IN THE UNITED STATES PATENT AND TRADEMARK OFFICE
Applicants: J. Bednorz et al.
Date: December 15, 1998
Serial No. 08/479,810
Group Art UniM405- / 7 JT /
Filed: June 7, 1995
Examiner: M. Kopec
For: NEW SUPERCONDUCTIVE COMPOUNDS HAVING HIGH
TRANSITION TEMPERATURE, AND METHODS FOR THEIR
USE AND PREPARATION
The Commissioner of Patents and Trademarks
Washington, D.C. 20231
AFFIDAVIT UNDER 37 CFR 1.132
I, Thomas M. Shaw, being duly sworn, do hereby depose and state:
I received a B.S. degree in Metallurgy from the University of Liverpool, Liverpool,
England and a M.S. and PhD. degree in Materials Science (1981) from the University
of California, Berkeley.
I have worked as a postdoctoral researcher in the Material Science Department of
Cornell University from 1981-1982. I worked at Rockwell International Science Center
in Thousand Oaks, California from 1 982-1984 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, N.Y.
from 1 984 to the present.
I have worked in the fabrication of and characterization of ceramic materials of various
types, including superconductors and related materials from 1984 to the present.
Attached is a resume of my publications. I have reviewed the above-identified patent
application and acknowledge that it represents the work of Bednorz and Mueller, which
is generally recognized as the first discovery of superconductivity above 26°K and that
subsequent developments in this field have been based on this work.
That all the high temperature superconductors which have been developed based on
the work of Bednorz and Mueller behave in a similar manner, conduct current in a
similar manner and have similar magnetic properties.
That once a person of skill in the art knows of a specific transition metal oxide
composition which is superconducting above 26°K, such a person of skill in the art,
using the techniques described in the above-identified patent application, which
includes all known principles of ceramic fabrication known at the time the application
was filed, can make the transition metal oxide compositions encompassed by the
claims in the above-identified application, without undue experimentation or without
requiring ingenuity beyond that expected of a person of skill in the art. This is why the
work of Bednorz and Mueller was reproduced so quickly after their discovery and why
so much additional work was done in this field within a short period of their discovery.
The general principles of ceramic science referred to by Bednorz and Mueller in their
patent application can be found in many books and articles published before their
discovery. An exemplary list of books describing the general principles of ceramic
1) Introduction to Ceramics, Kingery et al., Second Edition, John Wiley & Sons,
1976, in particular pages 5-20, 269-319, 381-447 and 448-513, a copy of
which is attached herewith.
2) Polar Dielectrics and Their Applications, Burfoot et al., University of California
Press, 1979, in particular pages 13-33, a copy of which is attached herewith.
3) Ceramic Processing Before Firing, Onoda et al., John Wiley & Sons, 1978,
the entire book, a copy of which is attached herewith.
4) Structure, Properties and Preparation of Perovskite-Type Compounds,
F.S. Glasso, Pergamon Press, 1969, in particular pages 159-181, a copy of
which is attached herewith.
An exemplary list of articles applying their general principles of ceramic fabrication to
the types of materials described in applicants' specification are (these references are
cited on applicant's 1449 form submitted August 5, 1987 and in PTO Form 892 in
Paper # 20, Examiner's action dated August 8, 1990):
1) Oxygen Defect K2NiF 4 - Type Oxides: The Compounds La 2 . x Sr x Cu04-x/2 + 6, Nguyen et
al., Journal of Solid State Chemistry 39, 120-127 (1981).
2) The Oxygen Defect Perovskite BaLa 4 Cu 5 -0i 3 .4, A Metallic Conductor , C. Michel et
al., Mat. Res. Bull., Vol. 20, pp. 667-671, 1985.
r ■ -
3) Oxygen intercalation in mixed valence copper oxides related to the perovskite, C.
Michel et al., Revue de Chemie minerale, p. 407, 1984.
4) Thermal Behaviour of Compositions in the Systems x BaTiOa + (1-x) Ba(Ln 05 B 0 .s) 0 3 ,
VS. Chincholkar et al. Therm. Anal. 6th, Vol. 2., p. 251-6, 1980.
