y 


Y 


29 


Sr,. x Nd x Cu0 2 


V 


V 




Y 


Y 


30 


Cai. x Sr x Cu0 2 




V 




Y 


N 


31 


Bao. 6 Ko.4Bi03 




V. 


* 


Y 


N 


32 


Rt^C 5C6O 




V 


* 


N 


Y 


33 


NdBa 2 Cu 3 0 7 




V 




Y 


Y 


34 


SmBaSrCuO? 




V 




Y 


Y 


35 


EuBaSrCu 3 0 7 




v 




Y 


Y 


36 


BaSrCu 3 0 7 






* 


Y 


N 


37 


DyBaSrCu 3 0 7 




V 




Y 


Y 


38 


HuBaSiCu 3 0 7 




V 




Y 


Y 


39 


ErBaSrCu 3 0 7 (Multiphase) 




V 




Y 


Y 


40 


TmBaSrCu 3 0 7 (Multiphase) 




V 




Y 


Y 



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41 


YBaSrCu 3 0 7 






* 


Y 


Y 


42 


HgBa 2 Cu0 2 






* 


Y 


N 


43 


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






* 


Y 


N 


44 


HgBa 2 Ca 2 Cu 3 0 8 






* 


Y 


N 


45 


HgBa 2 Ca 3 Cu4O, 0 






* 


Y 


N 



19. The first composition, Laz Cu 0 M , has the form RE 2 Cu0 4 which is explicitly 
taught by Bednorz and Mueller. The <5 indicates that there is a nonstoichiometric 
amount of oxygen. 



20. The Bednorz-Mueller application teaches at page 1 1 , line 1 9 to page 1 2, 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 RE 2 TM0 4 where RE stands for the rare earths (lanthanides) 
or rare earth-like elements and TM stands for a transition metal. In these 
compounds the RE portion can be partially substituted by one or more 
members of the alkaline earth group of elements. In these particular 
compounds, the oxygen content is at a deficit. For example, one such 
compound that meets this general description is lanthanum copper oxide 
La 2 Cu0 4 ... 

21 . The Bednorz-Mueller application at page 15, last paragraph states "Despite their 
metallic character, the Ba-La-Cu-O 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 O 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 
(1988) is directed to Bismuth (Bi) compounds. 



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

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

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

The samples were prepared by thoroughly mixing suitable amounts of 
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 
3hat = 880°C. 

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

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

The Bi-Sr-Ca-Cu-0 oxide samples were prepared from powder reagents 
of 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+1 5 and yellow HgO (98% purity, Aldrich). The 
precursor BazCuO^ 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. All 
these operations were carried out in a dry box. After evacuation, the 
tubes were sealed, placed in steel containers, as described in ref. 3, and 
heated for 5 h to reach ~800°C. The samples were then cooled in the 
furnace, reaching room temperature after ~1 0 h. 

This is according to the general principles of ceramic science known prior to 
applicants priority date. 

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

The preparative conditions for the new materials are considerably more 
stringent than for the previously known copper-based superconductors. 
Direct synthesis of members of this family by reaction of the component 
metal oxides or carbonates in air or oxygen at temperatures below 900°C 
is not possible because of the stability of the oxidized SrPbCVbased 
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 1 91 to 207 in 
the book "Structure, Properties and Preparation of Perovskite-Type Compounds" by F. 
S. Galasso, published in 1969, which is Attachment E hereto. This list contains about 
300 compounds. Thus, what the term "Perovskite-type" means and how to make these 
compounds was well known to a person of ordinary skill in the art in 1969, more than 17 
years before the Applicants' priority date (January 23, 1987). 

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

32. The standard reference "Landholt-Bornstein", Volumn 4, "Magnetic and Other 
Properties of Oxides and Related Compounds Part A" (1970) lists at page 148 to 206 
Perovskite and Perovskite-related structures. (See Attachment N). Section 3.2 starting 
at page 190 is entitled "Descriptions of perovskite-related structures". The German title 
is "Perowskit-anliche Strukturen". The German word "anliche" can be translated in 
English as "like". The Langenscheidt's German-English, English-German Dictionary 
1970, at page 446 translates the English "like" as the 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 Bornstein" book published in 1970, 
more than 16 years before Applicants' priority date (January 23, 1987), shows that the 
term -perovskite-like" or "perovskite related" is understood by persons of skill in the art 
prior to Applicants' priority date. Moreover, the "Landholt-Bornstein" book cites 
references for each compound listed. Thus a person of ordinary skill in the art of 
ceramic fabrication knows how to make each of these compounds. Pages 376-380 of 
Attachment N has figures showing the crystal structure of compounds containing Bi and 
Pb. 

33. The standard reference "Landholt-Bornstein, Volume 3, Ferro- and 
Antiferroelectric Substances' (1969) provides at pages 571-584 an index to 
substances. (See Attachment P). This list contains numerous Bi and Pb containing 
compounds. See, for example pages 578 and 582-584. Thus a person of ordinary skill 
in the art of ceramic fabrication would be motivated by Applicants' application to 
fabricate Bi and/or Pb containing compounds that come within the scope of the 
Applicants' claims. 

34. The standard reference "Landholt-Bornstein Volume 3 Ferro- and 
Antiferroelectric Substances" (1969) (See Attachment P) at page 37, section 1 is 
entitled "Perovskite-type oxides." This standard reference was published more than 17 
years before Applicants' priority date (January 23, 1987). The properties of 
perovskite-type oxides are listed from pages 37 to 88. Thus the term perovskite-type 
was well known and understood by persons of skill in the art of ceramic fabrication prior 
to Applicants' priority date and more than 17 years before Applicants' priority date 
persons of ordinary skill in the art knew how to make Bi, Pb and many other perovskite, 
perovskite-like, perovskite-related and perovskite-type compounds. 



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Docket: YO987-074BZ 



35. At page 1 4, line 1 0-1 5 of the Bednorz-Mueller application, Applicants' state 
"samples in the Ba-La-Cu-0 system, when subjected to x-ray analysis, revealed three 
individual crystallographic phases V.12. a first layer-type perovskite-like phase, related 
to the K2NiF 4 structure ..." Applicants' priority document EP0275343A1 filed July 27, 
1988, is entitled "New Superconductive Compounds of the K2NiF 4 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 K2MF4 structure. (See Attachment Q). Thus based on Applicants' teachings prior 
to Applicants' priority date, a person of ordinary skill in the art of ceramic fabrication 
would be motivated to fabricate Thallium based compounds to test for high Tc 
superconductivity. 

36. The book "Crystal Structures" Volume 4, by Ralph W. G. Wyckoff, Interscience 
Publishers, 1960 states at page 96 "This structure, like these of BUTiaO^ (IX, F12) and 
Ba BL» TU 0 4 (XI, 13) 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 ) 24 
(Ax-iB x 03x + i) 2 " have been reported (Smolenskii et al. 1961; Subbarao, 
1962), where A = Ca, Sr, Ba, Pb, etc., B = Ti, Nb, Ta and x = 2, 3, 4, or 5. 
The structure had been previously investigated by Aurivillius (1949) who 
described them in terms of Alternate (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 9 (T e = 703°K), BiBi 3 Ti 2 Ti0i 2 or 



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Bi 4 Ti 3 0i 2 (T c = 948°K), Ba2Bi4Ti 5 0i 8 (T c = 598°K) and Pb 2 Bi 4 Ti 5 0,8 (T c = 
583°K). Only bismuth titanate Bi 4 Ti 3 0i2 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-Bornstein, Volume 3, Ferro and 
Antiferroelectric Substances" (1969) at pages 107 to 1 14 (See Attachment T) list 
"layer-structure oxides" and their properties. Thus the term "layered compounds" was 
well known in the art of ceramic fabrication in 1 969 more than 1 6 years prior to 
Applicants' priority date and how to make layered compounds was well known prior to 
applicants priority date. 

39. Layer perovskite type Bi and Pb compounds closely related to the Bi and Pb high 
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 Nb0 5 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 0 2 2 + 
layers parallel to the basal plane and sheets of composition BfeTiaOV. 
The atomic arrangement within the BfeTiaOV 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 OV 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 "BiaNbTiCV. And at page 475 has a 
table of compounds having the "CaBi 2 Nb 2 0 9 structure" listing the following compounds 
BUNbTiOg, Bi 3 TaTi0 9 , CaBizNkOg, SrBi 2 Nb 2 0 9 , SrBi 2 Ta 2 0 9 , BaBi 2 Nb 2 0 9l PbBi 2 Nb 2 0 9 , 
NaBi 5 Nb40i 8 , KBi 5 Nb 4 0i 8 . 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 "n 
Structure of Bi 4 Ti 3 0i 2 ". And at page 510, Fig. 4 shows a crystal structure in which "A 
denotes a perovskite layer B'feTisOV, 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 "m 
Structure of BaEfoTUOis". 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 Nb20 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 BaBi 4 Ti 4 0i 5 . 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 Ni 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. 

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 (1 998), 



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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 little familiarity with the subtle 
physicochemical process involved in the transformation of a mixture of compounds into 
a superconductor." Poole 1988 further states at pages 61-62 B [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." 
Consequently, it is my opinion that Applicants have fully enabled high T c materials 
oxides and their claims. 



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Docket: YO987-074BZ 



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

At page 179 of Poole 1995 states: 

V. PEROVSKITE-TYPE SUPERCONDUCTING STRUCTURES 

In their first report on high-termperature superconductors Bednorz and 

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

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

confirmed that the new superconductors do indeed possess these 

characteristics. 

I agree with this statement. 

48. The book "The New Superconductors", by Frank J. Owens and Charles P. 
Poole, Plenum Press, 1996, referred to herein as Poole 1996 in Chapter 8 entitled 
"New High Temperature Superconductors" starting a page 97 (See Attachment AG) 
shows in Section 8.3 starting at page 98 entitled "Layered Structure of the Cuprates" 
schematic diagrams of the layered structure of the cuprate superconductors. Poole 
1996 states in the first sentence of Section 8.3 at page 98 "All cuprate superconductors 
have the layered structure shown in Fig. 8.1 ." This is consistent with the teaching of 
Bednorz and Mueller that "These compositions have a layer-type Crystalline Structure 
often Perovskite-like" as noted in paragraph 14 above. Poole 1996 further states in the 
first sentence of Section 8.3 at page 98 "The flow of supercurrent takes place in 
conduction layers and bonding layers support and hold together the conduction layers". 
The caption of Fig. 8.1 states "Layering scheme of the cuprate superconductors". Fig. 
8.3 shows details of the conduction layers for difference sequence of copper oxide 
planes and Fig. 8.4 presents details of the bonding layers for several of the cuprates 
which include binding layers for lanthanum superconductor La 2 Cu0 4 , neodymium 
superconductor Nd 2 Cu0 4 , yttrium superconductor YBa 2 Cu 3 0 2n+ 4, bismuth 



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superconductor Bi 2 Sr 2 Can-i CunO^, thallium superconductor TI 2 Ba 2 Ca,viCu n 02r>f4, and 
mercury superconductor HgBa2Ca n -iCun02rH.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 La 2 Cu0 4 . Fig. 8.1 1 at page 1 1 0 shows a schematic crystal structure showing the 
layering scheme for HgBa 2 Ca 2 Cu308 + x. The layering shown in Poole 1996 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 was 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 c 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. 





Thomas M. Shaw 




2005. 



Commission Expires March 16. tft=_ 7^CTf)*7 



DANIEL P. MORRIS 
NOTARY PUBLIC, State of New York 
No. 4888676 
Qualified in Westchester County 



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ATTACHMENT 1 



Thomas M. Shaw 



IBM Thomas J. Watson Research Center 
P.O. Box 218 
Yorktown Heights, NY 10598 
Phone: (914) 945-3196 

Education: 

1981 Ph.D. Materials Science - University of California at Berkeley 

1978 Masters of Science Materials Science - University of California at Berkeley 
1 975 Bachelors of Science Engineering in Metallurgy and Materials Science - University of 
Liverpool 

Work Experience: 

1994-Present Research Staff Member at IBM Thomas J. Watson Research Center working in 
Materials Science 

1984-1994 Research Staff Member at IBM Thomas J. Watson Research Center working in 
Ceramics Science 

1982-1984 Member of the technical staff at Rockwell International Science Center working in 
Ceramics Science 

1981-1982 Postdoctoral Associate at Cornell University working in Ceramics Science 

Professional Positions: 

A fellow of the American Ceramics Society 

Honors: 

1981 John E. Dorn Award for thesis. 
Publications: 

Has authored or co-authored more that 150 publications and 21 patents. 

His research interests include, ferroelectric thin films, processing and microstructure control of 
ceramic materials, microscopy of materials, interfacial energy driven processes, liquid phase 
sintering, porous materials, diffusion in thin films, electrical and mechanical properties materials 
and the reliability of interconnect structures. 



** TX STATUS REPORT ** 



AS OF fiPR 14 ' 05 15:06 PAGE. 01 
IBM 



DATE TirC TO/FROM 
09 04/14 14:59 917032991475 



MODE M IN/SEC PGS CMDtt STATUS 
IF— S 07*24" 029 OK 



BRIEF ATTACHMENT AN 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



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



Date: April 5, 2005 
Docket: YO987-074BZ 
Group Art Unit: 1751 
Examiner: M. Kopec 



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



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



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



FIFTH SUPPLEMENTAL AMENDMENT 



Sir: 



Serial No.: 08/479,810 



Page 1 of 5 



Docket: YO987-074BZ 




IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 

In re Patent Application of Date: April 4, 2005 

Applicants: Bednorz et al. Docket: YO987-074BZ 

Serial No.: 08/479.810 Group Art Unit: 1751 

Filed: June 7, 1995 Examiner M. Kopec 

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

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

AFFIDAVIT UNDER 37 C.F.R. 1.132 

Sir: 

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

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

2. I refer to Attachments A to Z and AA herein which were submitted in a separate 
paper designated as "FIRST SUPPLEMENTAL 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 g 
superconducting, amorphous and structured materials at the Thomas J. Watsjpn ^ 
Research Center of the International Business Machines Corporation in Yo^wvn'f' >_ 
Heights, New York from 1 973 to the present. ^ IJX 

s ~ * 

4. I have worked in the fabrication of and characterization of high temperature^ 
superconductor and related materials from 1 973 to the present. ^ 



Serial No.: 08/479,810 



Page 1 of 21 



Docket: YO987-074BZ 




J^cS 5 2g0S, 1 5f 37. .FR I BM-PLEXANDR I A 7032991476 TO 917008623281 P.05/06 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 
in re Patent Application of Date: April 4, 2005 

Applicants: Bednorzetal. Docket: YO987-074BZ 

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

Filed: June 7, 1995 Examiner M. Kopec 

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

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

AFFIDAVIT UNDER 37 C.F.R. 1.132 

Sir. 

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

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

2. I refer to Attachments A to Z and AA herein which were submitted in a separate 
paper designated as "FIRST SUPPLEMENTAL 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. 



Serial No.: 08/479,810 



Page 1 of 21 



Docket: YO987-0746Z 





IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



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



Group Art Unit: 1751 
Examiner: M. Kopec 



Date: April 4, 2005 
Docket: YO987-074BZ 



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

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



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

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

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

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

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



AFFIDAVIT UNDER 37 C.F.R. 1.132 



Sir: 



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Page 1 of 21 



Docket: YO987-074BZ 



5. 



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



6. This affidavit is in addition to my affidavit dated December 1 5, 1 998. I have 
reviewed the above-identified patent application (Bednorz-Mueller application) and 
acknowledge that it represents the work of Bednorz and Mueller, which is generally 
recognized as the first discovery of superconductivity in a material having a 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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10. Prior to 1986 a person having a bachelor's degree in an engineering discipline, 
applied science, chemistry, physics or a related discipline could have been trained 
within one year to reliably test a material for the presence of superconductivity and to 
flow a superconductive current in a superconductive composition. 

1 1 . Prior to 1 986 a person of ordinary skill in the art of fabricating a composition 
according to the teaching of the Bednorz-Mueller application would have: a) a Ph.D. 
degree in solid state chemistry, applied physics, material science, metallurgy, physics or 
a related discipline and have done thesis research including work in the fabrication of 
ceramic materials; or b) have a Ph.D. degree in these same fields having done 
experimental thesis research plus one to two years post Ph.D. work in the fabrication of 
ceramic materials; or c) have a master's degree in these same fields and have had five 
years of materials experience at least some of which is in the fabrication of ceramic 
materials. Such a person is referred to herein as a person of ordinary skill in the 
ceramic fabrication art. 

12. The general principles of ceramic science referred to by Bednorz and Mueller in 
their patent application and known to a person of ordinary skill in the ceramic fabrication 
art can be found in many books and articles published before their discovery, priority 
date (date of filing of their European Patent Office patent application EPO 0275343A1, 
January 23, 1987) and initial US Application filing date (May 22, 1987). An exemplary 
list of books describing the general principles of ceramic fabrication are: 

a) Introduction to Ceramics, Kingery et al., Second Edition, John 
Wiley & Sons, 1976, in particular pages 5-20, 269-319, 381-447 and 
448-51 3, a copy of which is in Attachment B. 

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



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c) Ceramic Processing Before Firing, Onoda et al., John Wiley & 
Sons, 1978, the entire book, a copy of which is in Attachment D. 

d) Structure, Properties and Preparation of Perovskite-Type 
Compounds, F. S. Galasso , Pergamon Press, 1969, in particular pages 
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 
La 2 -xSr x Cu04-x/2 + -, Nguyen et al., Journal of Solid State Chemistry 39, 
120-127(1981). See Attachment F. 

b) The Oxygen Defect Perovskite BaL.a4Cu5.O134, A Metallic (This is 
referred to in the Bednorz-Mueller application at page 21, lines 1-2) 
Conductor, C. Michel et al., Mat. Res. Bull., Vol. 20, pp. 667-671, 1985. 
See Attachment G. 

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

d) Thermal Behaviour of Compositions in the Systems x BaTi0 3 + 
(1-x) Ba(Ln 0 .s B 05 ) 0 3 , V.S. Chincholkar et al., Therm. Anal. 6th, Vol. 2., p. 
251-6,1980. See Attachment I. 



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14. The Bednorz-Mueller application in the paragraph bridging pages 6 and 7 states 
in regard to the high 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 NIB element of the periodic table, 
such as La. Substitutions can be found in the rare earth (or rare 
earth-like) site or in the transition metal sites of the compositions. For 
example, the rare earth site can also include alkaline earth elements 
selected from group HA of the periodic table, or a combination of rare 
earth or rare earth-like elements and alkaline earth elements. Examples 
of suitable alkaline earths include Ca, Sr, and Ba. The transition metal 
site can include a transition metal exhibiting mixed valent behavior, and 
can include more than one transition metal. A particularly good example 
of a suitable transition metal is copper. As will be apparent later, Cu- 
oxide based systems provide unique and excellent properties as high 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, Crete. 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. 

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

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



18. Composite Table 



1 


2 


3 


4 


5 


6 


7 


# 


MATERIAL 


RAO 


HANDBOOK 




ALKALINE 


RARE 






ARTICLE 


OFCHEM& 




EARTH 


EARTH 








PHYSICS 




ELEMENT 


ELEME 














NT 


1 


La 2 Cu0 4 +5 


V 




* 


N 


Y 


2 


La 2 -xSr x (Ba x )Cu0 4 


V 


V 




Y 


Y 


3 


La 2 Ca,. x Sr x Cu 2 06 


V 


V 




Y 


Y 



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4 


YBa 2 Cu 3 0 7 


V 


V 




Y 


Y 


5 


YBa 2 Cii40 8 


V 


V 




Y 


Y 


6 


Y 2 Ba4Cu 7 0i 5 


V 






Y 


Y 


7 


Bi 2 Sr 2 Cu0 6 


V 


V 




Y 


N 


8 


Bi 2 CaSr 2 Cu 2 O g 




V 




Y 


N 


9 


Bi 2 Ca 2 Sr 2 Gu 3 Oio 


V 


V 


* 


Y 


N 


10 


B^SrsCLriLxCex^CuzOio 




V 




Y 


Y 


11 


Tl 2 Ba 2 Cu0 6 




V 


* 


Y 


N 


12 


Tl 2 CaBa 2 Cu 2 0 8 


V 


V 




Y 


N 


13 


Tl 2 Ca 2 Ba 2 Cu 3 O 10 


V 


V 




Y 


N 


14 


Tl(BaLa)Cu0 5 


V 


V 




Y 


Y 


15 


Tl(SrLa)CuO s 


V 


V 




Y 


Y 


16 


(Tl 05 Pbo.5)Sr 2 Cu05 


V 


V 


* 


Y 


N 


17 


TlCaBa 2 Cu 2 0 7 


V 


V 


* 


Y 


N 


18 


(Tl 0 . 5 Pbo.5)CaSr 2 Cu 2 0 7 




V 


* 


Y 


N 


19 


TlSr 2 Y 0 . 5 Cao. 5 Cu 2 0 7 


V 


V 




Y 


Y 


20 


TlCa 2 Ba 2 Cu 3 0 8 


V 




* 


Y 


N 


21 


(Tl 0 . 5 Pbo-5)Sr 2 Ca 2 Cu 3 09 


V 


V 


* 


Y 


N 


22 


TlBa 2 (Lni. x Ce x ) 2 Cu 2 09 


V 


V 




Y 


Y 


23 


Pb 2 Sr 2 Lno. 5 Cao.5Cu 3 0 8 




V 




Y 


Y 


24 


Pb 2 (Sr,La) 2 Cu 2 0 6 


V 






Y 


Y 


25 


(Pb,Cu)Sr 2 (Ln,Ca)Cu 2 0 7 


V 


V 




Y 


Y 


26 


(Pb,Cu)(Sr,Eu)(Eu,Ce)Cu 2 O x 


V 






Y 


Y 


27 


Nd 2 . x Ce x Cu0 4 


V 




* 


N 


Y 


28 


Cai. x Nd x Cu0 2 








Y 


Y 


29 


Sr,. x Nd x Cu0 2 


V 






Y 


Y 


30 


Cai. x Sr x Cu0 2 






* 


Y 


N 


31 


Bao6Ko4Bi0 3 




V 


* 


Y 


N 


32 


Rb 2 CsC6o 








N 


Y 


33 


NdBa 2 Cu 3 0 7 








Y 


Y 


34 


SmBaSrCuO? 