Sworn to before me this
Thomas M. Shaw
day of flfifi&nbfaL , 1 9
1 Notary Public
.ry „ SANDRA M.EMMA
Notary Public. State of New York
r?« ah,,ed ,n Westchester County ,
commission Expires July 5,
1. D.R.Clarke and T.M.Shaw, D.P.Thompson, "Direct Observation of the Polytype Periodicities
in the Be-Si-O-N System/, J. Mat. Sci. 13 pages 217-219 (1978)
2. T.M. Shaw, 'Transmission Electron Microscopy Analysis of Complex Nitrogen Ceramics",
Proceedings of the 9th International Congress on Electron Microscopy, Toronto. Ed J.M.
Sturgess (Microscopical Society of Canada, 1978). Vol 1 Page 258.
3. D.R. Clarke and T.M. Shaw, "polytypism in Magnesium Sialon", in Processing of Crystalline
Ceramics (Materials Science Research Vol. 11), Edited by H. Palmour III, R.F. Davis and
T.M. Hare., Plenum press 1978.
4. T.M. Shaw and G. Thomas, 'Transmission Electron Microscopy: Direct Observation of
Crystal structure in Refractory ceramics",Science 202, pages 625-626 (1978)
5. O.L. Krivanek, T.M. Shaw and G. Thomas, "Imaging of Thin Intergranular Phases by Higji
resolution Electron Microscopy", J. Appl. Phys. 50, pages 4223-4227 (1979).
6. O.L. Krivanek T.M. Shaw and G. Thomas,"The Microstructure and Distribution of Impurities
in Hot-Pressed and Sintered Silicon Nitrides" J. Amer. Ceram. Soc. 62, pages 585-590 (1979)
7. T.M. Shaw O.L. Krivanek and G. Thomas, "Glass Free Grain Boundaries in Be-Si-N Ce-
ramics", J. Amer. Ceram. Soc. 62, pages 305-306 (1979).
8. T.M. Shaw and G. Thomas/'An Electron Microscopy Study of Crystallography and Phase
relationships in the Be-Si-N system", J. Solid State Chem. 33, pages 63-82 (1980).
9. T.M. Shaw and G. Thomas "The crystallization Behavior of a Mg- Si-O-N Glass " in Progress
in Nitrogen ceramics, Proceedings of the NATO Advanced Study Institute, Ed F.L.Riley,
Martinius Nijhoff (1983).
10. T.M. Shaw and C.B. Carter, "Faceting in Twin Boundaries in Spinel", Scripta Met. 16, pages
11. P.E.D. Morgan and T.M. Shaw, "Magnetoplumbite Related Barium Aluminates", Mat. Res
Bull. 18, pages 539-542 (1983).
12. P.E.D.Morgan, T.M.Shaw and E.A.Pugar "Ceramics For High Waste Loaded Commercial
Radwaste disposal'Tn Advances in Ceramics, Vol 8, Nuclear Waste Management. Ed
G.G. Wicks and W.A.Ross. Published Amer. Ceram. Soc. 1984.
13. P.E.D.Morgan, A.B.Harker, J.F.Flintoff, T.M.Shaw, and D.R.Clarke "Developments in SRP
"composite" Defense Ceramic Radwaste Forms"In Advances in Ceramics, Vol 8, Nuclear
Waste Management, Ed G.G. Wicks and W.A.Ross. Published Amer. Ceram. Soc. 1984.
14. T.M.Shaw, G.Thomas and R.E.Loehman "The formation and microstructure of Mg-Si-O-N
Glasses" J. Amer. Ceram. Soc. Nov 1984.
15. T.M.Shaw, J.W.Steeds and D.R.Clarke "Fault Structures in CVD silicon nitride" Proceedings
of M.R.S. Symposia on the Electron Microscopy of Materials. North Holland 1984.
16. T.M.Shaw and B.Pethica "The Preparation and Sintering of Homogeneous Silicon Nitride
Green Compacts" J. Amer. Ceram. Soc. Vol.69 P.27 (1986).
17. T.M.Shaw "Liquid Phase Redistribution During Liquid Phase Sintering" J. Amer. Ceram Soc
Vol.69 P.88 (1986)
18. T.M.Shaw "Movement of a drying front in a porous material" Proceedings of the M.R.S Better
Ceramics through Chemistry symposium , published Elsevier 1986.