Y 


Y 


35 


EuBaSrCu 3 0 7 








Y 


Y 


36 


BaSrCu 3 0 7 






* 


Y 


N 


37 


DyBaSrCu 3 0 7 








Y 


Y 


38 


HuBaSrCu 3 0 7 








Y 


Y 


39 


ErBaSrCu 3 0 7 (Multiphase) 








Y 


Y 


40 


TmBaSrCu 3 0 7 (Multiphase) 








Y 


Y 



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41 


YBaSrCu 3 0 7 




V 




Y 


Y 


42 


HgBa 2 Cu0 2 




V 


* 


Y 


N 


43 


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




V 




Y 


N 


44 


HgBa 2 Ca 2 Cu 3 08 




V 


* 


Y 


N 


45 


HgBa 2 Ca 3 Cii40io 






* 


Y 


N 



19. The first composition, La 2 Cu 0 4+(5 , has the form RE 2 Cu0 4 which is explicitly 
taught by Bednorz and Mueller. The S indicates that there is a nonstoichiometric 
amount of oxygen. 



20. The Bednorz-Mueller application teaches at page 1 1 , line 1 9 to page 1 2, 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 RE 2 TM0 4 where RE stands for the rare earths (lanthanides) 
or rare earth-like elements and TM stands for a transition metal. In these 
compounds the RE portion can be partially substituted by one or more 
members of the alkaline earth group of elements. In these particular 
compounds, the oxygen content is at a deficit. For example, one such 
compound that meets this general description is lanthanum copper oxide 
La 2 Cu0 4 ... 

21 . The Bednorz-Mueller application at page 1 5, last paragraph states "Despite their 
metallic character, the Ba-La-Cu-0 type materials are essentially ceramics, as are other 
compounds of the 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 O 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 
(1988) is directed to Bismuth (Bi) compounds. 



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

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

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

The samples were prepared by thoroughly mixing suitable amounts of 
TI2O3, CaO, 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 
3hat=880'C. 

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

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

The Bi-Sr-Ca-Cu-0 oxide samples were prepared from powder reagents 
of 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 Ba 2 Cu0 3+( $ 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. All 
these operations were carried out in a dry box. After evacuation, the 
tubes were sealed, placed in steel containers, as described in ref. 3, and 
heated for 5 h to reach ~800°C. The samples were then cooled in the 
furnace, reaching room temperature after -10 h. 

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

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

The preparative conditions for the new materials are considerably more 
stringent than for the previously known copper-based superconductors. 
Direct synthesis of members of this family by reaction of the component 
metal oxides or carbonates in air or oxygen at temperatures below 900°C 
is not possible because of the stability of the oxidized SrPb0 3 -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 1 91 to 207 in 
the book "Structure, Properties and Preparation of Perovskite-Type Compounds" by F. 
S. Galasso, published in 1969, which is Attachment E hereto. This list contains about 
300 compounds. Thus, what the term "Perovsk'rte-type" means and how to make these 
compounds was well known to a person of ordinary skill in the art in 1969, more than 17 
years before the Applicants' priority date (January 23, 1987). 

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

32. The standard reference "Landholt-Bornstein", Volumn 4, "Magnetic and Other 
Properties of Oxides and Related Compounds Part A" (1970) lists at page 148 to 206 
Perovskite and Perovskite-related structures. (See Attachment N). Section 3.2 starting 
at page 190 is entitled "Descriptions of perovskite-related structures". The German title 
is "Perowskit-anliche Strukturen". The German word "anliche" can be translated in 
English as "like". The Langenscheidt's German-English, English-German Dictionary 
1970, at page 446 translates the English "like" as the 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 Bornstein" book published in 1970, 
more than 16 years before Applicants' priority date (January 23, 1987), shows that the 
term "perovskite-like" or "perovskite related" is understood by persons of skill in the art 
prior to Applicants' priority date. Moreover, the "Landholt-Bornstein" book cites 
references for each compound listed. Thus a person of ordinary skill in the art of 
ceramic fabrication knows how to make each of these compounds. Pages 376-380 of 
Attachment N has figures showing the crystal structure of compounds containing Bi and 
Pb. 

33. The standard reference "Landholt-Bornstein, Volume 3, Ferro- and 
Antiferroelectric Substances" (1969) provides at pages 571-584 an index to 
substances. (See Attachment P). This list contains numerous Bi and Pb containing 
compounds. See, for example pages 578 and 582-584. Thus a person of ordinary skill 
in the art of ceramic fabrication would be motivated by Applicants' application to 
fabricate Bi and/or Pb containing compounds that come within the scope of the 
Applicants' claims. 

34. The standard reference "Landholt-Bornstein Volume 3 Ferro- and 
Antiferroelectric Substances" (1969) (See Attachment P) at page 37, section 1 is 
entitled "Perovskite-type oxides." This standard reference was published more than 17 
years before Applicants' priority date (January 23, 1987). The properties of 
perovskite-type oxides are listed from pages 37 to 88. Thus the term perovskite-type 
was well known and understood by persons of skill in the art of ceramic fabrication prior 
to Applicants' priority date and more than 17 years before Applicants' priority date 
persons of ordinary skill in the art knew how to make Bi, Pb and many other perovskite, 
perovskite-like, perovskite-related and perovskite-type compounds. 



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35. At page 14, line 10-15 of the Bednorz-Mueller application, Applicants' state 
"samples in the Ba-La-Cu-O system, when subjected to x-ray analysis, revealed three 
individual crystallographic phases V.12. a first layer-type perovskite-like phase, related 
to the K2NiF 4 structure ..." Applicants' priority document EP0275343A1 filed July 27, 
1988, is entitled "New Superconductive Compounds of the K 2 NiF 4 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 K 2 NiF 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, Interscience 
Publishers, 1960 states at page 96 "This structure, like these of Bi 4 Ti 2 Oi 2 (IX, F i2 ) and 
Ba B'u Ti 4 0 4 (XI, 13) 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 x .iBx0 3x+ i) 2 " have been reported (Smolenskii et al. 1 961 ; Subbarao, 
1962), where A = Ca, Sr, Ba, Pb, etc., B = Ti, Nb, Ta and x = 2, 3, 4, or 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 9 (T c = 703°K), BiBi 3 Ti 2 TiOi 2 or 



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Bi 4 Ti 3 0i2 (T c = 948°K), BazBUTUOis (T c = 598°K) and Pb 2 Bi 4 Ti 5 Oi 8 (T c = 
583°K). Only bismuth titanate Bi 4 Ti 3 0i 2 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 1 5 years before Applicants' priority date. 

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

39. Layer perovskite type Bi and Pb compounds closely related to the Bi and Pb high 
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 Nb0 5 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 OV. 
The atomic arrangement within the Bi 2 Ti 3 O 2 i 0 " 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 OV 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 9 , SrBi 2 Nb 2 0 9l SrBi 2 Ta 2 0 9 , BaBi 2 Nb 2 0 9 , PbBi 2 Nb 2 0 9 , 
NaBi 5 Nb 4 0i8, KBi 5 Nb 4 0i8. 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 4 Ti 3 0i 2 ". And at page 510, Fig. 4 shows a crystal structure in which "A 
denotes a perovskite layer BbTUOV, 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 "III 
Structure of BaBi 4 Ti 4 0i 5 ". 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 BaBi 4 Ti 4 0i 5 . 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 10 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 "[cjopper 
oxide superconductors with a purity sufficient to exhibit zero resistivity or to 
demonstrate levitation (Early) are not difficult to synthesize. We believe that this is at 
least partially responsible for the explosive worldwide growth in these materials". Poole 
1988 further states at page 61 "[i]n this section three methods of preparation will be 
described, namely, the solid state, the coprecipitation, and the sol-gel techniques 
(Hatfi). The widely used solid-state technique permits off-the-shelf chemicals to be 
directly calcined into superconductors, and it requires little familiarity with the subtle 
physicochemical process involved in the transformation of a mixture of compounds into 
a superconductor." Poole 1988 further states at pages 61-62 "[i]n the solid state 
reaction technique one starts with oxygen-rich compounds of the desired components 
such as oxides, nitrates or carbonates of Ba, Bi, La, Sr, Ti, Y or other elements. ... 
These compounds are mixed in the desired atomic ratios and ground to a fine powder 
to facilitate the calcination process. Then these room-temperature-stabile salts are 
reacted by calcination for an extended period (~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." 



Serial No.: 08/479,810 



Page 18 of 21 



Docket: YO987-074BZ 



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 1995 entitled "Superconductivity" 
Academic Press which has a Chapter 7 on "Perovskite and Cuprate Crystallographic 
Structures". (See Attachment Z). This book will be referred to as Poole 1995. 

At page 179 of Poole 1995 states: 

V. PEROVSKITE-TYPE SUPERCONDUCTING STRUCTURES 

In their first report on high-termperature superconductors Bednorz and 

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

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

confirmed that the new superconductors do indeed possess these 

characteristics. 

I agree with this statement. 

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



Serial No.: 08/479,810 



Page 19 of 21 



Docket: YO987-074BZ 




planes and Fig. 8.4 presents details of the bonding layers for several of the cuprates 
which include binding layers for lanthanum superconductor La 2 Cu0 4 , neodymium 
superconductor Nd 2 Cu0 4 , yttrium superconductor YBa 2 Cu 3 0 2n +4, bismuth 
superconductor Bi 2 Sr 2 Ca n .i Cu n 0 2n+ 4, thallium superconductor TI 2 Ba 2 Ca n .iCun0 2 n + 4, and 
mercury superconductor HgBa 2 Ca„.iCu n 0 2 n +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 La 2 Cu0 4 . Fig. 8.1 1 at page 1 1 0 shows a schematic crystal structure showing the 
layering scheme for HgBa 2 Ca 2 Cu 3 CW The layering shown in Poole 1996 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 was 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 c superconductors without undue experimentation. 



Serial No.: 08/479,810 



Page 20 of 21 



Docket: YO987-074BZ 





50. I have personally made many samples of high Tc superconductors following the 
teaching of Bednorz and Mueller as found in their patent applications. In making these 
materials it was not necessary to use starting materials in stoichiometric proportions to 
produce a high 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 1 8 of the United States Code and that such willful false statements made 
jeopardize the validity of the application or patent issued thereon. 





Chang C. Tsuei 




2005. 



NOTARY PUBLIC, state of New York 
No. 4888876 
Qualified in Westchester County 
Commission Expires March 16, tfra*. 



Serial No.: 08/479,810 



Page 21 of 21 



Docket: YO987-074BZ 



Attachment 1 




Chang C. Tsuei 



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



Education: 

Ph.D. 1966 Materials Science - California Institute of Technology 

M.S. 1 963 Materials Science - California Institute of Technology 

B.S. 1 960 Mechanical Engineering - National Taiwan University 

Professional Positions: 

IBM Thomas J. Watson Research Center 

1993 -Present 

1983- 1993 

1979-1983 

1974-1975 

1973- 1979 
Universite Paris-Sud 

1996-1997 
Harvard University 

1980 (summer) 
Stanford University 

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

1 972 - 1 973 Senior Research Associate in Applied Physics 

1 969 - 1972 Senior Research Fellow in Materials Science 

1 966 - 1 969 Research Fellow in Materials Science 



Research Staff Member, Superconductivity 
Manager, Physics of Structured Materials 
Manager, Physics of Amorphous Materials 
Acting Manager, Superconductivity 
Research Staff Member 

Invited Professor in Solid State Physics 

Visiting Scholar in Applied Physics 



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. 
1 998 Co-recipient of the Oliver E. Buckley Condensed Matter Physics Prize of the American 
Physical Society 

1 996-1 997 Appointment as Invited Professor at the Universite Paris-Sud 
1996 Elected to Academia Sinica 

1 996 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 flux 

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 
1 984 IBM Invention Achievement Award 



Chang C. Tsuei - page 2 



1980 Invention Achievement Award 
Professional Societies Honors: 

200 1 Fellow of the American Association for the Advancement of Science 
1996 Academician of Academia Sinica 
1 974 Fellow of American Physical Society 



Publications: available upon request 



BRIEF ATTACHMENT AO 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



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



Group Art Unit: 1751 
Examiner: M. Kopec 



Date: April 5, 2005 
Docket: YO987-074BZ 



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



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



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



FIFTH SUPPLEMENTAL AMENDMENT 



Sir: 



Serial No.: 08/479,810 



Page 1 of 5 



Docket: YO987-074BZ 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 




Date: April 4, 2005 

Docket: YO987-074BZ 

Group Art Unit: 1751 

Examiner. M. Kopec 

„ HAVING HIGH TRANSITION 
V USE AND PREPARATION 



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

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

AFFIDAVIT UNDER 37 C.F.R. 1.132 

Sir: 

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

1 . I received a B. S. degree in Ceramic Engineering (1 981 ) from Jew York"ltate 
College of Ceramics. Alfred University, an M. S. degree (1983) and a Ph.D. degree 
(1986), both in Materiai Science from the University of California at B irkeley. 



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



res ponse ti 



AG v 



3. I have worked as a research staff member in Material Science 
Watson Research Center of the International Business Machines 
Yorktown Heights, New York from 1986 to 2001 . From 2001 to the p 
worked as an l/T Manager in the IBM Chief Information Officer organ 



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



:xrjo 
■23 



submitted in a separate 
to the 
which were 
AMENDMENT' 



Coroorati 



at the Thomas J. 

[ion in 
esent, I have 
zation. 



temperature 



Serial No.: 08/479,810 



Pagel of 21 



Docket: YO987-074BZ 



APR 05 2005 15:38 FR I BM-flLEXANDR I A 



7032991476 TO 917008623281 



IN THE UNITED STATES PATENT ANO TRADEMARK OFFICE 



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

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




Date: April 4, 2005 
Docket YO987-074BZ 
Group Art Unit 1751 
Examiner: M. Kopec 
IDS HAVING HIGH TRANSITION 
" AJSE AND PREPARATION 



AF FIDAVIT UNDER 37 C.F.R. 1.132 

Sir. 

I, Timothy Dinger, being duly sworn, do hereby depose and ste I 

1 . I received a B. S. degree in Ceramic Engineering (1 981} from Jew York State 
College of Ceramics, Alfred University, an M. S. degree (1983) and a Ph.D. degree 
(1986), both in Materia* Science from the University of California at Berkeley. 



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



3. I have worked as a research staff member in Material Science at the Thomas J. 
Watson Research Center of the International Business Machines Corporation in 
Yorktown Heights, New York from 19B6 to 2001 . From 2001 to the p esent, I have 
worked as an l/T Manager in the IBM Chief Information Officer organ zation. 

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



in a separate 

to the 
which were 
SUPPLEMENTAL AMENDMENT' 



response 
AG 



Serial No.: 08/479,810 



Pagel of 21 



Docket YO987-074BZ 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



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



Group Art Unit: 1751 
Examiner: M. Kopec 



Date: April 4, 2005 
Docket: YO987-074BZ 



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

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



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

1 . I received a B. S. degree in Ceramic Engineering (1 981 ) from New York State 
College of Ceramics, Alfred University, an M. S. degree (1983) and a Ph.D. degree 
(1986), both in Material Science from the University of California at Berkeley. 

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

3. I have worked as a research staff member in Material Science at the Thomas J. 
Watson Research Center of the International Business Machines Corporation in 
Yorktown Heights, New York from 1986 to 2001 . From 2001 to the present, I have 
worked as an l/T Manager in the IBM Chief Information Officer organization. 

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



AFFIDAVIT UNDER 37 C.F.R. 1.132 



Sir: 



Serial No.: 08/479,810 



Page 1 of 21 



Docket: YO987-074BZ 



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

6. This affidavit is in addition to my affidavit dated December 15, 1998. I have 
reviewed the above-identified patent application (Bednorz-Mueller application) and 
acknowledge that it represents the work of Bednorz and Mueller, which is generally 
recognized as the first discovery of superconductivity in a material having a 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. 



Serial No.: 08/479,810 



Page 2 of 21 



Docket: YO987-074BZ 




10. Prior to 1986 a person having a bachelor's degree in an engineering discipline, 
applied science, chemistry, physics or a related discipline could have been trained 
within one year to reliably test a material for the presence of superconductivity and to 
flow a superconductive current in a superconductive composition. 

1 1 . Prior to 1 986 a person of ordinary skill in the art of fabricating a composition 
according to the teaching of the Bednorz-Mueller application would have: a) a Ph.D. 
degree in solid state chemistry, applied physics, material science, metallurgy, physics or 
a related discipline and have done thesis research including work in the fabrication of 
ceramic materials; or b) have a Ph.D. degree in these same fields having done 
experimental thesis research plus one to two years post Ph.D. work in the fabrication of 
ceramic materials; or c) have a master's degree in these same fields and have had five 
years of materials experience at least some of which is in the fabrication of ceramic 
materials. Such a person is referred to herein as a person of ordinary skill in the 
ceramic fabrication art. 

12. The general principles of ceramic science referred to by Bednorz and Mueller in 
their patent application and known to a person of ordinary skill in the ceramic fabrication 
art can be found in many books and articles published before their discovery, priority 
date (date of filing of their European Patent Office patent application EPO 0275343A1, 
January 23, 1987) and initial US Application filing date (May 22, 1987). An exemplary 
list of books describing the general principles of ceramic fabrication are: 

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

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

Attachment C. 



Serial No.: 08/479,810 



Page 3 of 21 



Docket: YO987-074BZ 



c) Ceramic Processing Before Firing, Onoda et al., John Wiley & 
Sons, 1978, the entire book, a copy of which is in Attachment D. 

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

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

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

a) Oxygen Defect K 2 NiF 4 - Type Oxides: The Compounds 
La 2 -xSr x Cu04-x/2 + -, Nguyen et al., Journal of Solid State Chemistry 39, 
120-127(1981). See Attachment F. 

b) The Oxygen Defect Perovskite BaLa 4 Cu5-Oi3. 4 , A Metallic (This is 
referred to in the Bednorz-Mueller application at page 21, lines 1-2) 
Conductor, C. Michel et al., Mat. Res. Bull., Vol. 20, pp. 667-671, 1985. 
See Attachment G. 

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

d) Thermal Behaviour of Compositions in the Systems x BaTiOa + 
(1-x) Ba(Ln 0 5 Bo.?) 0 3 , V.S. Chincholkar et al., Therm. Anal. 6th, Vol. 2., p. 
251-6,1980. See Attachment I. 



Serial No.: 08/479,810 



Page 4 of 21 



Docket: YO987-074BZ 



14. The Bednorz-Mueller application in the paragraph bridging pages 6 and 7 states 
in regard to the high 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 NIB element of the periodic table, 
such as La. Substitutions can be found in the rare earth (or rare 
earth-like) site or in the transition metal sites of the compositions. For 
example, the rare earth site can also include alkaline earth elements 
selected from group HA of the periodic table, or a combination of rare 
earth or rare earth-like elements and alkaline earth elements. Examples 
of suitable alkaline earths include Ca, Sr, and Ba. The transition metal 
site can include a transition metal exhibiting mixed valent behavior, and 
can include more than one transition metal. A particularly good example 
of a suitable transition metal is copper. As will be apparent later, Cu- 
oxide based systems provide unique and excellent properties as high 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. 



Serial No.: 08/479,810 



Page 5 of 21 



Docket: YO987-074BZ 



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

16. The following table (in paragraph 18) is compiled from the Table 1 of the Article 
by Rao (See Attachment AB) and the Table of high T c 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 DJB element." I disagree for the reasons given herein. 



18. Composite Table 



1 


2 


3 


4 


5 


6 


7 


# 


MATERIAL 


RAO 

ARTICLE 


HANDBOOK 
OF CHEM & 
PHYSICS 




ALKALINE 

EARTH 

ELEMENT 


RARE 
EARTH 
ELEME 
NT 


1 


La 2 Cu0 4 ^ 


V 






N 


Y 


2 


La 2 .xSr x (Ba x )Cu0 4 


V 






Y 


Y 


3 


La 2 Ca,. x Sr x Cu 2 0 6 


V 






Y 


Y 



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Docket: YO987-074BZ 



4 


YBa 2 Cu 3 0 7 




V 




Y 


Y 


5 


YBa 2 Cu40 8 




V 




Y 


Y 


6 


Y 2 Ba4Cu 7 0 15 


V 






Y 


Y 


7 


Bi 2 Sr 2 Cu0 6 


V 


V 


* 


Y 


N 


8 


Bi 2 CaSr 2 Cu 2 0 8 


V 


V 


* 


Y 


N 


9 


Bi 2 Ca 2 Sr 2 Cu 3 Oio 


V 


V 


* 


Y 


N 


10 


Bi 2 Sr 2 (Ln,. x Ce x ) 2 Cu 2 0,o 








Y 


Y 


11 


Tl 2 Ba 2 Cu0 6 


V 




* 


Y 


N 


12 


Tl 2 CaBa 2 Cu 2 0 8 


V 


V 


* 


Y 


N 


13 


Tl 2 Ca 2 Ba 2 Cu 3 Oi 0 


V 




* 


Y 


N 


14 


Tl(BaLa)Cu0 5 


V 


V 




Y 


Y 


15 


Tl(SrLa)CuO s 


V 






Y 


Y 


16 


(Tl 0 .5Pbo.5)Sr 2 Cu0 5 


V 


V 


* 


Y 


N 


17 


TlCaBa 2 Cu 2 0 7 


V 


V 


* 


Y 


N 


18 


(Tl 0 .5Pbo.5)CaSr 2 Cu 2 0 7 


V 


V 


* 


Y 


N 


19 


TlSr 2 Y 0 .5Cao. 5 Cu 2 0 7 


V 


V 




Y 


Y 


20 


TlCa 2 Ba 2 Cu 3 08 


V 


V 


* 


Y 


N 


21 


(Tl 0 .5Pbo.5)Sr 2 Ca 2 Cu 3 0 9 


V 




* 


Y 


N 


22 


TlBa 2 (Ln,. x Ce x ) 2 Cu 2 09 


V 






Y 


Y 


23 


Pb 2 Sr 2 Lno. 5 Cao.5Cu 3 08 


V 






Y 


Y 


24 


Pb 2 (Sr,La) 2 Cu 2 0 6 


V 


V 




Y 


Y 


25 


(Pb,Cu)Sr 2 (Ln,Ca)Cu 2 0 7 


V 


V 




Y 


Y 


26 


(Pb,Cu)(Sr,Eu)(Eu,Ce)Cu 2 O x 


V 


V 




Y 


Y 


27 


Nd 2 . x Ce x Cu0 4 


V 




* 


N 


Y 


28 


Cai. x Nd x Cu0 2 


V 






Y 


Y 


29 


Sri. x NdxCu02 


V 


V 




Y 


Y 


30 


Cai. x Sr x Cu0 2 






* 


Y 


N 


31 


Bao.6Ko.4Bi0 3 






* 


Y 


N 


32 


Rb 2 CsC6o 




V 


* 


N 


Y 


33 


NdBa 2 Cu 3 0 7 




V 




Y 


Y 


34 


SmBaSrCuO? 




V 




Y 


Y 


35 


EuBaSrCu 3 0 7 




V 




Y 


Y 


36 


BaSrCu 3 0 7 






* 


Y 


N 


37 


DyBaSrCu 3 0 7 








Y 


Y 


38 


HuBaSrCu 3 0 7 




V 




Y 


Y 


39 


ErBaSrCu 3 0 7 (Multiphase) 




V 




Y 


Y 


40 


TmBaSrCu 3 0 7 (Multiphase) 








Y 


Y 



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Docket: YO987-074BZ 



41 


YBaSrCu 3 0 7 




V 


* 


Y 


Y 


42 


HgBa 2 Cu0 2 




V 


* 


Y 


N 


43 


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




V 


* 


Y 


N 


44 


HgBa 2 Ca 2 Cu 3 0 8 




V 




Y 


N 


45 


HgBa 2 Ca 3 Cu40io 




V 


* 


Y 


N 



19. The first composition, La 2 Cu 0 A *s , has the form RE 2 Cu0 4 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 RE 2 TM0 4 where RE stands for the rare earths (lanthanides) 
or rare earth-like elements and TM stands for a transition metal. In these 
compounds the RE portion can be partially substituted by one or more 
members of the alkaline earth group of elements. In these particular 
compounds, the oxygen content is at a deficit. For example, one such 
compound that meets this general description is lanthanum copper oxide 
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 O 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 
(1988) is directed to Bismuth (Bi) compounds. 



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

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

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

The samples were prepared by thoroughly mixing suitable amounts of 
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 
3hat^880-C. 

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

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

The Bi-Sr-Ca-Cu-0 oxide samples were prepared from powder reagents 
of 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+1 $ and yellow HgO (98% purity, Aldrich). The 
precursor Ba 2 Cu0 3+<5 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. All 
these operations were carried out in a dry box. After evacuation, the 
tubes were sealed, placed in steel containers, as described in ref. 3, and 
heated for 5 h to reach ~800°C. The samples were then cooled in the 
furnace, reaching room temperature after -10 h. 

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

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

The preparative conditions for the new materials are considerably more 
stringent than for the previously known copper-based superconductors. 
Direct synthesis of members of this family by reaction of the component 
metal oxides or carbonates in air or oxygen at temperatures below 900°C 
is not possible because of the stability of the oxidized SrPb0 3 -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. 

32. The standard reference "Landholt-Bornstein", Volumn 4, "Magnetic and Other 
Properties of Oxides and Related Compounds Part A" (1970) lists at page 148 to 206 
Perovskite and Perovskite-related structures. (See Attachment N). Section 3.2 starting 
at page 190 is entitled "Descriptions of perovskite-related structures". The German title 
is "Perowskit-anliche Strukturen." The German word "anliche" can be translated in 
English as "like". The Langenscheidt's German-English, English-German Dictionary 
1970, at page 446 translates the English "like" as the 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 Bornstein" book published in 1970, 
more than 16 years before Applicants' priority date (January 23, 1987), shows that the 
term "perovskite-like" or "perovskite related" is understood by persons of skill in the art 
prior to Applicants' priority date. Moreover, the "Landholt-Bornstein" book cites 
references for each compound listed. Thus a person of ordinary skill in the art of 
ceramic fabrication knows how to make each of these compounds. Pages 376-380 of 
Attachment N has figures showing the crystal structure of compounds containing Bi and 
Pb. 

33. The standard reference "Landholt-Bornstein, Volume 3, Ferro- and 
Antiferroelectric Substances" (1969) provides at pages 571-584 an index to 
substances. (See Attachment P). This list contains numerous Bi and Pb containing 
compounds. See, for example pages 578 and 582-584. Thus a person of ordinary skill 
in the art of ceramic fabrication would be motivated by Applicants' application to 
fabricate Bi and/or Pb containing compounds that come within the scope of the 
Applicants' claims. 

34. The standard reference "Landholt-Bornstein Volume 3 Ferro- and 
Antiferroelectric Substances" (1969) (See Attachment P) at page 37, section 1 is 
entitled "Perovskite-type oxides." This standard reference was published more than 17 
years before Applicants' priority date (January 23, 1987). The properties of 
perovskite-type oxides are listed from pages 37 to 88. Thus the term perovskite-type 
was well known and understood by persons of skill in the art of ceramic fabrication prior 
to Applicants' priority date and more than 17 years before Applicants' priority date 
persons of ordinary skill in the art knew how to make Bi, Pb and many other perovskite, 
perovskite-like, perovskite-related and perovskite-type compounds. 



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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 K2NiF 4 structure ..." Applicants' priority document EP0275343A1 filed July 27, 
1988, is entitled "New Superconductive Compounds of the K 2 NiF 4 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 KzNiF 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, Interscience 
Publishers, 1960 states at page 96 "This structure, like these of Bi 4 Ti 2 0i 2 (IX, F12) and 
Ba Bi 4 Ti 4 0 4 (XI, 13) 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 x .iB x 0 3 x + i) 2 " have been reported (Smolenskii et al. 1961; Subbarao, 
1962), where A = Ca, Sr, Ba, Pb, etc., B = Ti, Nb, Ta and x = 2, 3, 4, or 5. 
The structure had been previously investigated by Aurivillius (1949) who 
described them in terms of Alternate (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 9 (T c = 703°K), BiBi 3 Ti 2 Ti0 12 or 



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Bi 4 Ti 3 0i2 (T c = 948°K), Ba 2 Bi 4 Ti50i8 (T c = 598°K) and Pb 2 Bi 4 Ti 5 Oi8 (T c = 
583° K). Only bismuth titanate BUTi 3 0i 2 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-Bdrnstein, 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 1969 more than 16 years prior to 
Applicants' priority date and how to make layered compounds was well known prior to 
applicants priority date. 

39. Layer perovskite type Bi and Pb compounds closely related to the Bi and Pb high 
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 Nb0 5 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 OY 
layers parallel to the basal plane and sheets of composition Bi 2 Ti 3 O 2 i 0 \ 
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 OV 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 09 structure" listing the following compounds 
Bi 3 NbTi0 9 , Bi 3 TaTi0 9 , CaBi 2 Nb 2 0 9 , SrBi 2 Nb 2 0 9 , SrBi 2 Ta 2 0 9 , BaBi 2 Nb 2 0 9 , PbBi 2 Nb 2 0 9 , 
NaBi 5 Nb 4 0i8, KBi 5 Nb 4 0i 8 . 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 4 Ti 3 0i 2 ". And at page 510, Fig. 4 shows a crystal structure in which "A 
denotes a perovskite layer Bi 2 Ti 3 O 2 i 0 ", 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 "III 
Structure of BaBi 4 Ti 4 0i 5 ". 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 BaBi 4 Ti 4 0i 5 . 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 Ni 0 O 3 F structure. 

45. Attachment AA is a list of Hg containing solid state compounds from the 1989 
Powder Diffraction File Index. Applicants do not have available to them an index from 
prior to Applicants' priority date. The Powder Diffraction File list is a compilation of all 
known solid state compounds with reference to articles directed to the properties of 
these compositions and the methods of fabrication. From Attachment AA it can be 
seen, for example, that there are numerous examples of Hg based compounds. 
Similarly, there are examples of other compounds in the Powder Diffraction File. A 
person of ordinary skill in the art is aware of the Powder Diffraction File and can from 
this file find a reference providing details on how to fabricate these compounds. Thus 
persons of ordinary skill in the art would be motivated by Applicants' teaching to look to 
the Powder Diffraction File for examples of previously fabricated composition expected 
to have properties similar to those described in Applicants' teaching. 



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46. It is generally recognized that it is not difficult to fabricate transition metal oxides 
and in particular copper metal oxides that are superconductive after the discovery by 
Applicants of composition, such as transition metal oxides, that are high 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 "[i]n this section three methods of preparation will be 
described, namely, the solid state, the coprecipitation, and the sol-gel techniques 
(Hatfi). The widely used solid-state technique permits off-the-shelf chemicals to be 
directly calcined into superconductors, and it requires little familiarity with the subtle 
physicochemical process involved in the transformation of a mixture of compounds into 
a superconductor." Poole 1988 further states at pages 61-62 "[i]n the solid state 
reaction technique one starts with oxygen-rich compounds of the desired components 
such as oxides, nitrates or carbonates of Ba, Bi, La, Sr, Ti, Y or other elements. ... 
These compounds are mixed in the desired atomic ratios and ground to a fine powder 
to facilitate the calcination process. Then these room-temperature-stabile salts are 
reacted by calcination for an extended period (~20hr) at elevated temperatures 
(~900°C). This process may be repeated several times, with pulverizing and mixing of 
the partially calcined material at each step." This is generally the same as the specific 
examples provided by Applicants and as generally described at pages 8, line 19, to 
page 9, line 5, of the Bednorz-Mueller application which states "[t]he methods by which 
these superconductive compositions can be made can use known principals of ceramic 
fabrication, including the mixing of powders containing the rare earth or rare earth-like, 
alkaline earth, and transition metal elements, coprecipitation of these materials, and 
heating steps in oxygen or air. A particularly suitable superconducting material in 
accordance with this invention is one containing copper as the transition metal." 



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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 1995 entitled "Superconductivity" 
Academic Press which has a Chapter 7 on "Perovskite and Cuprate Crystallographic 
Structures". (See Attachment Z). This book will be referred to as Poole 1995. 

At page 179 of Poole 1995 states: 

V. PEROVSKITE-TYPE SUPERCONDUCTING STRUCTURES 

In their first report on high-termperature superconductors Bednorz and 

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

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

confirmed that the new superconductors do indeed possess these 

characteristics. 

I agree with this statement. 

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



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planes and Fig. 8.4 presents details of the bonding layers for several of the cuprates 
which include binding layers for lanthanum superconductor La 2 Cu0 4 , neodymium 
superconductor Nd 2 Cu0 4 , yttrium superconductor YBa 2 Cu 3 0 2n+4 , bismuth 
superconductor Bi 2 Sr 2 Can-i Cu n 0 2n+4 , thallium superconductor TI 2 Ba 2 Ca n -iCun0 2 n + 4, and 
mercury superconductor HgBa 2 Can-iCu n CW 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 La 2 Cu0 4 . Fig. 8.1 1 at page 110 shows a schematic crystal structure showing the 
layering scheme for HgBa 2 Ca 2 Cu 3 0 8+ x. The layering shown in Poole 1996 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 was 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 c 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 . ^UJ </ ; Zoos 

Sworn to before me this ^\ day of April. 2005. 



Notary Public / y^* 1 *^^ 



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PPR 04 '05 10=02 FF 



IBM B-3 2H-04 



914 766 3794 TQ 88623281 



P.02 



50. I have personally made many samples of high Tc superconductors following the 
teaching of Bednorz and Mueller as found in the:, patent applications. In making these 
materials it was not necessary to use starting materials in stoichiometric proportions to 
produce a high 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 e 
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 e 
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: 






Notary Public 




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RPR 04 '05 15=12 



914 766 3794 



** TOTAL PAGE. 02 ** 
} PAGE. 02 



Attachment 1 





Timothy R. Dinger 
Resume 



April 5, 2005 



Timothy R. Dinger 
IBM Corporate Headquarters 
Enterprise On Demand Transformation and CIO Organization 
294 Route 100 
Somers,NY 10589 



Telephone: (914) 766-3507 
FAX: (914)766-7145 
e-mail address: dinger@us.ibm.com 



Title 



IBM Corporate Headquarters, Enterprise On Demand Transformation and CIO Organization - 
Manager, B2B Technology Strategy and Architecture, (2001 - present). Responsibility to define 
B2B technology strategy and architecture for IBM's On Demand Infrastructure and reduce that 
strategy to practice by developing and maintaining IBM's edge-of-enterprise B2B Gateway in 
support of the IBM Business Unit B2B strategies. 



Ph.D. (1986) - Materials Science and Engineering, University of California at Berkeley 
M.S. (1983) - Materials Science and Engineering, University of California at Berkeley 
B.S. (1981) - Ceramic Engineering, Alfred University 

Professional Experience 

Information Systems Department, IBM Research Division, Yorktown Heights, NY, Senior 
Manager/Research Staff Member - Watson Information Systems, (1998-2001). Responsibilities 
included financial planning and decision-making for IBM's worldwide Research Division (8 
laboratories worldwide) and formation of and coordination of the Research Division's program 
to influence and support the goals of the IBM CIO. 

Information Systems Department, IBM Research Division, Yorktown Heights, NY, 
Manager/Research Staff Member - Server Systems Engineering, (1997 - 1 998). 

Physical Sciences Department, IBM Research Division, Yorktown Heights, NY, 
Manager/Research Staff Member - Center for Scalable Computing Solutions, (1994-1996). 

Semiconductor Research and Development Center, IBM Microelectronics Division, East 
Fishkill, NY, Manager/Research Staff Member - Advanced Logic Interconnection Technology, 
(1993-1994). 



Education 



Page 1 



. , „ ™- W W April 5, 2005 

Timothy R. Dinger y 

Resume 



Semiconductor Research and Development Center, IBM Microelectronics Division East 
Fishkill, NY, Technical Assistant to John E. Kelly JH, the Director of the SRDC (1993). 

IBM Thomas J Watson Research Center, Yorktown Heights, NY, Manager/Research Staff 
Member, Interconnection Performance and Reliability Group, Semiconductor Research and 
Development Center (1991 - 1993). 

IBM T.J. Watson Research Center, Research Staff Member, Ceramic Materials Group, System 
Technology and Science Department (1987 - 1991). 

IBM T J Watson Research Center, Postdoctoral Fellow, Exploratory Packaging Materials and 
Processes Group, Semiconductor Science and Technology Department (1986-1987). 

University of California, Berkeley, CA, Graduate Student Research Assistant (1981-1985). 

Lawrence Livermore National Laboratory, Livermore, CA, Research Assistant, Ceramic Science 
Group (1981). 

Selected Publications (currently author/coauthor of 47 publications, 5 U.S. Patents) 

T P Smith IH T R. Dinger, D.C. Edelstein, J.R. Paraszczak, and T.H. Ning, "The Wiring 
Challenge: Complexity and Crowding," Future Trends in Microelectronics: Reflections on 
^n^tnNanotechnologv, S. Luryi, J. Xu, and A. Zaslavsky, eds.NATO ASI Series, Vol. 323, 
Kluwer Academic Publishers, Boston, pp. 45-56, 1996. 

T R Dinger T.K. Worthington, W.J. Gallagher and R.L. Sandstrom, "Direct Observation of 
Electronic Anisotropy in Single-Crystal Y,Ba 2 Cu 3 0x," Phys. Rev. Lett., 58, [25], 
2687-2690(1987). 

T K Worthington W.J. Gallagher, and T.R. Dinger, "Anisotropic Nature of High-Temperature 

T.R. Dinger and S.W. Tozer, "Old Behaviour in New Materials," Nature, 332, 204, 17 March 
1988. 

T R Dinger R S Rai and G. Thomas, "Crystallization Behavior of a Glass in the Y 2 0 3 -Si0 2 -A1N 
System," J. Am. Cer. Soc, 71_, [4] , 236-44(1988). 

G J Dolan G.V. Chandrashekhar, T.R. Dinger, C. Feild and F. Holtzberg, "Vortex Structure in 
YBa 2 Cu 3 0 7 and Evidence for Intrinsic Pinning," Phys. Rev. Lett., 62, [7], 827-830(1989). 

G J Dolan F Holtzberg, C. Feild, and T.R. Dinger, "Anisotropic Vortex Structure in 
Y',Ba 2 Cu,6 7 ," Phys. Rev. Lett., 62, [18], 2184-2187(1989). 

Page 2 



Timothy R. Dinger 
Resume 



April 5, 2005 



T.R. Dinger, G.J. Dolan, D. Keane, T.R. McGuire, T.K. Worthington, R.M. Yandrofski and Y. 
Yeshurun, "Flux Pinning in Single-Crystal YBa2Cu 3 07-x ," High Temperature Superconducting 
Compounds: Processing and Related Properties , Proceedings of the 1989 Symposium on High 
Temperature Superconducting Oxides: Processing and Related Properties, 1 18th Annual 
Meeting of TMS-AIME, Las Vegas, Nevada, February 27 - March 3, 1989, Edited by S.H. 
Whang and A. DasGupta, The Minerals, Metals & Materials Society, Warrendale, PA, 1989, pp. 
23-40. 

Awards 

IBM Major Outstanding Technical Achievement Award - 2005 

IBM Outstanding Technical Achievement Award - 2004 

IBM Second Plateau Invention Achievement Award - 1994 

IBM First Plateau Invention Achievement Award - 1991 

IBM Outstanding Technical Achievement Award - 1989 

IBM First Patent Application Award - 1989 

Atlantic Richfield Foundation Fellowship (U.C. Berkeley) - 1985 

Regent's Fellowship (U.C. Berkeley) - 1984 

A.L. Ehrman Memorial Scholarship and S.M. Tasheira Scholarship (U.C. Berkeley) - 1982 

Summa Cum Laude (Alfred University, College of Engineering, 1st in class) - 1981 

Alcoa Scholarship (Alfred University) - 1981 

Refractories Foundation Scholarship (Alfred University) - 1980 

Kodak Scholarship (Alfred University) - 1979 

Tredennick Scholarship - 1988 through 1981 

Pennsylvania State University Scholar (declined) - 1 997 : 
National Merit Scholarship Competition finalist -1977 



Page 3 



Timothy R. Dinger 
Resume 



April 5, 2005 



Professional Organizations and Affiliations 

Chairman, Technical Advisory Board, E2open Corporation 
Association of Computing Machinery (ACM) 
Institute of Electonics and Electrical Engineers (IEEE) 



Page 4 



BRIEF ATTACHMENT AP 



RECEIPT 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 

In re Patent Application of Date: April 12. 2006 

Applicants: Bednorzetal. Docket: YO987-074BZ 

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

Filed: June 7, 1995 Examiner: M. Kopec 

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

Mail Stop: AF 

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



SECOND AMENDMENT 
AFTER FINAL REJECTION 



In response to the Final Office Action dated October 20, 2005 and the Advisory 
Action dated December 28, 2005, please consider the following: 




Serial No.: 08/479.810 



Page 1 ofl38 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



In re Patent Application of 



Date: April 10, 2006 



Applicants: Bednorz et al. 



Docket: YO987-074BZ 



Serial No.: 08/479,810 



Group Art Unit: 1751 



Filed: June 7, 1995 



Examiner: M. Kopec 



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

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



I, Dennis Newns, declare that: 

1. I received a B. A. degree in Chemistry form Oxford University United Kingdom in 
1964 and a Ph.D. degree in Theoretical Physical Chemistry form the University of 
London in 1967. 



AFFIDAVIT OF DENNIS NEWNS 



UNDER 37 C.F.R. 1.132 



Sir: 



Page 1 of 16 



I am a theoretical solid state scientist. My resume and curriculum vitae are 
attached. 

The USPTO response dated October 20, 2005 at page 4 regarding the subject 
application cites Schuller et al "A Snapshot View of High Temperature 
Superconductivity 2002" (report from workshop on High Temperature 
Superconductivity held April 5-8, 2002 in San Diego) which the examiner states 
"discusses both the practical applications and theoretical mechanisms relating to 
superconductivity." 

The Examiner at page 4 of the Office Action cites page 4 of Schuller et al which 
states: 

"Basic research in high temperature superconductivity, because the 
complexity of the materials, brings together expertise from materials 
scientists, physicists and chemists, experimentalists and theorists... It 
is important to realize that this field is based on complex materials and 
because of this materials science issues are crucial. Microstructures, 
crystallinity, phase variations, nonequilibrium phases, and overall 
structural issues play a crucial role and can strongly affect the physical 
properties of the materials. Moreover, it seems that to date there are 
no clear-cut directions for searches for new superconducting phases, 
as shown by the serendipitous discovery of superconductivity in MgB 2 . 
Thus studies in which the nature of chemical bonding and how this 
arises in existing superconductors may prove to be fruitful. Of course, 
"enlightened" empirical searches either guided by chemical and 



Page 2 of 16 



materials intuition or systematic searches using well-defined strategies 
may prove to be fruitful. It is interesting to note that while empirical 
searches in the oxides gave rise to many superconducting systems, 
similar (probable?) searches after the discovery of superconductivity in 
MgB 2 have not uncovered any new superconductors. " 

The Examiner at pages 4 -5 of the Office Action cites pages 5- 6 of Schuller et al 

which state: 

"The theory of high temperature superconductivity has proven to be 
elusive to date. This is probably as much caused by the fact that in 
these complex materials it is very hard to establish uniquely even the 
experimental phenomenology, as well as by the evolution of many 
competing models, which seem to address only particular aspects of 
the problem. The Indian story of the blind men trying to characterize 
the main properties of an elephant by touching various parts of its 
body seems to be particularly relevant. It is not even clear whether 
there is a single theory of superconductivity or whether various 
mechanisms are possible. Thus it is impossible to summarize, or even 
give a complete general overview of all theories of superconductivity 
and because of this, this report will be very limited in its theoretical 
scope." 

The Examiner at page 5 of the Office Action cites page 7 of Schuller et al which 
states: 



Page 3 of 16 



"Thus far, the existence of, a totally new superconductor has proven 
impossible to predict from first principles. Therefore their discovery has 
been based largely on empirical approaches, intuition, and. even 
serendipity. This unpredictability is at the root of the excitement that 
the condensed matter community displays at the discovery of a new 
material that is superconducting at high temperature." 
7. I am submitting this declaration to clarify what is meant by predictability in theoretical 
solid state science. All solid state materials, even elemental solids, present 
theoretical problems. That difficulty begins with the basic mathematical formulation 
of quantum mechanics and how to take into account all interactions that are 
involved in atoms having more than one electron and where the interactions 
between the atoms may be covalent, ionic or Van der Waals interactions. A theory 
of a solid is based on approximate mathematical formalisms to represent these 
interactions. A theoretical solid state scientist makes an assessment using physical 
intuition, mathematical estimation and experimental results as a guide to focus on 
features of the complex set of interactions that this assessment suggests are 
dominate in their effect on the physical phenomena for which the theorist is 
attempting to develop a theory. This process results in what is often referred to as 
mathematical formalism. This formalism is then applied to specific examples to 
determine whether the formalism produces computed results that agree with 
measured experimental results. This process can be considered a "theoretical 
experiment." For example, applying the theoretical formalism to a particular crystal 



Page 4 of 16 




structure comprised of a particular set of atoms to compute a value of a desired 
property is in this context a "theoretical experiment." 

8. Even when a successful theoretical formalism is developed, that formalism does 
not produce a list of materials that have a particular property that is desired. Rather 
for each material of interest the same "theoretical experiment" must be conducted. 
Moreover, even if such a "theoretical experimenf indicates that the particular 
material investigated has the property, there is no assurance that it does without 
experimentally fabricating the material and experimentally testing whether it has that 
property. 

9. For example, semiconductors have been studied both experimentally and 
theoretically for more than 50 years. The theory of semiconductors is well 
understood. A material is a semiconductor when there is a filled valence band that 
is separated from the next empty or almost empty valence band by an energy that is 
of the order of the thermal energy of an electron at ambient temperature. The 
electrical conductivity of the semiconductor is controlled by adding dopants to the 
semiconductor crystal that either add electrons to the empty valence band or 
remove electrons from the filled valence band. Notwithstanding this theoretical 
understanding of the physical phenomena of semiconductivity, that understanding 
does not permit either a theoretical or experimental solid state scientist to know a 
priori what materials will in fact be a semiconductor. Even with the well developed 
semiconductor theoretical formalisms, that theory cannot be asked the question 
"can you list for me all materials that will be a semiconductor? 11 Just as an 
experimentalist must do, the theoretical scientist must select a particular material for 



Page 5 of 16 



examination. If the particular material already exists an experimentalist can test that 
material for the semiconducting property. If the particular material does not exist, 
the theoretical solid state scientist must first determine what the crystal structure will 
be of that material. This in of itself may be a formidable theoretical problem to 
determine accurately. Once a crystal structure is decided on, the theoretical 
formalism is applied in a "theoretical experiment" to determine if the material has the 
arraignment of a fully filled valence and an empty valence band with the correct 
energy spacing. Such a theoretical experiment generally requires the use of a 
computer to compute the energy band structure to determine if for the selected 
composition the correct band configuration is present for the material to be a 
semiconductor. This must be verified by experiment. Even with the extensive 
knowledge of semiconducting properties such computations are not 1 00% accurate 
and thus theory cannot predict with 1 00% accuracy what material will be a 
semiconductor. Experimental confirmation is needed. Moreover, that a theoretical 
computation is a "theoretical experimenf in the conceptual sense not different than 
a physical experiment. The theorist starting out on a computation, just as an 
experimentalist staring out on an experiment, has an intuitive feeling that, but does 
not know whether, the material studied will in fact be a semiconductor. As stated 
above solid state scientists, both theoretical and experimental, are initially guided 
by physical intuition based on prior experimental and theoretical work. Experiment 
and theory complement each other, at times one is ahead of the other in an 
understanding of a problem, but which one is ahead changes over time as an 
understanding of the physical phenomena develops. 



Page 6 of 16 




10. This description of the semiconductor situation is for illustration of the capability of 
theory in solid state science where there is a long history of both experimental and 
theoretical developments. 

11. Superconductivity was first discovered by H. Kammerlingh Onnes in 191 1 and the 
basic theory of superconductivity has been known many years before Applicants' 
discovery. For example, see the book "Theory of Superconductivity", M. von Laue, 
Academic Press, Inc., 1952 (See Attachment AD of the Third Supplementary 
Amendment dated March 1 , 2005). Prior to applicants' discovery superconductors 
were grouped into two types: Type I and Type II. 

12. The properties of Type I superconductors were modeled successfully by the efforts 
of John Bardeen, Leon Cooper, and Robert Schrieffer in what is commonly called 
the BCS theory. A key conceptual element in this theory is the pairing of electrons 
close to the Fermi level into Cooper pairs through interaction with the crystal lattice. 
This pairing results from a slight attraction between the electrons related to lattice 
vibrations; the coupling to the lattice is called a phonon interaction. Pairs of 
electrons can behave very differently from single electrons which are fermions and 
must obey the Pauli exclusion principle. The pairs of electrons act more like bosons 
which can condense into the same energy level. The electron pairs have a slightly 
lower energy and leave an energy gap above them on the order of .001 eV which 
inhibits the kind of collision interactions which lead to ordinary resistivity. For 
temperatures such that the thermal energy is less than the band gap, the material 
exhibits zero resistivity. 



Page 7 of 16 




13. There are about thirty pure metals which exhibit zero resistivity at low temperatures 
and have the property of excluding magnetic fields from the interior of the 
superconductor (Meissner effect). They are called Type I superconductors. The 
superconductivity exists only below their critical temperatures and below a critical 
magnetic field strength. Type I and Type II superconductors (defined below) are well 
described by the BCS theory. 

14. Starting in 1930 with lead-bismuth alloys, a number of alloys were found which 
exhibited superconductivity; they are called Type ll_superconductors. They were 
found to have much higher critical fields and therefore could carry much higher 
current densities while remaining in the superconducting state. 

15. Ceramic materials are expected to be insulators - certainly not superconductors, 
but that is just what Georg Bednorz and Alex Muller, the inventors of the patent 
application under examination, found when they studied the conductivity of a 
lanthanum-barium-copper oxide ceramic in 1986. Its critical temperature of 30 K 
was the highest which had been measured to date, but their discovery started a 
surge of activity which discovered materials exhibiting superconducting behavior in 
excess of 1 25 K. The variations on the ceramic materials first reported by Bednorz 
and Muller which have achieved the superconducting state at much higher 
temperatures are often just referred to as high temperature superconductors and 
form a class of their own. 

16. It is generally believed by theorists that Cooper pairs result in High Tc 
superconductivity. What is not understood is why the Cooper pairs remain together 
at the higher temperatures. A phonon is a vibration of the atoms about their 



Page 8 of 16 



equilibrium positiins in a crystal. As temperature increases these vibrations are 
more complex and the amplitude of these vibrations is larger. How the Cooper pairs 
interact with the phonons at the lower temperature, when these oscillations are less 
complex and of lower amplitude, is understood, this is the BCS theory. Present 
theory is not able to take into account the more complex and larger amplitude 
vibrations that occur at the higher temperatures. 

17. The article of Schuller referred to by the Examiner in paragraphs 4, 5 and 6 present 
essentially the same picture. 

18. In paragraph 4 above Schuller states "Of course, 'enlightened' empirical searches 
either guided by chemical and materials intuition or systematic searches using 
well-defined strategies may prove to be fruitful. It is interesting to note that while 
empirical searches in the oxides gave rise to many superconducting systems, similar 
(probable?) searches after the discovery of superconductivity in MgB 2 have not 
uncovered any new superconductors." Schuller is acknowledging that experimental 
researchers using intuition and systematic searches found the other known high Tc 
superconductors. Systematic searching is applying what is known to the 
experimental solid state scientist, that is, knowledge of how to fabricate compounds 
of the same class as the compounds in which Bednorz and Muller first discovered 
High Tc superconductivity. That a similar use of intuition and systematic searching 
"after the discovery of superconductivity in MgB 2 have not uncovered any new 
superconductors" is similar to a "theoretical experiment" that after the computation 
is done does not show that the material studied has the property being investigated, 
such as semiconductivity. The Schuller article was published in April 2002 



Page 9 of 16 




approximately one year after the expermental discovery of superconductivity in 
MgB 2 was reported on in March 2001 (Reference 8 of the Schuller article. See 
paragraph 19 of this affidavit.) This limited time of only one year is not sufficient to 
conclude that systematic searching "after the discovery of superconductivity in MgB 2 
" cannot uncover any new superconductors. Experimental investigations of this 
type are not more unpredictable than theoretical investigations since the 
experimental investigation has a known blue print or course of actions, just as does 
a "theoretical experiment." Just as an physical experimental investigation may lead 
to a null result a "theoretical experiment" may lead to a null result. In the field of 
High Tc superconductivity physical experiment is as predictable as a well developed 
theory since the experimental procedures are well known even though very 
complex. Experimental complexity does not mean the field of High Tc 
superconductivity is unpredictable since the methods of making these material are 
so well known. 

19. In paragraph 4 above Schuler refers the discovery of MgB 2 citing the paper of 
Nagamatsu et al. Nature Vol. 410, March 2001 in which the MgB 2 is reported to 
have a Tc of 39 K, a layered graphite crystal structure and made from powders 
using know ceramic processing methods. MgB 2 has a substantially simpler structure 
than the first samples reported on my Bednorz and Muller and therefore can be 
more readily investigated theoretically. There have been recent reports by Warren 
Pickett of the University of California at Davis and by Marvin L. Cohen and Steven 
Louie at the University of California at Berkeley describing progress in a theoretical 
understanding of the Tc of MgB 2 . It is not surprising that progress in the theory of 



Page 10 of 16 




superconductivity at 39 K has been made based on this relatively simple material. 

In fact a few months after the Schuller article was published in April 20002 Marvin 

.L Cohen and Steven Louie were authors on an article Choi, HJ; Roundy, D; Sun, 

H; Cohen, ML; Louie, SG "First-principles calculation of the superconducting 

transition in MgB 2 within the anisotropic Eliashberg formalism " PHYSICAL REVIEW 

B; JUL 1 , 2002; Vol. 66; p 2051 3. The following is from the Abstract of this article: 

" We present a study of the superconducting transition in MgB 2 using the 
ab initio pseudopotential density-functional method, a fully anisotropic 
Eliashberg equation, and a conventional estimate for /i*. Our study shows 
that the anisotropic Eliashberg equation, constructed with ab initio 
calculated momentum-dependent electron-phonon interaction and 
anharmonic phonon frequencies, yields an average electron-phonon 
coupling constant A=0.61 , a transition temperature Tc=39 K, and a boron 
isotope-effect exponent a(B)=0.32. The calculated values for Tc. L and 
g(B) are in excellent agreement with transport, specific-heat, and 
isotope-effect measurements, respectively . The individual values of the 
electron-phonon coupling A(k,k(')) on the various pieces of the Fermi 
surface, however, vary from 0.1 to 2.5. The observed Tc is a result of both 
the raising effect of anisotropy in the electron-phonon couplings and the 
lowering effect of anharmonicity in the relevant phonon modes." 
(Emphasis added) 



Thus the statement of the Schuller article in paragraph 5 above "The theory of high 
temperature superconductivity has proven to be elusive to date" is not totally accurate 
since shortly after the publication of the Schuller article a theory of the Tc of MgB 2 was 
published by Marvin .L. Cohen and Steven Louie. 



A month later they expanded on this in the article Choi, HJ; Roundy, D; Sun, H; 

Cohen, ML; Louie, SG "The origin of the anomalous superconducting properties of 

MgB2" NATURE, AUG 15, 2002;Vol 418; pp 758-760. The following is from the 

Abstract of this article: 

" Magnesium diboride ... differs from ordinary metallic superconductors in 
several important ways, including the failure of conventional models ... to 
predict accurately its unusually high transition temperature, the effects of 
isotope substitution on the critical transition temperature, and its 

Page 11 of 16 




anomalous specific heat .... A detailed examination of the energy 
associated with the formation of charge-carrying pairs, referred to as the 
'superconducting energy gap', should clarify why MgB 2 is different. Some 
early experimental studies have indicated that MgB 2 has multiple gaps.... 
Here we report an ab initio calculation of the superconducting gaps in 
MgB 2 and their effects on measurable quantities. An important feature is 
that the electronic states dominated by orbitals in the boron plane couple 
strongly to specific phonon modes, making pair formation favourable. This 
explains the high transition temperature, the anomalous structure in the 
specific heat, and the existence of multiple gaps in this material. Our 
analysis suggests comparable or higher transition temperatures mav 
result in layered materials based on B. C and N with partially filled planar 
orbitals. (Emphasis added) 



Thus the statement in the Schuller article in paragraph 5 above "Thus far, the existence 
of, a totally new superconductor has proven impossible to predict from first principles" 
was shown by the work of Marvin .L. Cohen and Steven Louie published shortly after 
the article of Schuller also to be not totally accurate. 

20. In paragraph 5 above Schuller states "The theory of high temperature 
superconductivity has proven to be elusive to date." As stated above although solid 
state theorist believe that Cooper Pairs are the mechanism of the High Tc 
superconductors, we do not as of yet completely understand how to create a 
mathematical formalism that takes into account the atomic vibrations at these higher 
temperatures to theoretically permit that electrons to remain paired. 

21. In paragraph 5 above Schuller further states "This is probably as much caused by 
the fact that in these complex materials it is very hard to establish uniquely even the 
experimental phenomenology." Even though these materials are complex that 
complexity does not have to be understood to make these material since 
experimental solid state scientists well understand the method of making these 
materials. The book "Copper Oxide Superconductors" by Charles P. Poole, Jr., 

Page 12 of 16 



Timir Datta and Horacio A. Farach, John Wiley & Sons (1998), [(See Attachment 23 
of The Fifth Supplemental Amendment dated March 1 , 2004)] referred to herein as 
Poole 1988 states in Chapter 5 entitled "Preparation and Characterization of 
Samples" states at page 59: 

"Copper oxide superconductors with a purity sufficient to exhibit zero resistivity 
or to demonstrate levitation (Early) are not difficult to synthesize. We believe 
that this is at least partially responsible for the explosive worldwide growth in 
these materials". 

Poole et al. further states at page 61 : 

"In this section three methods of preparation will be described, namely, the solid 
state, the coprecipitation, and the sol-gel techniques (Hatfi). The widely used 
solid-state technique permits off-the-shelf chemicals to be directly calcined into 
superconductors, and it requires little familiarity with the subtle physicochemical 
process involved in the transformation of a mixture of compounds into a 
superconductor." 

22.lt is thus clear that experimentalists knew, at the time of Benorz and Muller's 
duscovery, how to make the High Tc class of material and that to do so it was not 
necessary to precisely understand the experimental phenomenology. 

23. Charles Poole et al. published another book in 1995 entitled "Superconductivity" 
Academic Press which has a Chapter 7 on "Perovskite and Cuprate Crystallographic 
Structures". (See Attachment Z of the First Supplementary Amendment dated 



Page 13 of 16 



March 1 , 2005). This book will be referred to as Poole 1995. At page 179 of Poole 
1995 states: 

"V. PEROVSKITE-TYPE SUPERCONDUCTING STRUCTURES 

In their first report on high-termperature superconductors Bednorz and Mailer 
(1986) referred to their samples as "metallic, oxygen-deficient ... perovskite-like 
mixed-valence copper compounds." Subsequent work has confirmed that the 
new superconductors do indeed possess these characteristics." 

24. Thus Poole 1988 states that the high 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 (the patent application 
currently under examination) describes these new superconductors to have. 

25. In paragraph 5 above Schuller states: 

"The theory of high temperature superconductivity has proven to be 
elusive to date. This is ....caused by the fact ... the evolution of many 
competing models, which seem to address only particular aspects of 
the problem. The Indian story of the blind men trying to characterize 
the main properties of an elephant by touching various parts of its 
body seems to be particularly relevant. It is not even clear whether 
there is a single theory of superconductivity or whether various 
mechanisms are possible. Thus it is impossible to summarize, or even 
give a complete general overview of all theories of superconductivity 
and because of this, this report will be very limited in its theoretical 
scope." 



Page 14 of 16 




The initial development of a theory always considers the problem from many 
different aspects until the best and most fruitful approach is realized. That at this 
time "It is not even clear whether there is a single theory of superconductivity or 
whether various mechanisms are possible" does not mean that experimental solid 
state scientists do not know how make this class of High Tc materials. As stated by 
Poole 1988 and Poole 1995 the experimental solid state scientist does know how to 
make this class of High Tc materials. 
26. The Examiner at page 5 of the Office Action cites page 7 of Schuller et al which 
states: 

"Thus far, the existence of, a totally new superconductor has proven 
impossible to predict from first principles. Therefore their discovery has 
been based largely on empirical approaches, intuition, and. even 
serendipity. This unpredictability is at the root of the excitement that 
the condensed matter community displays at the discovery of a new 
material that is superconducting at high temperature." 
A first principles theory that accurately predicts all physical properties of a material 
does not exist for as simple a material as water in its solid form as ice which may 
very well be the most extensively studied solid material. Most theories of solid state 
materials have phenomenological components that are approximations based on 
empirical evidence. As stated above solid state theoretical scientists have not as of 
yet formulated a theoretical formalism that accounts for electrons remaining paired 
1 as Cooper pairs at higher temperatures. But this does not prevent experimental 
scientists from fabricating materials that have structurally similar properties to the 



Page 15 of 16 



materials first discovered by Bednorz and Muller. This is particularly true since the 
basic theory of superconductivity were also well known at the time of their discovery 
and the methods of making these materials was well known at the time of their 
discovery. It was not necessary at the time of their discovery to have the specific 
theoretical mechanism worked out in detail in order to make samples to test for High 
Tc superconductivity. Even Schuller acknowledges "empirical searches in the 
oxides gave rise to many superconducting systems." 
27. 1 hereby declare that all statements made herein of my knowledge are true and that 
all statements made on information and belief are believed to be true; and further, 
that these statements were made with the knowledge that willful false statements 
and the like so made are punishable by fine or imprisonment, or both, under Section 
1001 of Title 18 of the United States Code and that such willful false statements 
made jeopardize the validity of the application or patent issued thereon. 




Page 16 of 16 




Dr. Dennis M. Newns 

Address: Physical Science Division, IBM T.J. Watson Laboratory, Yorktown Hgts, NY. 
Phone: (914) 945-3014 
E-mail: dennisn@us.ibm.com 

Professional Preparation and Appointments 

1986-Present Physical Science Division, IBM T.J. Watson Laboratory. 
1981 Reader, Imperial College London. 
1971 Lecturer, Imperial College London. 

1969 Postdoctoral Fellow, Department of Physics, Cambridge University. 
1967 Postdoctoral Fellow, James Franck Institute, University of Chicago. 
1967 Ph.D, Imperial College London. 

Relevant Publications 

1. "Polaronic Effects in Mixed and Intermediate Valence Compounds", 
D.M. Newns and A. C. Hewson, 

J. Phys. C, 12 1665 (1979). 

2. "Mott transition field effect transistor", 
D.M. Newns, J.A. Misewich, and C.C. Tsuei, 
Appl. Phys. Lett. 73 780 (1998). 

3. "Room-temperature ferromagnetic nanotubes controlled by electron or hole doping", 
L. Krusin-Elbaum, D.M. Newns and H. Zeng, 

Nature 431 672 (2004). 

4. "Charge-exchange in atom-surface scattering - thermal versus quantum-mechanical non-adiabaticity" , 
R. Brako and D.M. Newns, 

Surf. Sci. 108 253 (1981). 

5. "Desorption induced by multiple electronic-transitions", 
JA Misewich, TF Heinz and D.M. Newns, 

Phys. Rev. Lett. 68 3737 (1992). 



1 



Significant Publications 



1. "On the solution of the Coqblin-Schrieffer Hamiltonian by the large-N expansion technique", 
N. Read and D.M. Newns, 

J. Phys. C716 3273 (1983). 

2. "Anomalous isotope effect and vanhove singularity in superconducting Cu oxides" 

C. C. Tsuei, D.M. Newns and C.C. Chi, 
Phys. Rev. Lett. 65 2724-2727 (1990). 

3. "Effect of parallel velocity on charge fraction in ion-surface scattering" , 
J. Vanwunnik, R. Brako, K. Makoshi and D.M. Newns, 

Surf. Sci. 12 618-623 (1983). 

4. "Quasi-classical transport at a van hove singularity in cuprate superconductors" 

D. M. Newns, C.C. Tsuei and R.P. Huebener, 
Phys. Rev. Lett. 73 1695-1698 (1994). 

5. "Self-Consistent Model of Hydrogen Chemisorption" D. Newns, Phys. Rev. 178 1123-1135 
(1969). 

Synergistic Activities 

1. Work with undergraduate and high school interns as part of the IBM summer research pro- 
gram. 

2. Interact with students at APS March meeting lunches. 

Recent Collaborators 

W. Donath, M. Shabes, B. Lengfield, M. Eleftheriou, P. Pattnaik, C. Zhou, I. Morgenstern, T. 
Husslein, P.B. Moore, Q.F. Zhong, L. Krusin-Elbaum, H. Zeng, H.J. Wen, R. Ludeke, T. Dode'rer, 
M.L. Klein, J.A. Misewich, C.C. Tsuei, and G.J. Martyna. 

Graduate and Postdoctoral Advisors 

Thesis Advisor : E.P. Wohlfarth, Imperial College, London. 
Postdoctoral Advisor : P.W. Anderson, University of Chicago. 
Postdoctoral Advisor : P.W. Anderson, Princeton University. 



BRIEF ATTACHMENT AQ 



RECEIPT 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 

In re Patent Application of Date: April 12, 2006 

Applicants: Bednorzetal. Docket: YO987-074BZ 

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

Filed: June 7, 1995 Examiner: M. Kopec 

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

Mail Stop: AF 

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



SECOND AMENDMENT 
AFTER FINAL REJECTION 




In response to the Final Office Action dated October 20, 2005 and the Advisory 
Action dated December 28, 2005, please consider the following: 



Serial No.: 08/479,810 



Pagelof138 





IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



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



Date: February 2, 2006 
Docket: YO987-074BZ 
Group Art Unit: 1751 
Examiner: M. Kopec 



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

Commissioner for Patents 
P.O. Box 1450 
Alexandria, VA 2231 3-1 450 



I, J.Georg Bednorz , declare that: 

1 . I am a coinventor of the referenced application. 

2. I received a M. S. Degree in Minerology/Crystallography (1 976) from the 
University of Muenster in Germany and a Ph.D. degree in Natural Science (1 982) 
from the Swiss Federal Institute of Technology (ETH) in Zuerich - Switzerland. 

3. The USPTO response dated October 20, 2005 at page 7 cites the following web 
page http://www.nobelchannel.c»rn/leamingstudio/introduction.sps?id=295&eid=0 
Which states 

It is worth noting that there is no accepted theory to explain the 
high-temperature behavior of this type of compound. The BCS theory. 
which has proven to be a useful tool in understanding 
lower-temperature materials, does not adequately explain how the 
Cooper pairs in the new compounds hold together at such high 
temperatures. When Bednorz was asked how high-temperature 
superconductivity works, he replied, "If I could tell you, many of the 
theorists working on the problem would be very surprised." 

4. This declaration is to explain the meaning of the statement attributed to me "If 
I could tell you, many of the theorists working on the problem would be very 
surprised" in response to a question from the interviewer about the mechanism of 
High Tc superconductivity. 



DECLARATION OF GEORG BEDNORZ 
UNDER 37 C.F.R. 1.132 



Sir: 



Page I of 2 




• 



5. Following the discovery of the High Tc superconductivity in oxides by my 
coinventor Alex Mueller and me, the enormous research effort conducted by 
experimentalist specialized in different disciplines of solid state science created a 
very complex scenario. After our discovery new layered perovskite-like 
CuO-compounds with comparable and higher Tc were discovered of the type that are 
reported on in our original publication and that are described in our patent 
application. These new materials were made according to known principles of 
ceramic science that we described in our patent application. The rapid experimental 
developments were guided by previous work on materials having related the 
composition and structure. This enormous amount of new information collected over 
a short period of time made it hard to get a clear picture at that time of the 
experimental situation for both experimental specialists and theorists. In addition to 
showing superconductivity at temperatures higher than previously observed, this new 
information included novel and unusual properties, so far unexplained in the 
superconducting and normal state. I am an experimental scientist and in the field of 
solid state science, because of the complexities of theory and experiment, workers in 
the field are either experimentalist or theorist and typically not both. In this field, 
including the»field of high Tc superconductivity, theory utilizes complex mathematical 
procedures about which theorists are experts. Thus theorists working in the field 
would have been surprised if, I, as an experimentalist, had been the sole person in 
the field to gain a sufficient overview and experimental and theoretical insight, to 
propose a final theory of high temperature superconductivity at this early stage of 
research. " v> 

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




Page 2 of 2 



BRIEF ATTACHMENT AR 




IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



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



Group Art Unit: 1751 
Examiner: M. Kopec 



Date: March 1, 2004 
Docket: YO987-074BZ 



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



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



FIFTH SUPPLEMENTAL AMENDMENT 



Sir: 



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



ATTACHMENT 57 



... . -a 



STATED 



° ^ l V^ TC ^25? ,T ° F COMMERCE 
and Trademark Office 

: COMMISSIONER Of PATENTS AND TRADEMARK " 
Washington. O.C. 33231 ■~*ru^ J> 



SERIAL NUMBER ' HUNG DATE 



FIRST NAMED INVENTOR 



J ATTCBNeVOOCKET K< 



J. DAVID ELLE'f T 

j r« 1 Ml £.1.1X01 UAl. F ROrKRT' 

P.O. SOX 21S 

Vf-:* J OiJN HcJGHlS:. liV ) <<':< 



PAPHR KIWBP! 



£2 Thtsat, 

xJ far response to this adon is tot to expire J — 



Parti THE FOULOWTMG ATTACHUENTfS) ARE PART OF THIS ACTION: . V? ^SjlP 

1. □ Notice of References Cited by Examiner. PT0892- 2- □ Notice re Patau Drawing. PTO-94«. 

S. D Notice o» Art C^tyAfpScanLPTO-I^W. <• □ Notice of Ink*™* Paten. Appfication. Form PTO-1S2 

5. □ Information cn How to Effect Drawing Changes. PTO-1474. 6. □ _ : 



P.rtH SUMMARY OF ACTION 



s I ? - It 4 ^ f ^"^Tf ■■ + L y... ^wn .rd^sideration. 



7^ CD 



iDcbi 

Claims. 



2; haveteen canned. 



or election requirement. 



7.DTteapc*ca«k»hasbe e n.Sedwim«^^ 
, t. Q Fome< drawings ore roourod in response to this OSes action. 

9. □ Tho corrected or subsfcrto drawings have boon tecoived cn : , L . Under 37 C.F.R. 1.84 these drawings 

, . m q aooeptable: Q not acceptable (see expfanaSon or Notice re Patent Drawing. PT0648). 

10. E]The proposed aoVMoneJ or «ubs<itote«fcae«s)oi drawings. Sed on : has (have) been D approved by the 

. examiner: Q dbapproved by tt» examirier (see exptanation). 

11. □ The proposed drawing correction. «ed_ .ha. been Q approved:. □ dsapproved (see explanation). 

12 . DAcfaiowkKJG*Hner«rs.nadeofto U.S.C.119. The certified copy has D been received □ not been received 

O been Bed in parent application, serial no. . _;Hedon . , 



• 



1. Applicant's election with traverse of Group I in Paper No. 22 
is acknowledged. The traversal is on the ground (s) that the claims 
of Groups T, II and TIT are not distinct. This is not found 
persuasive because the Examiner maintains that the superconductive 
product, process of making and method of use are directed to 
patentally distinct inventions. Although there are broad "process" 
and "method" claims that appear to encompass a great .deal of 
subject matter, the limitations in the dependent claims distinguish 
the claims of the Groups I, TT and III. 

The requirement is still deemed proper and is therefore made 
FINAL. 

2. The objection to the specification and objection of claims 1- 
11. 27-35, 40-54, 60-63 and 65-68 under 35 (JSC 112, first 
paragraph, is maintained. 

3. The following is a quotation of the first paragraph of 35 
U.S.C. § 112: 

The specification shall contain a written description of the 
invention, and of the manner and process of making and using 
it, in such full, clear, concise, and exact terms as to enable 
any person skilled in the art to which it pertains, or wi-th 
which it is most nearly connected, to make and use the same 
and shall set forth the best mode contemplated by the inventor 
of carrying out his invention. 

The specification is objected to under 35 U.S.C. § 312, first 
paragraph, as failing to provide an enabling disclosure 
commensurate with the scope of the claims. 

4. The Applicants assert that "the scope of the claims as 
presently worded is reasonable and fully merited" (page 17 of 




Serial No. 07/53,307 ~ 
Art. Unit. 33 5 

response). The Examiner disagrees- The present claims are broad 
enough to include a substantia] number of inoperable compositions. 

5. The rejection of claims 1-11. 27-35, 40-54. 60-63 and 65-68 
under 35 USC 112, second paragraph is maintained. 

6. Claims 1-11, 27-35, 40-54. 60-63 and 65-68 are rejected 
under 35 U.S.C. § 112, second paragraph, as being indefinite for 
failing to particularly point out and distinctly claim the subject 
matter which applicant regards as the invention. 

7. The amended term "rare earth-like" is vague, with respect to 
the lack of stoichiometry, Applicants argue the superconductive 
properties can be measured as the composition is varied. This is 
unpersuasive because the present claims broad enough to require an 
undue amount of experimentation. 

8. The Examiner maintains that the term "doping" is vague. 
Neither the claim or the specification discuss the limits of the 
effective amounts of doping. 

9. The Applicants assert that a discussion of "electron-phonon 
interactions to produce superconductivity" is found in the 
specification. The Examiner maintains that the term is not 
adequately .explained. The specification fails to teach how one 
determines how to enhance the "electron-phonon" interactions? 

30. The term "at least four elements" is indefinite considering 
the number of elements* in the periodic table. 



Serial No. 07/53,307 
Art Unit 115 



11. The rejection of claims 1-11. 27-35, 40-54, 60-63 and 65-68 
under 35 USC 102/103 is mai ntai ned . 

12. Claims 1-11, 27-35, 40-54, 60-63 and 65-68 are rejected under 
35 U.S.C. § 102(b) as anticipated by or, in the alternative, under 
35 U.S.C. § 103 as obvious over each of Shaplygin et.al., Nguyen 
et.al., Michel et.al. < Mat- Res. Bull, and Revue de Chimie ) . 

13. The Applicants argue that "no prima facie case has been made 
that the composition anticipates or renders obvious the subject 
matter" (page 28 of response) . The Examiner maintains that these 
materials appear to be identical to those presently claimed except 
that the superconductive properties are not disclosed. Applicants 
have not provided any evidence that the compositions of the cited 
references are in any way excluded by the languange of the present 
claims, i.e. Applicants have failed to show that these materials 
are not superconductive. Applicant's composition claims do not 
appear to exclude these materials. 

1.4. Applicants further argue that under United States patent law 
they are entitled to claim compositions which might happen to 
overlap a portion of the concention ranges broadly recited in the 
cited references. "The broad statement of a concentration range in 
the prior art does not necessarily preclude later invention within 
the concentration range" (page 29 of response). The Examiner fails 
to understand how Applicant's incredibly broad claims, some of 



* 



Seria] No. 07/53,307 5 
Art. Unit. 33 5 

which require only the presence of a "doped transition .eta] oxide" 
(see claim 42), in anyway fall "within" the scope of the 
compositions disclosed in the prior art- The cited references 
discJose very specific compostions that not. only fall within the 
scope of the claims, but appear to he identical to those 
compositions disclosed in the specification as being 
superconducting. The Examiner maintains that these materials are 
inherently superconductive and therefore render the claim 
unpatentable . 

15. With respect to Applicants arguements under 35 USC 103 
regarding the "question of non-analogous art" and the assertion the 
cited prior art is irrevelant to the present claii. the Examiner 
m aint.ains that for the present "composition" claims the references 
directed to what appear to be identical materials (both in 
composition and inherent properties) are clearly relevant. The 
cited individual disclosures appear to be sufficient to maintain 
the rejection, the Examiner is not relying on any secondary 
references to modify the teachings in the references. 

16. The rejection of claims 3-2, 5-11, 40-44, 46. 48, 53-54, 60, 
" 62 and 66 under 35 USC 102/103 is maintained. 

17 . Claims 1-2, 5-31. 40-44, 46, 48, 51-54, 60, 62 and 66 are 
rejected under 35 U.S.C. § 102(b) as anticipated by or, in the 
alternative, under 35 U.S.C. § 103 a* obvious over each of Perron- 



Serial No. 07/53,307 
Art. Unjt. 135 



-6- 



Simon et.al-, Mossner et.al., Chincholkar et.al., Amad et.al., 
Blasse et.al., Kurihara et.al. and Anderton et.al. 
18. This rejection is maintained for the reasons set forth in the 
previous paragraphs. The Examiner maintains that the cited 

references appear to disclose materials which inherently provide 
superconductive properties and therefore render the present claims 
unpatentable . 



19. THIS ACTION IS MADE FINAL- Applicant is reminded of the 
extension of time policy as set forth in 37 C.F.R. § 1.136(a). 



A SHORTENED STATUTORY PERIOD FOR RESPONSE TO THIS FINAL. ACTION 
IS SET TO EXPIRE THREE MONTHS FROM THE DATE OF THIS ACTION. IN THE 
EVENT A FIRST RESPONSE IS FILED WITHIN TWO MONTHS OF THE MAILING 
DATE OF THIS FINAL ACTION AND THE ADVISORY ACTION IS NOT MAILED 
UNTIL AFTER THE END OF THE THREE-MONTH SHORTENED STATUTORY PERIOD, 
THEN THE SHORTENED STATUTORY PERIOD WILL EXPIRE ON THE DATE THE 
ADVISORY ACTTON IS MAILED, AND ANY EXTENSION FEE PURSUANT TO 37 
C F R § 3.136(a) WILL BE CALCULATED FROM THE MAILING DATE OF THE 
ADVISORY ACTION. IN NO EVENT WTI.T, THE STATUTORY PERIOD FOR 
RESPONSE EXPIRE LATER THAN SIX MONTHS FROM THE DATE OF THIS FINAL 
ACTION . 



Any inquiry concerning this communication or earlier 
communications from the examiner should be directed to John Boyd 
whose telephone number is (703) 308-3314. , 

Any inquiry of a genera] nature or relating to the status of 
this application should be directed to the Group receptionist whose 
telephone number is (703) 308-0661. 




PAUL LfEBERMAK 
SUPERVISORY PRIMARY EXAMINES 
ART UNIT 115 



BRIEF ATTACHMENT AS 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



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



Group Art Unit: 1751 
Examiner: M. Kopec 



Date: March 1,2004 
Docket: YO987-074BZ 



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



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



FIFTH SUPPLEMENTAL AMENDMENT 



Sir: 



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



ATTACHMENT 39 



Coptrioht, 1952 

BT 

John WnatT & Sons, Inc. 
AU Right* Reserved 

Thu book or any part thereof must not be repro- 
duced tn any form without the written pa-mission 
of the publisher. 



Library of Congress Catalog Card Number: 62-7487 

PRINTED IN THE UNITED STATES OP AMERICA. 



Emphasis up 
quite generally 
istry, inorganic 
followed by the 
istry, and, sub: 
strongly empha 
More recently, 
inorganic chem 
rather than up 
remarkable the 
and continue U 
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expanded in a ( 
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Those who 1 
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sequence, thej 



Ou6 



Summary of Bond Types 



22S 



ric compounds as opposed to the normal Daltonide or stoichiometric 
compounds. As examples, one may cite certain metallic hydrides 
such as VHVh, CeHi.,, (p. 411); certain oxides such as TiO,. T _,.«, 
FeO !.«»», WOtu-ttiJ euch sulfides, selenides, and tellurides as Cux.,8, 
Cu L «Se, Cu L „Te, CuFeS LM ; the tungsten bronzes, Na,WO,; etc. 
Combinations of these types are particularly common among minerals. 

Lack of true stotehiometry of this type is associated with so-called 
defect crystal lattice*. Defects in a crystal lattice amount to variations 
from the regularity which characterizes the material as a whole. 
They are of two types: 

1. Frenkcl defect*, in which certain atoms or ions have migrated to 
interstitial positions some distance removed from the "holes" which 
they vacated. 

2. Schottky defects, in which "holes" are left in random fashion 
throughout the crystal because of migration of atoms or ions to the 
surface of the material 

Although both types of defect probably characterize crystals of non- 
stoiehiometric compounds, the Schottky defects are the more impor- 
tant. Obviously detectable departure from true stoichiometric com- 
position can result only if serious defects are present. It would follow, 
therefore, that many apparently stoichiometric compounds are not 
truly so. If excess metal is present in a crystal, it may also result 
from partial reduction of high-valent cations; whereas if excess non- 
metal is present, higher valent cations or lower valent anions than 
those normally present may be responsible. Many instances are 
known of multiple oxidation number in a single crystal. Non- 
stoicbiometric compounds often show semi-conductivity, fluorescence, 
and centers of color. For a comprehensive discussion of this rather 
complex subject, a detailed review** should be consulted. 

SUMMARY OF BOND TYPES 
The important linkages which hold together the components of 
crystalline solids and their general characteristics may be summarized 
as follows: 

1. Ionic linkages, in which the crystals are made up of regular geo- 
metrical arrangements of positive and negative ions. Such solids 
tend to possess high melting and boiling points, are hard and difficult 
to deform, and tend to be soluble in polar solvents. When dissolved 
in such solvents or fused, they are excellent conductors. Crystals 
J. S. Anderaon: Ann. Reports, 43, 104 (1946). 



1 



Valency and the Chemical Bond 



Ch. 6 



overcome. Such cage compounds have been called dathraU com- 
pounds" (Latin claihraiut, enclosed by cross bars of a grating). In 
general, they occur when mixtures of the components are crystallized 
under optimum conditions. Their properties are roughly those of 
the enclosing material Such compounds are stable at ordinary 
temperatures with respect to decomposition into their components, 
but melting or dissolution permits the enclosed component to escape. 
Examples are hydroquiiioae compounds 'which approach the com- 
position (CH«0,).-X(X «= HO, HBr, HA CH.OH, SO* CO* HCN, 
etc)- amine compounds containing eulfurous acid, eg. (p-HtNC«H«- 
NH0.-HJ3O,; phenol compounds, eg. (CH«0)«-SO,, (C«H«0), SO,, 
(C«H/))»<X>t; and certain compounds of the inert gas elements 
(pp. 382-383). 

It is obvious that the conditions under which clathrate compounds 
can form are limited and highly specific. Among those of importance ; 
are: •; 

1 An open crystal structure in the enclosing component. This i 
necessitates directed linkages holding the molecule and crystal together, ; 
sufficient extension of the groups to form a cavity of suitable sire, | 
and a rigid structure. _ , 1 

2. Small access holes to the enclosed cavity. This may result from | 
either proper disposition of groups in the formation of the crystal or j 
Bufficient surface area in the enclosing groups. \| 

3. Ready availability of the trapped component at the tune when | 
the cavity is closed. 

Such compounds are of considerable theoretical interest but « 
lacking in practical importance. Information on possible arrant 
ments in clathrate compounds and the structures which lead to them ^ 
to be found in Powell's discussions." 

NON-STOICHIOMETRIC COMPOUNDS 

The law of definite proportions is one of the basic tenets of c_„ 
Its validity is indicated by the restrictions imposed upon bond f « 
tion where electrons are involved as already outlined, and its app 
tion is generally the assumed basis for any type of chemical comtan 
tion. There are, however, many instances of apparent departure fro 
thia rule among solid compounds. Such compounds do not possess^ 
exact compositions which are predicted from electronic conaderatw 
alone and are commonly referred to as BerthoUide or non-stoichioi 

«• E. M. Powell: /. Chan. Soc, IMS, 61; Endeavour, 9, 154 (1950); ReuarA, jj 
353 (1947-1948). ' 



The textaftkit book vattetin Monotype 
modkkn 8a printed and bound by The Maple Prett Company. 
The book it printed on Tkor Cote Plate by Bergtirom Paper 
Company. The binding it Tonero effect clofk, 
Arkwrigkl-InteHaken Inc. 

The detign of Ike text and cover vaf created by Betty Binns. 
The drawing* are by F. W. Taylor. 



COFTRIGHT © 1966, BT ACADEMIC ITiCSS INC 

All rights reserved. 

No part of this book may be reproduced in any form, 
by photostat, microfilm, or any other means, without 
written permission from the publishers. 



Ill Fifth Avenue, New York, New York 10003 
United Kingdom Edition published by 

ACADEMIC FRE88 INC. (loNOOM) LTD. 

Berkeley Square House, London W.l 



Library of Congrett catalog card number: 65-26049 
First Printing, January, 1966 
Second Printing, April, 1966 

PRINTED IN THE UNITED STATES OF AMERICA 




4.2 THE LAW OF DEFINITE PROPORTIONS 




EXAuru: 1 10.0 g of .ilicon dust. Si, is exploded with 100.0 g of oxj 
forming silicon dioxide, SiO,. How many grama of SiO, arc formed 



answm Sine* 4«.7 * of Si combine, with 53J g of Ob, the quantity of O, 
quired per gram of Si is 

S3JgQ, 

46.7 g Si 

and, therefore, for 10.0 g of Si, the quantity of O, required is 



Hence, the weight of SiO, formed is 10.0 , + lU g . tlA g and the weight <rf 
uncombtned O, is 100.0 g - 11.4 g ■= 88.6 g. 

4.3 THE ATOMIC THEORY 

The weight relationships of substances participating in chemical reactions 
are clearly explained in terms of the atomic theory. Although John 
Dalton (1803) is generally recognixed as the inventor of the theory, he 
was anticipated by other scientists, particularly William Higgins (1789) 
Thus, it appears that the law of multiple proportions (Section 4.4) was 
foreshadowed by Higgms and Dalton from their respective atomic 
theories. A verified prediction made by a theory constitutes the strongest 
argument in its favor. However, the novel and central point of Dalton's 
activities was the attempt to determine the relative weights of atoms. 
This goal focused attention upon the theory, and revealed a new field of 
human endeavor that ultimately made chemistry a systematized body of 
knowledge. 
The assumptions of the atomic theory were 
(0 The elements are Composed of indivisible particles called atoms, 
(it) All the atom* of a given dement possess identical properties, for 
example, mass. 



4. Atoms and moleculet 





BRIEF ATTACHMENT AT 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



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



Group Art Unit: 1751 
Examiner: M. Kopec 



Docket: YO987-074BZ 



Date: March 1 , 2004 



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



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



FIFTH SUPPLEMENTAL AMENDMENT 



Sir: 



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



ATTACHMENT 42 




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BRIEF ATTACHMENT AU 



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

(g> H DESCRIPTION 

Technical Field 



5 This invention relates to a new class of superconducting 

compositions having high superconducting transition 
temperatures and methods for using and preparing these 
compositions, and more particularly to superconducting 
compositions including copper and/or other transition 

0 metals, the compositions being characterized by a 

superconducting phase and a layer-like structure. 



Background Art 

Superconductivity is usually defined as the complete 
loss of electrical resistance of a material at a well- 
defined temperature. It is known to occur in many ma- 
terials, including about a quarter of the elements of 
the periodic table and over 1000 alloys and other 
multi-component systems. Generally, superconductivity 



Y0987-07A/; 



is considered to be a property of the metallic state of 
a material since all known superconductors are metallic 
under the conditions that cause them to be supercon- 
ducting. A few normally non-metallic materials, for 
example, become superconducting under very high pressure 
wherein the pressure converts them to metals before they 
exhibit superconducting behavior. 

Superconductors are known to be very attractive for the 
generation and energy-saving transport of electrical 
power over long distances , and as materials used to form 
the coils of very strong magnets. These magnets are used 
in, for example, plasma and nuclear physics, nuclear 
magnetic resonance medical diagnosis systems, and in 
connection with the magnetic levitation of fast trains. 
Other potential uses of superconducting materials occur 
in power generation systems using thermonuclear fusion 
where very large magnetic fields must be provided, 
superconducting magnets being the only possible means 
for providing such high fields. In addition to these 
applications, superconductors are known in high speed 
switching devices, s&ch as Josephson type switches, and 
in high density packaging and circuit layouts. Super- 
conductors also are used in different types of elec- 



Y0987-074*. 



tronic instrumentation, such as magnetic susceptotneters 
and magnetometers. 

While the advantages of superconductors are quite obvi- 
ous to scientists and engineers, the common disadvantage 
of all presently known superconductive materials lies 
in their very low transition temperature. This temper- 
ature is often called the critical temperature T* c and 
is the temperature above which superconductivity will 
not exist. Usually is on the order of a few degrees 
Kelvin. The element with the highest T^ is niobium whose 
T^ is 9.2°K. The composition having the highest previ- 
ously known T is Nb.Ge which exhibits a T of about 23°K 
c 3 c 

at ambient pressure. Transition metal alloy compounds 
of the A15(Nb 3 Sn) and Bl(NbN) structure have been shown 
to have high superconducting transition temperatures. 
Among the A15 compounds is the aforementioned composi- 
tion Nb^Ge. Some of these compositions are described 
in J. Muller, Rep. Prog. Phys. 43, 663 (1980), and M. 
R. Beasley et al, Phys. Today, 37 (10), 60 (1984). 

It is known in the art that a small number of oxides will 
exhibit superconductivity. Reference is made to D.C. 
Johnston et al, Mat. Res. Bull. 8, 777 (1973), which 
describes high temperature superconductivity in the Li- 



Y0987-074Y. 



Ti-0 system with superconducting onsets as high as 
13.7°K. These materials have multiple crystal lographic 
phases including a spinel structure exhibiting the high 
T . Other metallic oxides, such as the perovskite Ba- 
Pb-Bi-0 system^ can exhibit superconductivity due to high 
electron-phonon coupling in a mixed valent compound, as 
described by G. Binnig et al, Phys. Rev. Lett., 45, 1352 
(1980), and A.W. Sleight et al, Solid State Communi- 
cations, 17, 27 (1975). 



As is evident from the foregoing, superconductors pres- 
ently known require liquid helium for cooling and this, 
in turn, requires an elaborate technology and a consid- 
erable investment in cost and energy. Accordingly, it 
is a primary object of the present invention to provide 
new compositions which exhibit high and methods for 
using and producing the same. 

It is another object of the present invention to provide 
new superconducting compositions and methods for using 
and making them wh^re cooling with liquid helium is not 
required in order to have superconductive properties in 
the compositions. 



YO987-074)< 



It is another object of the present invention to provide 
novel superconductive materials that are multi-valent 
oxides including transition metals, the compositions 
having a perovskite-like structure- 
It is a further object of the present invention to pro- 
vide novel superconductive compositions that are oxides 
including rare earth and/or rare earth-like atoms, to- 
gether with copper or other transition metals that can 
exhibit mixed valent behavior. 

It is a still further object of the present invention 
to provide novel superconductive compositions exhibiting 
high T" c , where the compositions are oxides including a 
phase having a layer-like structure and including cop- 
per. 

It is a still further object of the present invention 
to provide new superconductive compositions exhibiting 
high T c> where the superconductive compositions include 
layered structures including a rare earth and/or rare 
earth -like element and a transition metal. 

It is another object of this invention to provide a new 
class of superconducting compositions characterized by 



Y0987-074V: 




a T c greater than 26 °K, and methods for making and using 
these compositions. 

It is another object of this invention to provide new 
compositions and methods for using them, where the com- 
5 positions include a multi-valcnt oxide of copper and 

exhibit a T greater than 26°K. 

The basis for our invention has been described by us in 
the following previously published article: J.G. 
Bednorz and K.A. Muller, Zeitschrift fur Physik B - 
Condensed Matter. 64, pp. 189-193^ 

Another article of interest. by us is J.G. Bednorz, K.A. • 
Muller, M. Takashige, Europhysics Letters, 3(3), pp. 
379-385 (1987). 



Summary of the Invention 

This invention relates to novel compositions exhibiting 
superconductivity at temperatures higher than those ob- 
tained in prior known superconductive materials, and to 
methods for using and forming these compositions . These 
compositions can carry supercurrents (i,.e., electrical 



20 



Y0987-074X 



currents in a substantially zero resistance state of the 
composition) at ^temperatures ^iC'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^fis one 
whose properties make it essentially a rare earth ele- 
ment. An example is a group IIIB element of the periodic 
table, such as La. Substitutions can be found in the 
rare earth (or rare earth-like) site or in the transi- 
tion metal sites of the compositions. For example, the • 
rare earth site can also include alkaline earth elements 
selected from group IIA of the periodic table, or a 
combination of rare earth or rare earth- like elements 
and alkaline earth elements. Examples of suitable 
alkaline earths include Ca, Sr, and Ba. 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 appar- 
ent later, Cu- oxide based systems provide unique and 
excellent properties as high T superconductors. 



Y0987-074X 



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. If an alkaline 
earth element (AE) were also present, the 'compos it ion 
would be represented by the general formula RE-AE-TM-O. 

The ratio (AE,RE) : TM is generally approximately 1:1, 
but can vary from this as will be shown by examples where 
the ratio (AE.RE) : TM is 2:1. Of course, the amount 
of oxygen present in the final composition will adjust 
depending upon the processing conditions and will be 
such that the valence requirements of the system are 
satisfied. 

The methods by which these superconductive compositions 
can be made can use known principles of ceramic fabri- 
cation, including the mixing of powders containing the 
rare earth or rare earth-like, alkaline earth, and 



Y0987-074X 



- 8 - 



transition metal elements, coprccipitation of these ma- 
terials, and heating steps in oxygen or air. 

A particularly suitable superconducting material in ac- 
cordance with this invention is one containing copper 

2+ 

as the transition metal. Copper can exist in a Cu~ or 
Cu"* + mixed valence state. The statc(s) assumed by cop- 
per in the overall composition will depend on the amount 
of oxygen present and on any substitutions in the crys- 
talline structure. Very high T_ has been found in Cu- 
oxide systems exhibiting mixed valence states, as 
indicated by conductivity and other measurements. Cop- 
per oxide systems including a rare earth or rare earth- 
like element, and an alkaline earth element, are unique 
examples of this general class of superconducting lay- 
ered copper oxides which exhibit greater than 26°K. 

These and other objects, features, and advantages will 
be apparent from the following more particular de- 
scription of the preferred embodiments. 



Brief Description of the Drawings 



Y0987-074y 



FIG. 1 is a schematic illustration of a representative 
circuit used to measure dc conductivity in the high T 
superconductors of this invention. 

FIG. 2 is a plot of the temperature dependence and 

resistivity in the composition Ba La,. Cu,.OL,., . for 
x 5-x 5 5(3-y) 

samples "with x(Ba)=l (upper two curves, left scale) and 
x(Ba)=0.75 (lower curve, right scale). The influence 
of current density through the composition is also 
shown . 

FIG. 3 is a plot of the low temperature dependence of 
resistivity in the composition Ba^La^ ^Cu^O^^ ^ with 
x(Ba))=l, for different annealing conditions (i.e., 
temperature and oxygen partial pressure. 

FIG. A is a plot of the low-temperature resistivity of 
the composition Ba x La 5_ x Cu 5 0 5 ( 3 _ y j with x(Ba)= 0.75, 
recorded for different densities of electrical current 
through the composition. 



Description of the Preferred Embodiments 



Y0987-074Y 



- 10 - 



The superconductive compositions of this invention are 
transition metal oxides generally having a mixed valence 
and a layer-like crystalline structure, and exhibit T c 's 
higher than those of previously known superconducting 
materials. These compositions can also include a rare 
earth site in the layer-like structure where this site 
can be occupied by rare earth and rare earth- like atoms, 
and also by alkaline earth substitutions such as Ca, Sr, 
and Ba. The amount of oxygen present will be such that 
the valence requirements of the system are satisfied, 
the amount of oxygen being somewhat a function of the 
processing steps used to make the the superconductive 
compositions. Non-stoichioraetric amounts of oxygen can 
be present in these compositions. The valence state of 
the elements in the oxide will be determined by the final 
composition in a manner well known to. chemists . For 

example, the transition metal Cu may be present in some 

2+ 3+ 
compositions in both a Cu and a Cu state. 

An example of a superconductive compound having a 
layer-type structure in accordance with the present in- 
vention is an oxide; of the general composition RE^TMO^, 
where RE stands for the rare earths (lantliaaidcs) or 
rare earth-like elements and TM stands for a transition 
metal. In these compounds the RE portion can be par- 



Y0987-074X 



tially substituted by one or more members of the 
alkaline earth group of elements. In these particular 
compounds, the oxygen content is at a deficit.- 

For example, one such compound that meets this general 
description is lanthanum copper oxide La 2 CuO^ in which 
the lanthanum - which belongs to the IIIB group of 
elements - is in part substituted by one member of the 
neighboring IIA group of elements, viz. by one of the 
alkaline earth metals (or by a combination of the mem- 
bers of the IIA group), e.g., by barium. Also, the ox- 
ygen content of the compound can be incomplete such that 
the compound will have the general composition 
La 2 _ x Ba x CuO^_ y , wherein x < 0.3 and y < 0.5. 

Another example of a compound meeting this general for- 
mula is lanthanum nickel oxide wherein the lanthanum is 
partially substituted by strontium, yielding the general 
formula La 2 ^Sr^NiO^ y . Still another example is cerium 
nickel oxide wherein the cerium is partially substituted 

by calcium, resulting in Ce„ Ca NiO. 

2-x x A-y 

The following description will mainly refer to barium 
as a partial replacement for lanthanum in a La 7 CuO^ 
compound because it is in the Ba-La-Cu-0 system that 



Y0987-074X 



- 12 - 



many laboratory tests have been conducted. Some com- 
pounds of the general Ba-La-Cu-0 system have l>een de- 
scribed by C. Michel and B. Raveau in Rev. Chira. Min. 
21 (1984) 407, and by C. Michel, L. Er-Rakho and B. 
Raveau in Hat. Res. Bull., Vol. 20, (1985) 667-671. They 
did not, however, find or try to find superconductivity. 
These references and their teachings regarding 
perovskite-like layered oxides of mixed valent transi- 
tion metals, and their preparation, are herein incorpo- 
rated by reference. 

Experiments conducted in connection with the present 

invention have revealed that high-T^ superconductivity 

is present in compounds where the rare earth or rare 

earth-like element is partially replaced by any one or 

more of the members of the IIA group of elements, i.e., 

the alkaline earth metals. Actually, the T of 
2+ 

La^CuO^, ^ with the substitution Sr is higher and its 

superconductivity- induced diamagnetism larger than that 

2+ 2+ 
found with the substitutions Ba and Ca 

The Ba-La-Cu-0 system can exhibit a number of 
crystal lographic phases, namely with mixed-valcnt copper 
constituents which have itinerant electronic states be- 
tween non-Jahn-Teller Cu"* and Jahn-Teller Cu^ + ions. 



Y0987-074X 



This applies likewise to systems where nickel is used 

in place of copper, with Ni^ + being the Jahn-Teller 
2+ 

constituent, and Ni being the non-Jahn-Tcller con- 
stituent. The existence of Jahn-Teller polarons in 
conducting crystals was postulated theoretically by K.H. 
Hoeck, H. Nickisch and H. Thomas in Helv. Phys. Acta 56 
^ 1983) ^23^. Polarons have large electron-phonon inter- 
actions and, therefore, are favorable to the occurrence 
of superconductivity at higher critical temperatures. 

Samples in the Ba-La-Cu-0 system, when subjected to X- 
ray analysis, revealed three individual crystal lographic 
phases, viz. 

• a first layer-type perovskite-like phase, related ' 
to the 

K 2 NiF^ structure, with the general composition 

La„ Ba CuO. , with 
2-x x A-y' 

x « 1 and y > 0; 

• a second, non-conducting CuO phase; and 

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



Y0987-07AK 



- 14 - 



Of these three phases the first one appeared to be re- 
sponsible for the observed high-T c superconductivity, 
the critical temperature showing a dependence on the 

barium concentration in that phase. Obviously, the Ba^ + 

2+ 

substitution caused a mix ed-va lent state of Cu and 
3+ 

Cu to preserve charge neutrality. It is assumed that 
the oxygen deficiency, y, is the same -in the doped and 
undoped crystallites. 



In this application, the terms transition metal oxide, 
copper oxide, Cu-oxide, etc. are meant to broadly in- 
clude the oxides which exhibit superconductivity at 
temperatures greater than 26°K. Thus, the term copper 
oxide can mean, among other things, an oxide such as 

CuO, in the mixed oxide composition La„ Ba CuO. 
4-y 2-x x 4-y 

Both La 2 Cu0 4 and LaCuC> 3 are metallic conductors at high 
temperatures in the absence of barium. Actually, both 
are metals like LaNi0 3 - Despite their metallic charac- 
ter, the Ba-La-Cu-0 type materials are essentially ce- 
ramics, as are the other compounds of the RE^TMO^j^ type, 
and their manufacture generally follows the known prin- 
ciples of ceramic fabrication. The preparation of a 
superconductive Ba-La-Cu-0 compound, for example, in 



Y0987-074/ 



accordance with the present invention typically involves 
the following manufacturing steps: 

• Preparing aqueous solutions of the respective 
nitrates of barium, lanthanum and copper and 
coprecipitation thereof in their appropriate ra- 
tios, 

• adding the coprecipitate to oxalic acid and 
forming an intimate mixture of the respective 
oxalates. 

• decomposing the precipitate and causing a solid- • 
state reaction by heating the precipitate to a 
temperature between 500 and 1200°C for one to eight 
hours. 

• pressing the resulting product at a pressure of 
about 4 kbar to form pellets. 

• re-heating the pellets to a temperature between 
500 and 900°C for one half hour to three hours for 
sintering. 



Y0987-07AX 



- 16 - 



It will be evident to those skilled in the art that if 
the partial substitution of lanthanum by another 
alkaline earth element, such as strontium or calcium, 
is desired, the particular nitrate thereof will have to 
be used in place of the barium nitrate of the example 
process described above. Also, if the copper of this 
example is to be replaced by another transition metal, 
the nitrate thereof will obviously have to be employed. 
Other precursors of metal oxides, such as carbonates or 
hydroxides, can be chosen in accordance with known 
principles. 

Experiments have shown that the partial contents of the 

individual compounds in the starting composition play 

an important role in the formation of the phases present 

in the final product. While, as mentioned above, the 

final Ba-La-Cu-0 system obtained generally contains the 

said three phases, with the second phase being present 

only in a very small amount, the partial substitution 

of lanthanum by strontium or calcium (and perhaps 

beryllium) will result in only one phase existing in the 

final La Sr CuO C- or La.. Ca CuO, , respectively. 

2-x x A-y 2-x x 4-y v J ' 

provided xi< 0.3. 



Y09S7-074K 



With a ratio of 1:1 for the respective (Ba, La) and Cu 
contents, it is expected that the three phases will oc- 
cur in the final product. Setting aside the second 
phase, i.e. the CuO phase whose amount is negligible, 
the relative volume amounts of the other two phases are 

dependent on the barium content in the La„, Ba CuO. 

2-x x A-y 

complex. At the 1:1 ratio and with an x = 0.02, the 
onset of a localization transition is observed, i.e., 
the resistivity increases with decreasing temperature, 
and there is no superconductivity. 

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

With a (Ba, La) versus Cu ratio of 2:1 in the starting 

composition, the composition of the La^CuO^Ba phase, 

which appears to be responsible for the 

superconductivity, is imitated, with the result that now 

only two phases are present, the CuO phase not existing. 

With a barium content of x = 0.15, the resistivity drop 

occurs at T = 26°K. 
c 

The method for preparing these Ba-La-Cu-0 sample com- 
plexes used two heat treatments for the precipitate at 



Y0987-074* 



- 18 - 



an elevated temperature for several hours. In the ex- 
periments carried out in connection with the present 
invention it was found that best results were obtained 
at 900°C for a decomposition and reaction period of 5 
hours, and again at 900°C for a sintering period of one 
hour. These values apply to a 1:1 ratio composition as 
well as to a 2:1 ratio composition. 

For the 2:1 ratio composition, a somewhat higher tem- 
perature is permissible owing to the higher melting 
point of the composition in the absence of excess copper 
oxide. However, a one-phase compound was not achieved 
by a high temperature treatment. 



Y0987-07A/ 



- 19 - 




Conductivity Measurements (FIGS. 1-4) 

The dc conductivity of representative Ba-La-Cu-0 com- 
positions was measured to determine their low temper- 
ature behavior and to observe their high T c - These 
measurements were performed using the well known four- 
point probe technique, which is schematically illus- 
trated in FIG. 1. Rectangular shaped samples 10 of 

Ba x\ La 5-x\ Cu 5°5(3-y) Were cut from sinter e d pellets, and 
provided with gold sputtered electrodes 12A and 12B, 
about 0.5 microns thick. Indium wires 14A and 14B con- 
tact electrodes 12A and 12B, respectively. The sample 
was contained in a continuous flow cryostat 16 
(Leybold-Hereaus) and measurements were made over a 
temperature range 300-4*Z°K. 

Electrodes 12A and 12B are connected in a circuit in- 
cluding a current source 18 and a variable resistor 20. 
Indium leads 22A and 22B are pressed into contact with 
sample 10 and fixed with silver paint 24. Leads 22A, 
22B are connected to a voltage reading instrument 26. 
Since the current and voltage are accurately determined, 
the resistivity of the sample 10 is then known. In the 
configuration used for these measurements, a computer 
was used to provide a computer-controlled fully- 



YO987-074X. 



- 20 - 



automatic system for temperature variation, data acqui- 
sition and processing. 



In FIG. 2, the low temperature dependence of resistivity 
lut*^ ty, measured in ohm-cms) in the composition 

of x. For the upper two curves, the value of x(Ba) is 
1 and the left side vertical scale is used. For the 
lower curve, the value of x is 0.75, and the resistivity 
scale on the right hand side of the figure is used. The 

data is taken for different values of current density: 

2 2 
0.25 A/ cm for the top curve and 0.50 A/cm for the 

middle and bottom curves. 

For barium-doped samples with x(Ba) < 1.0, for example 
with x < 0.3, at current densities of 0.5A/cm 2 , a high- 
temperature metallic behavior with an increase in 
resistivity at low temperatures was found as depicted 
in FIG. 2. At still lower temperatures, a sharp drop 
in resistivity (> 90%) occurred which for higher current 
densities became partially suppressed (FIG. 1 upper 
curves, left scale). This characteristic drop was 
studied as a function of the annealing conditions, i.e. 
temperature and oxygen partial pressure as shown in FIG. 
2. For samples annealed in air, the transition from 



Y0987-074X 



itinerant to localized behavior , as indicated by the 
minimum in resistivity in the 80°K range, was not found 
to be very pronounced. Annealing in a slightly reducing 
atmosphere, however, led to an increase in resistivity 
and a more pronounced localization effect. At the same 
time, the onset of the resistivity drop was shifted to- 
wards the 30°K region. Curves A and 5 (FIG. 3), recorded 
for samples treated at 900°C, show the occurrence of a 
shoulder at still lower temperatures, more pronounced 
in curve 6. At annealing temperatures of 1040°C, the 
highly conducting phase has almost vanished. Long 
annealing times and/or high temperatures will generally 
destroy the superconductivity. 

The mixed -va lent state of copper is of importance for 
electron-phonon coupling. Therefore, the concentration 
of electrons was varied by the Ba/La ratio. A typical 
curve for a sample with a lower Ba concentration of 0.75 
is shown in FIG. 2(right scale). Its resistivity de- 
creases by at least three orders of magnitude, giving 
evidence for the bulk being superconducting below 13°K 
with an onset around 35°K, as shown in FIG. 4 on an ex- 
panded temperature scale. FIG. A also shows the influ- 
ence of the current density, typical for grauulur 



Y09S7-07AX 



- 22 - 



compounds. Current densities of 7.5, 2.5, and 0.5 A/cm 2 
were passed through the superconducting composition. 

When cooling the samples from room temperature, the 
resistivity data first show a metal-like decrease. At 
low temperatures, a change to an increase occurs in the 
case of Ca substituted compounds and for the Ba- 
substituted samples. This increase is followed by a 
resistivity drop, showing the onset of superconductivity 
at 22 ± 2°K and 33 ± 2° K for the Ca and Ba compounds, 
respectively. In the Sr compound, the resistivity re- 
mains metallic down to the resistivity drop at AO ± 1°K. 
The presence of localization effects, however, depends 
strongly on alkaline-earth ion concentration and sample 
preparation, that is to say, on annealing conditions and 
also on the density, which have to be optimized. All 
samples with low concentrations of Ca, Sr, and Ba show 
a strong tendency to localization before the resistivity 
drops occur. 

Apparently, the onset of the superconductivity, i.e. the 
value of the critical temperature 7^, is dependent on, 
among other parameters, the oxygen content of the final 
compound. It seems that for certain materials, an oxy- 
gen deficiency is necessary for the material to have a 



Y0987-074X 



- 23 - 




high-T. behavior. In accordance with the present in- 
vention, the method described above for making the 
La 2 Cu0 4 :Ba cora P lex is complemented by an annealing step 
during which the oxygen content of the final product can 
be adjusted. Of course, what was said in connection with 
the formation of the La^uO^rBa compound likewise ap- 
plies to other compounds of the general formula REJIMO, 
: AE (where AE is an alkaline earth element), such as, 
e.g. Nd 2 NiO A :Sr. 

In the cases where a heat treatment for decomposition 
and reaction and/or for sintering was performed at a 
relatively low temperature, i.e., at no more than 950°C, 
the final product is subjected to an annealing step at 
about 900°C for about one hour in a reducing atmosphere. 
It is assumed that the net effect of this annealing step 
is a removal of oxygen atoms from certain locations in 
the matrix of the RE^IO^ complex, thus creating a dis- 
tortion in its crystalline structure. The 0^ partial 
pressure for annealing in this case may be between 10 _1 
and 10 "* bar. 

In those cases where a relatively high temperature 
(i.e., above 950°C) is employed for the heat treatment, 
it might be advantageous to perform the annealing step 



Y0987-07AX 



- 2U - 



in a slightly oxidizing atmosphere. This would make up 
for an assumed exaggerated removal of oxygen atoms from 
the system owing to the high temperature and resulting 
in a too severe distortion of the system's crystalline 
structure. 

Resistivity and susceptibility measurements as a func- 
tion of temperature of Sr 2+ and Ca 2+ -doped La CuO 

2 4-y 

ceramics show the same general tendency as the 
2+ 

Ba -doped samples: a drop in resistivity p (T) , and a 
crossover to diamagnetism at a slightly lower temper- 
ature. The samples containing Sr 2+ actually yielded a 
higher onset than those containing Ba 2+ and Ca 2+ . Fur- 
thermore, the diamagnetic susceptibility is about three . 
times as large as for the Ba samples. As the ionic ra- 
dius of Sr 2+ nearly matches that of La 3 *, it seems that 
the size effect does not cause the occurrence of 
superconductivity. On the contrary, it is rather ad- 
verse, as the data on Ba 2+ and Ca 2+ indicate. 

The highest T. for each of the dopant ions investigated 
occurred for those concentrations where, at room tem- 
perature, the RE 2 _ x TMO A _ y structure is close to the 
or thorhombic- tetragonal structural phase transition, 
which may be related to the substantial electron -phonon 



Y0987-074X 



- 25 - 



interaction enhanced by the substitution. The 
alkaline-earth substitution of the rare earth metal is 
clearly important, and quite likely creates TM ions with 
no e g Jahn-Tellcr orbitals. Therefore, the absence of 
these Jahn-Teller orbitals, that is, Jahn-Teller holes 
near the Fermi energy, probably plays an important role 
in the T enhancement. 



While examples have been given using different transi- 
tion metal elements in the superconducting compositions, 
copper oxide compositions having mixed valence appear 
to be unique and of particular importance, having 
superconducting properties at temperatures in excess of 
26°K. These mixed valent copper compositions can in- 
clude a rare earth element and/or a rare earth-like el- 
ement which can be substituted for by an alkaline earth 
element. The amount of oxygen in these compositions 
will vary depending upon the mode of preparation and 
will be such as to meet the valence requirements of the 
composition. These copper-based compositions have a 
layer-like structure, often of a perovskite type. For 
a more detailed description of some of the types of 
crystal lographic structures that may result, reference 
is made to the aforementioned publication by Michel and 



Y0967-07A>< 



- 26 - 



Raveau in Rev. Chin. Min. 21, 407 (1984), and to C. 
Michel et al, Nat. Res. Bull., Vol. 20, 667-671 (1965). 

While the invention has been described with respect to 
particular embodiments thereof, it will be apparent to 
those of skill in the art that variations can be made 
therein without departing from the spirit and scope of 
the present invention. For example, while the range of 
compositions includes rare earth elements and transition 
metal elements, the ratios of these elements can be 
varied because the crystalline structure can accommodate 
vacancies of these elements and still retain a layer- 
like structural phase exhibiting superconductivy. 

Further, the stoichiometry or degree of non- 
stoichiometry of oxygen content (i.e., oxygen deficit 
or surplus) of these compositions can be varied by using 
reducing or oxidizing atmospheres during formation of 
the compounds and by using different doping amounts in 
the rare earth and transition metal sites of the crystal 
structure. This type of distortion of the crystal 
structure and the many forms that it can encomposs are 
readily apparent from reference to the a foremen Lioned 
Michel and Ravcau publications. Thus, the invention 
broadly relates to mixed (doped) transition metal oxides 



Y0987-074 >( 



having a layer- like structure that exhibit supercon- 
ducting behavior at temperatures Ln excess of 26°K. 
these materials, a mixed copper oxide having multi- 
valent states provides high T c and favorable supercon 
ducting properties. 



YO987-074y. 



- 28 - 



Having thus described our invention what we claim as new 
and desire to secure as Letters Patent, is: 



1 1. A superconductive composition having a transition 
^ temperature greater than 26°K, the composition in- 

^^vv«*^ ^ eluding a rare earth or -naar^rare earth- like ele- 

^ ment, a transition metal element capable of 

r ^|^1 exhibiting multivalent states and oxygen, and in- 



^ eluding at least one phase that exhibits 



7 



superconductivity at temperature in excess of 26°K. 



2. The composition of claim 1, further including an 

alkaline earth element substituted for at least one 
atom of said rare earth or rare earth- like element 
in said composition. 



The composition of claim 2, where said transition 
metal is Cu . 



Y0987-074"K 



- 29 - 



I 

3 



i 

3 



4 



i 



A. The composition of claim 3. where said alkaline earth 
. element is selected from the group consisting of 
^ Ca, Ba, and Sr. 



5. The composition of claim 1, where said transition 

metal element is selected from the group consisting 
of Cu, Ni, and Cr. 



6. The composition of claim 2, where said rare earth 
or rare earth-like element is selected from the 
group consisting of La, Nd, and Ce. 



7. The composition of claim 1, where said phase is 
crystalline with a perovskite-like structure. 



8. The composition of claim 2, where said phase is 
crystalline with a perovskite-like structure. 



9. The composition of claim 1, where said phase exhibits 
a layer- like crystalline structure. 



Y0987-074X 



- 30 - 



10. The composition of claim 1, where said phase is a 
mixed copper oxide phase. 

11. The composition of claim 1, where said composition 
is comprised of mixed oxides with alkaline earth 
doping. 

12. A superconducting combination, including a 
superconductive composition having a transition 
temperature > 26°K, 

means for passing a superconducting electrical 
current through said composition while said compo- 
sition is at a temperature > 26°K. , and 

cooling means for cooling said composition to a 
superconducting state at a temperature in excess 
of 26°K. 

13. The combination of claim 12. where said 

superconductive composition includes a transition 
metal oxide. 



Y0987-074X 



- 31 - 



14. The combination of claim 12, where said 

superconductive composition includes Cu-oxide. 

15- The combination of claim 12, where said 

superconductive composition includes a multivalent 
transition metal, oxygen, and at least one addi- 
tional element. 

16. The combination of claim 15, where said transition 
metal is Cu. 

17. The combination of claim 15, where said additional 
element is a rare earth or rare earth-like element. 



The combination of claim 15, where said additional 
element is. an alkaline earth element. 



19. The combination of claim 12, where said compositio 
includes a perovskite-like superconducting phase. 



Y0987-074/ 



- 32 - 



1 20. Tlie combination of claim 12, where said composition 
includes a substituted transition metal oxide. 

| 21. The combination of claim 20, where said substituted 

3, transition metal oxide includes a multivalent 

^ transition metal element. 

/ 22. The combination of claim 20, where said substituted 

^~ transition metal oxide is an oxide of copper. 

1 23. The combination of claim 20, where said substituted * 
^ transition metal oxide has a layer-like structure. 

| 24. A method including the steps of forming a transition 

^ metal oxide having a phase therein which exhibits 

2 a superconducting state at a critical temperature 
7 in excess of 26° K, 

5 jlowcringjthe temperature of said material atQeast 

C to] said critical temperature to produce said 

7 superconducting state in said phase, and 



Y0987-074X 



- 33 - 



passing an electrical supercurrent through said 
transition metal oxide while it is in said super- 
conducting state. 

25. The method of claim 24, where said transition metal 
oxide is comprised of a transition metal capable 
of exhibiting multivalent states. 

26. The method of claim 24, where said transition metal 
oxide is comprised of a Cu oxide. 

27. A superconducting composition having a transition 
temperature in excess of 26°K, said composition 
being a substituted Cu-oxide including a supercon- 
ducting phase having a structure substantially 
close to the orthorhombic-tetragonal phase transi- 
tion of said composition. 

28. The composition of claim 27, where said substituted 
Cu-oxide includes a rare earth or rare earth- like 
element. 



Y0987-074X 



- 34 - 



I 29. The composition of claim 27-, where said substituted 
°^ Cu-oxide includes an alkaline earth element. 



/ 30. The composition of claim 29, where said alkaline 
^» earth element is atomically large with respect to 

3 ... 



| 31. The composition of claim 27, where said composition 
^ has a crystalline structure which enhances 

3 electron-phonon interactions to produce 

superconductivity at a temperature in excess of 
26°K. 



V 

r 



J 32. The composition of claim 31, where said crystalline 
^ *^ structure is layer-like, enhancing the number of 

" Jahn-Teller polarons in said c o mpo s it e?" Cow* Jj^jj+K)' 

I 33. A superconducting composition having a supercon- 
3 ducting onset temperature in excess of 26°K. , the 

3 composition being comprised of a copper oxide doped 

u 

/ with an alkaline earth element where the concen- 



Y0987-074)C 



- 35 - 



S tration of said alkaline earth element is near to 

^ the concentration of said alkaline earth element 

~~j where the superconducting copper oxide phase in 

2 said composition undergoes an orthorhombic to 

^ tetragonal structural phase transition. 

| 34. A superconducting composition having a supercon- 

^ ducting onset temperature in excess of 26°K, the 

^ composition being comprised of a mixed copper oxide 

y doped with an element chosen to create Cu"* + ions 
in said composition. 

/ 35. The composition of claim 34, where said doping el- 

•3- ement includes an alkaline earth .element. 

f 36. A combination comprising: 

A a composition having a superconducting onset tem- 

^ perature in excess of 26°K, said composition being 

y comprised of a substituted copper oxide exhibiting 

JjT" mixed valence states and at least one other element 

h in its crystalline structure, 



Y0987-074X- 



- 36 - 



•3 



7 
1 

lo 
it 

'So 



means for passing a superconducting electrical 
current through said composition while said compo- 
sition is at a temperature in excess of 26 "Sjj^fftidJ^ 

/cooling means for cooling said composition to a 
superconducting state at a temperature in excess 
of 26°^T?J 



' 37. The combination of claim 36, where said at least 
one other element is an alkaline earth element. 



/ 38. The combination of claim 36, where said at least 
3 ions in said composition. 



39. The composition of claim 36, where said at least 

one other element is an element chosen to create 
2+ 3+ 

the presence of both Cu and Cu ions in said 
composition. 



Y09S7-074X 



- 37 - 



' 40. A superconductor exhibiting a superconducting onset 

•) at a temperature in excess of 26°K, said supercon- 
ductor being comprised of at least four elements, 

v 

' none of which is itself superconducting. 

/ 41. The superconductor of claim 40, where said elements 

«^ include a transition metal and oxygen. 

} 42. A superconductor having a superconducting onset 

^ temperature greater 26°K, said superconductor being 

3 a doped transition metal oxide, where said transi- 

^/ tion metal is itself non-superconducting. 

J 43. The superconductor of claim 42, where said doped 

^ transition metal oxide is multivalent in said 

3 superconductor. 

/ 44. The superconductor of claim 42, further including 

2f an element which creates a mixed valcnt state of 

3 said transition metal. 



Y0987-074K 



- 38 - 



} 45. The superconductor of claim 43, where said transi- 
^ tion metal is Cu. 



/ 46. A superconductor having a superconducting onset 

temperature greater than 26°K, said superconductor 
^ being an oxide having multivalent oxidation states 

/J<****^_ y and including a metal, said oxide having a crys- 



5 talline structure which is oxygen deficient. 



j 47. The superconductor of claim 46, where said transi- 
oV tion metal is Cu. 



/ 48. A superconductive composition comprised of a tran- 

^ sition metal oxide having substitutions therein, 

3 the amount of said substitutions being sufficient 

y to produce sufficient electron-phonon interactions. 

^ in said composition that said composition exhibits 

£ a superconducting onset at temperatures greater 

-j than 26°K. 



Y0987-074 )< 



- 39 - 



49. The composition of claim 48, where said transition 
metal oxide is multivalent in said composition. 



50. The composition of claim A8, where said transition 
metal is Cu. 



51. The composition of claim 48, where said substi- 
tutions include an alkaline earth element. 



52. The composition of claim 48, where said substi- 
tutions include a rare earth or rare earth-like 
element. 



53. A superconductor comprised of a copper oxide having 
a layer-like crystalline structure and at least one 
additional element substituted in said crystalline 
structure, said structure being oxygen deficient 
and exhibiting a superconducting onset temperature 
in excess of 26°K. 



Y0987-074 



- 40 - 



/ 

3 



54. The superconductor of claim 53, where said addi- 
tional element creates a mixed valent state of said 
copper oxide in said superconductor. 



J 55. A combination, comprising: 

a transition metal oxide having an oxygen defi- 
^ ciency, said transition metal being non- 

If- superconducting and said oxide having multivalent 

y 

states, 



{p means for passing an electrical superconducting 

~J current through said oxide while said oxide is at 

g, 2 a temperature greater than 26°ICt ..and— 



9 
lo 



cool-ing— means — for—cooling sa id oxide in a super - 
■GondacJLijig r _S-t_ate- J a-t a-JLcwpof -at-tiro great - cr ti tan 



/ 56. The combination of claim 55, where said transition 
metal is Cu. 



Y0987-074K 



- 41 - 



57. A combination including; 



a superconducting oxide having a superconducting onset 
temperature in excess of 26°K and containing at least 3 
non-superconducting elements, 

means for passing a supercurrcnt through said oxide 
while said oxide is maintained at a temperature greater 
than 26°K, and 

means for maintaining said oxide in a superconducting 
state at a temperature greater than 26°K. 



58. A combination, comprised of: 

a copper oxide superconductor including an element which 
creates a mixed valent state in said oxide, said oxide 
being crystalline and having a layer-like structure, 

means for passing a supercurrcnt through said copper 
oxide while it is maintained at a temperature greater 
than 26°K, and 



Y0987-07*»X 



- 42 - 



P means forfcooling^said copper oxide^to^ a superconducti' 
^ state at a temperature greater than 26°K. 



I 59. A combination, comprised of: 

^ a superconducting ceramic- like material having an 

^ onset of superconductivity at a temperature in ex- 

Y cess of 26°K., 

■* J"" means for passing a supercurrent through said 
(y superconducting ceramic-like material while said 
7 ceramic-like material is maintained at a temper- 
ed ature in excess of 26°K. , and 



^ means for{coolingjsaid superconducting ceramic-like 

material ^tcJ a superconductive state at a temper- 
I f ature greater than 26°K. 



J 60. A superconductor comprised of a transition metal 
^ oxide, and at least one additional clement, said 

superconductor having a distorted crystalline 
y" structure characterized by an oxygen deficiency and 



Y0987-074X 



- 43 - 



exhibiting a superconducting onset temperature in 
excess of 26°K. 

61. The superconductor of claim 60, where said transi- 
tion metal is Cu. 

62. A superconductor comprised of a transition metal 
oxide and at least one additional element, said 
superconductor having a distorted crystalline 
structure characterized by an oxygen excess and 
exhibiting a superconducting onset temperature in 
excess of 26°K. 

63. The superconductor of claim 62, where said transi- 
tion metal is Cu. 

64. A combination, comprising: 

a mixed copper oxide composition having enhanced 
polaron formation, said composition including an 
element causing said copper to have a mixed valent 



Y0987-074-/s 



- 44 - 



i state in said composition, said composition further 
^ having a distorted octahedral oxygen environment 
leading to a T c greater than 26°K. , 

$ means for providing a supercurrent through said 
0**^ ^ composition at temperatures greater than 26*K.^3nd — 

^0 cooling-aneans- f<>r-Goo4rW»g^a-id--€oiaposJjJiin to a 



// temperatnre-great£r than 26 0 k7^ 



j 65. A- superconducting composition exhibiting 

^ superconductivity at temperatures greater than 

^ 26°K, said composition being a ceramic-like mate- 

Y rial in the RE-AE-TM-0 system, where RE is a rare 

^ earth or near rare earth element,. AE is an alkaline 

Q earth element, TM is a multivalent transition metal 
■7 

' element having at least two valence states in said 
/ 

0 composition, and 0 is oxygen, the ratio of the 

amounts of said transition metal in said two va- 

iO lence states being determined by the ratio RE : AE. 



/ 66. A superconductive composition having a transition 
2. temperature greater than 26°K, the composition in- 



Y0987-074-)C 



- 45 - 



J eluding a multivalent transition metal oxide and 

7 at least one additional element, said composition 

r having a distorted orthorhombic crystalline struc- 

C> ture. 

J 67. The composition of claim 66, where said transition 

^ metal oxide is a mixed copper oxide. 

/ 68. The composition of claim 67, where said one addi- 

^ tional element is an alkaline earth element. 

/ 69. A superconductive combination, comprising: 

o| a superconducting composition exhibiting a super- 

J conducting transition temperature greater than 

y 26°K, said composition being a transition metal 

$ oxide having a distorted orthorhombic crystalline 

^ structure, and 

J means for passing a superconducting electrical 

current through said composition while said compo- 
sition is at a temperature greater than 26°K. 



Y0987-074X 



- 46 - 



J 70. 



The combination of claim 69, where said transition 
metal oxide is a mixed copper oxide. 



) 71. The combination of claim 70, where said mixed copper 
oxide includes an alkaline earth element. 

J 72. The combination of claim 71, where said mixed copper 

^ oxide further includes a rare earth or rare earth- 

3 like element. 

J 73. A method for making a superconductor having a 

^ superconducting onset temperature > 26°K, said 

J method including the steps of: 

y preparing powders of oxygen-containing compounds 

$~ of a rare earth or rare earth-like element, an 

£ alkaline earth element, and copper, 

-7 mixing said compounds and firing said mixture to 

y create a mixed copper oxide composition including 

J said alkaline earth element and said rare earth or 
rare earth- like element, and 



Y0987-074Y, 



- 47 - 



/ / annealing said mixed copper oxide composition at 
1^ an elevated temperature less than about 950°C in 
/ 3 an atmosphere including oxygen to produce a super- 
^ conducting composition having a mixed copper oxide 
phase exhibiting a superconducting onset tcmpcr- 
aturc greater than 26°K, said superconducting com- 
\~J position having a layer-like crystalline structure 
/ P after said annealing step. 



J 74. The method of claim 73, where the amount of oxygen 
^ incorporated into said composition is adjusted by 

2 said annealing step, the amount of oxygen therein 

y affecting the critical temperature T, of the 

superconducting composition. 



I 75. A method for making a superconductor having a 

^ superconducting onset temperature greater than 

j 26°K, said superconductor being comprised of a rare 

y earth or rare earth-like element (RE), an alkaline 

S earth element <AE) , copper (CU), and oxygen (0) and 

C having the general formula RE-AE-CO-0, said method 

~j including the steps of combining said rare earth 

f> or rare earth-like element, said alkaline earth 



Y0987-074X 



- 48 - 



7 element and said copper in the presence of oxygen 

lo to produce a mixed copper oxide including said rare 

// earth or rare earth-like element and said alkaline 

/^L_ earth element therein, and 

heating said mixed copper oxide to produce a 

iy superconductor having a crystalline layer-like 

I ^ structure and exhibiting a superconducting onset 

J ^ temperature greater than 26°K, the critical tran- 

J-j sition temperature of said superconductor being 

/$ dependent on the amount of said alkaline earth el- 

^9 ement therein. 

J 76. The method of claim 75, where said heating step is 
done in an atmosphere including oxygen. 

j 77. A combination, comprising: 

^ a mixed copper oxide composition including an 

^ alkaline earth element (AE) and a rare earth or 

y rare earth- like element (RE), said composition 

y having a layer-like crystalline structure and 

^ multi-valent oxidation states, said composition 



Y0987-074X. 



- 49 - 



"7 exhibiting a substantially zero resistance to the 

h % flow of electrical current therethrough wlienfoooied 

^ ^ a su P ercon ducting state at a temperature in ex- 

lO cess of 26°K, and 



jj electrical means for passing an electrical super- 

lQ current through said composition when said compo- 

1 ^ sition exhibits substantially zero resistance at a 

/ y temperature greater than 26°K. 



J 78. The combination of claim 77, where the ratio 
(AE.RE) : Cu is substantially 1:1. 



a^^J- / 79. The combination of claim 77, where the ratio 



(AE,RE) : Cu is substantially^!. 



/ 80. The combination of claim 77, where said crystalline 
^ structure is perovskite-like. 



YO987-074 X 



- 50 - 



I 81. Tlie combination of claim 77, where said mixed copper 
oxide composition has a non-stoichiometric amount 

3 of oxygen therein. 

/ 82. A method for making a superconductor having a 

Q superconducting onset temperature greater than 26°, 

^ said superconductor being comprised of a rare earth 

V or rare earth-like element (RE), an alkaline earth 

£ element (AE), a transition metal element (TM) , and 
oxygen (0) and having the general formula 

~J RE-AE-TM-0, said method including the steps of 

^ combining said rare earth or rare earth-like ele- 

^ ment, said alkaline earth element and said transi- • 

f 0 tion metal element in the presence of oxygen to 

M produce a mixed transition metal oxide including 

/^L said rare earth or rare earth-like clement and said 

/ J alkaline earth element therein, and 

/y heating said mixed transition metal oxide to 
/J produce a supcrcoductor having a crystalline 

layer-like structure and exhibiting a supercon- 
I ~J ducting onset temperature greater than 26°K, said 

/ P 

'° superconductor having a non-stoicliiomctric amount 

// 

of oxygen therein. 



YO987-07A)( 



I 83. 

3l. 



The method of claim 82, where said transition metal 



is copper. 



j 84. A superconducting combination, comprising: 

a mixed transition metal oxide composition con- 

^ taining a non-stoichiometric amount of oxygen 

Kj, therein, a transition metal and at least one addi- 

i tional element, said composition having substan- 
tially zero resistance to the flow of electricity 

-j therethrough whenGooled t^a superconducting state 

% at a temperature greater than 26°K, and 

^ electrical means for passing an electrical super- 

10 current through said composition when said corapo- 

1 1 sition is in said superconducting state at a 
/ temperature greater than 26°K. 

/ 85. The combination of claim 84, where said transition 

^ metal is copper. 

/ 86. A method, comprising the steps of: 



Y0987-074X 



- 52 - 



forming a composition including a transition metal, 
^ a rare earth or rare earth-like element, an 
j£ alkaline earth element, and oxygen, where said 
£~ composition is a mixed transition metal oxide hav- 
£ ing a non-stoichiometric amount of oxygen therein 
~~] and exhibiting a superconducting state at a teni- 
$ perature greater than 26°K, 

/ fcooling^said composition JtoJ said superconducting 
state at a temperature greater than 26°K, and 

h passing an electrical current through said compo- 
/^L sition while said composition is in said supercon- 
^3 ducting state. 



/ 87. Tlie method of claim 86, where said transition metal 
3 

is tenner. 



J 88. A method, including the steps of: 



forming a composition exhibiting a superconductive 
state at a temperature in excess of 26°K, 



Y0987-07AX 



- 53 - 



V 

r 

b 

7 

1 



I 89 



/ 90. 



jcoolingjsaid composition |toy a temperature in excess 
of 26°K at which temperature said composition ex- 
hibits said superconductive state, and 

passing an electrical current through said compo- 
sition while said composition is in said 
superconductive state. 



The method of claim 88, where said composition is 
comprised of a metal oxide. 



The metal of claim 88, where said composition is 
comprised of a transition metal oxide. 



Y0987-074X 



- 54 - 



2/3 
Y09-87-07U 



FIG. 3 

© 900°C 2h 

© 540°c ismin 

(D 630°C 12 h 

© 900°C ismin 

© 900°C ih 

(D 950°C ih 

® 1040°C ismin 




TEMPERATURE (K) 



3/3 

Y09-87-074X 



FIG. 4 



0.008 - 



0.006 



. 0.004 



0.002 



0 7.5 A/cm 2 
x 2.5 A/cm 2 
• 0.5 A/cm 2 



J L 



10 2 0 30 40 50" 
TEMPERATURE ( K) 



BRIEF ATTACHMENT AV 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



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



Group Art Unit: 1751 
Examiner: M. Kopec 



Date: March 1 , 2004 
Docket: YO987-074BZ 



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



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



FIFTH SUPPLEMENTAL AMENDMENT 



Sir: 



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



ATTACHMENT 6 



r r- 




frora ASAHI SHIl&UN 

International Satellite Edition 
28. 11. 1986 (London) 




DISCOVERY OF NEW SUPERCONDUCTING MATERIAL 

" CERAMIC WITH SUFFICIENT SUPERCONDUCTIVE POWER IN 
HIGH TEMPERATURE REGION " 

A new ceramic with a very high T c of 30K of .the superconducting 
transition has been found. The possibility of high T - super- 
conductivity has been reported by scientists in Switzerland in 
this spring. The group of Prof. Shoji TANAKA, Dept. Appl Phys 
Faculty of Engineering at the University of Tokyo confirmed in 
November that this is true. V s of all superconducting materi- 
als which we have in practical application till now are lower 

inT I ,' T ref ° re ^ lar9e IB " 0U » t of "W" He for cool- 

in. No e that the price of liguid He is very expensive. But 

W In ^ B ?-'-^ U " Ch **™ H, for cooling, 

a neaTH "° ^ ^^-tions such 

as linear motorcars, electricity transport systems, etc. 

The ceramic newly discovered 

with Ba ^ v „ scovered ' is a " oxide compound of La and Cu 
There are a lot of wiuuu., for practical applications of 

r*n n rA ^ c laboratory is around 23. 2K. This 

record has not been broken since 1973 

nit",: 6aCh 1 j 08 ^^^ us ^ superconductors is operated by 

ot 30K, we can not only use liauid h k,.* i c 
boiling point of 27k! 2 3130 UqUld Ne With 3 

v«T S ^: P ra P l Ca t ti0n ° H f . SUP —- tors to many fields, such as 

incL::i: : ; h :i :t q ;ii:t machines ' etc - shw — 

competitive all over tne wo d ^ *° S ^°^^ i- high- 



4 



** TOTAL PflGE.005 ** 



BRIEF ATTACHMENT AW 



IN THE UNITED STATES PATENT AND TRADEMARK OFFICE 



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



Group Art Unit: 1751 
Examiner: M. Kopec 



Date: March 1 , 2004 



Docket: YO987-074BZ 



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



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



FIFTH SUPPLEMENTAL AMENDMENT 



Sir: 



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



ATTACHMENT 23 



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 Datia. 

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

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

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

QC6I1.98.C64P66 1988 
539.6'23-dc 19 88-18S69 C1P 
ISBN 0-471 -©2342-3 

Printed in the United States of America 

I0 9876S432I 




PREFACE 



The unprecedented worldwide effort in superconductivity researdwthat 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 
superconductmry above the temperature of liquid nitrogen. The time is now ripe 
to bring together m one place the results of this research effort so that scientists 
working ,n 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 

fZT7,i y S^o Mtt,,Cr in ApfU 1986 ttBtil a few the 
award of the Nobel 1 Pnze 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. USrCuO. TIBaCaCuO and YBa- 
CuO has emerged. At the same time there has been a continual debate on the 

roo. n v to £* thC 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 o"he 
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 ,s 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 



^nyomiss.ocu in the citing and discussion of articles ~ f ° r 

moto. P. K. Gallagher, R. Goldfarb J E. Graebn^ R i ^ ^ 



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



Columbia. South Carolina 
Jufyim 



Hi 



"^oftheBCStheory.however, 

'^^iledt^tmentoftheprop- 
«* the extent to which the, con- 
ey agree with some of the other 
"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 temperaturev 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 




0 100 200 300 



Fig. V-l. Effects of heat treatments on the resistivity transition of BiSrdCuOi., Ul 
calcined at 860°C, (fc) calcined at 88S°C, (c) calcined at 901 °C, (</) alura'mura-dojri 
sample calcined at 875°C, prolonged annealing, (e) copper-rich sample calcined a 
860°C. {f) aluminum-doped sample calcined at 885°C, slow quenching and (g) aiaaei 
at 885°C, prolonged annealing, and slow quenching (ChuzS). 



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

Polycrystalline samples are the easiest to prepare, and much of the early wort 
was carried out with them. Of greater significance is work carried out with thk 
films and single crystals, and these require more specialized preparation tech- 
niques. More and more of the recent work has been done with such samples. 

Many authors have provided sample preparation information, and otben 
have detailed heat treatments and oxygen control. Some representative tech- 
niques will be discussed. 

The beginning of this chapter will treat methods of preparing bulk supereo* 
ducting samples in general, and then samples of special types such as thin fib* 
and single crystals. The remainder of the chapter will discuss ways of checkia| 
the composition and quality of the samples. The thermodynamic or subsoudw 
phase diagram of the ternary Y-Ba-Cu oxide system illustrated in Fig. V-2 cot 
tains several stable stoichiometric compounds such as the end-point oxide 
Y 2 0 3 , BaO, and CuO at the apices, the binary oxides stable at 950°. (BajCiKW 
Ba 2 CuOj, BaCu0 2 , Y 2 Cu 2 O s . Y 4 Ba 3 0,. Y 2 Ba0 4 , and (Y 2 Ba 4 0 7 ). along * 
edges, and ternary oxides such as (YBa 3 Cu 2 0 7 ), the semiconducting green pna» 
Y 2 BaCuO s , and the superconducting black solid YBa 2 Cuj0 7 _s in the interio 
(Beye2, Bour3, Capol. Eagll, Frase, Hosoy, Jonel, Kaise, Kurth..Kuxn 
Leez3, Lianl, Malil, Schni, Schnl, Schul, Takay, Torra, Wagne). Compound 
in parentheses are not on the figure, but are reported by other workers. 1 
existence of a narrow range of solid solution was reported (Panso), and 
argued against (Wagne) by the same group. 



vMfLES 




300 



ransition of BiSrCaCuOy^ (a) 
t 901 °C, (d) lluminum-doped 
•pper-rich sample calcined at 
3W quenching and (g) calcined 
.z5). 



annealed in the same tern- 
re. 

nd much of the early work 
rork carried out with thin 
cialized preparation tech- 
ione with such samples, 
information, and others 
k>me representative tech- 
preparing bulk supercon- 
al types such as thin films 
discuss ways of checking 
modynamic or subsolidus 
lustrated in Fig. V-2 con- 
as the end-point oxides 
table at 950°, (Ba,CuO<). 
id (Y 2 Ba<0 7 ), along the 
liconducting green phase 
a^CujO?.* in the interior 
, Kaise, Kurth, Kuzzz, 
ra, Wagne). Compounds 
i by other workers. The 
orted (Panso), and then 



METHODS OF PREPARATION 




Compound 


Stowty cooled 




*> room temperature 




Oj 


W3-YBa«CijjOu., 


o» 




o« 




O9 


211 - YjBaCuOj 






2» 



other expounds are shown in the interior of SlX»fS3^ 



B. METHODS OF PREPARATION 



superb" telSrr * m,XtUre ° f C ° mp ° Unds into a 
more competence in analytical procedures * KqmKS 



« PREPARATION AND CHARACTERIZATION OF SAMPtES 

several times, with pulverkinVand i^i *P ' ™ ,s P 1 ^ may be repeated 
each step. As the ^^^^^^^»-Sf3 
usually ends with . ft* ^ ^S^^* ma *~ 
temperature of the powder, or peJlefa Z ? ° W 0001 down to room 
cold or hot press. Sfatering fc^ ^t^^ h * ***** « a 

transit and other measu^e^ ^^0 ^ ** 
•zed. A number of researchers have n^SS^f^ havC ^ materia l Peliet- 
action approach (e.g., A^^TST? Ration on this solid-state*- 
Herrm, Hikal. ^^^S^U^J^^^^ 
Qadri, Rhyne, ^ ^l£Z?&^ 

suspension of the calcined powder fa T^t^T' ""P 1 *** a 

product was obtained by cCenfiona" 2^""° ^ 

spraying, or coating. * mdast ™i Processes such as extruding, 

^7. Wa„ g 2). This has the adva^S * Z£ ™Z ^ (e 8 - Asda ' Bedn °. 
scale. In addition the predpitateZ^fo™ W § ^ ~ nstitue ^ °* an atomic 
be controlled, which can elLfaTte som^^ ^ Unifonnit y ca ° 

been dried, calciningcan beg« Z tn Z^M^ ^ *** "« 
vantage of this method, at IeS« to« £^T^ A ^ 

tist is concerned, is that it reouirel «,ncS ^ 8 phySIast or trials scien- 
. A «ot«er procedurefor oSS^^ » ^ical procedures 
•n which an aqueous uMon^^^J^^^**^ 
nitrates is emulsified fa an organic ph^^fh ^ ° f Ba ' an * Y 
the addition of a high-moIecSa^wSghTprimat aK * e,,ed b > 

acd. This process was initially apS ^ WWch extracts idbfc 

fected for YBaCuO as well (SS^ 6 U materialS » but has Per- 

recommended. G^S^^^^ ^UU 
are thoroughly mixed and placed faTSll? e P°^ered precursor materials 
betaken to ensure the caa^^^^ZS ^ n ^ 

obvute reaction and corrosion proems * Ceram,C w »h the chemicals to 

1>^^J^^^ ~ (.*. c ran2) . 

*X>°C for ,5 h, During t^i^cT™? " °^ e " 

green Y 2 BaCuO s phase to the da7 gn£ Jfia Cat ^ "** fr ° m the 

O-. at thisstagethen^terial^™-^