19. C.B. Carter, Z. Elgat and T.M. Shaw "First-Order Twin Boundaries parallel to the common
(111) Plane in spinel Phil. Mag. Vol 55. P.l (1987)
20. C.B. Carter, Z. Elgat and T.M. Shaw "Lateral Twin Boundaries in Spinel. Phil. Mae Vol
55 P.21 (1987).
21. T.M. Shaw "Drying as an Immiscible Displacement Process with Fluid Counterflow" Phys
Rev. Lett. Vol. 59, P. 1671-1674, (1987).
22. WJ. Gallagher, R.L. Sandstrom, T.R. Dinger, T.M. Shaw and D.A. Chance, "Identification
and Preparation of Single Phase 90K Oxide Superconductor and Structural Determination by
Lattice Imaging", Solid State Communications Vol.63 P. 147 (1987).
23. R. Beyers, G. Iim, E.M. Engler, RJ. Savoy, T.M. Shaw, T.R. Dinger, W.J. Gallagher and
R.L. Sandstrom "Crystallography and Microstructure of :f.Y sub 1 Ba sub 2 Cu sub 3 O sub
9-x:ef., A Perovskite-Based Superconducting Oxide" Appl. Phys. Lett Vol.50 p.1918 (1987).
24. R. Beyers, G. Lim, E.M. Engler, V.Y. Lee, M.L. Ramirez, R.J. Savoy, R.D. Jacowitz, T.M.
Shaw, S. La Placa, R. Boehme , C.C. Tsuei, S.I. Park, M.W. Shafer, W.J. Gallagher "On the
Relationship Between Processing, Structure, and Superconductivity inrf.Y sub 1 Ba sub 2 Cu
sub 3 O sub 9-x:ef.'. Appl. Phys. Lett. 51, p 614-616 (1987)
25. R. Beyers, G. Lim, E.M. Engler, V.Y. Lee, M.L. Ramirez, R.J. Savoy, R.D. Jacowitz, T.M.
Shaw, F.G. Frase, E.G.Linger, D.R. Clarke, S. La Placa, R. Boehme , C.C. Tsuei, S.I. Park,
M.W. Shafer, W.J. Gallagher and G.V. Chandrashekhar. "On the Relationship Between
Processing, Structure, and Superconductivity in :f.Y sub 1 Ba sub 2 Cu sub 3 O sub 9-x:ef..
Proceedings of the M.R.S symposium on Superconductivity, published Elsevier 1987.
26. T.M. Shaw "Drying Behavior in Porous Materials". Extended abstracts of the M.R.S sym-
posium on Fractal aspects of materials published MRS 1987.
27. R. F. Cook, T.M. Shaw and P.R. Duncombe "Fracture Properties of Polycrystaline :f.Y sub
1 Ba sub 2 Cu sub 3 O sub 9-x:ef.". In Ceramic superconductors Ed. D.R. Clarke and D.W.
Johonson, Published American Ceramis Society (1987).
28. T.R. McGuire, T.R. Dinger, P.J.P. Freitas, W.J. Gallagher, T.S. Plaskett, R.L. Sandstrom
and T.M. Shaw, "Magnetic Properties of Y-Ba-Cu-O Superconductors" Phys. Rev B Vol.36,
29. T.R. McGuire, F. Holtzberg, D.L. Kaiser, T.M. Shaw and S. Shinde. "Magnetic Properties
of Y-Ba-Cu-O Superconductors" Proceedings of the 3M Conference. To be published J. Appl.
Phys. vol 62 march (1988).
30. W. Krakow and T.M. Shaw "An Evaluation of High Resolution Electron Microscopy as a
Method For Studying Y-Ba-Cu-O Superconductors", To be published J. Electron Microscoov
1 echmque ( 1987). y *
31. W Krakow and T M. Shaw "High Resolution Electron Microscopy and Electron Diffraction
of :f.Y sub 1 Ba sub 2 Cu sub 3 O sub 7-x:ef.". Proceedings of the MRS Fall Symposium on
Superconductivity published Elsevier 1987. ^
31 I' 1 ^ L ShaW ' S A * Shivashankar > S.J. La Placa, J.J. Cuomo, T.R. McGuire R.A. Roy K H
Kelleher and D.S. Yee "Incommensurate structure in the Bi-Sr-Ca-Cu-0 80K Superconduc-
tor" Phys. Rev. B 37(16), 9856 (1988). superconouc
33. T R. McGuire, S.A. Shivashankar, S.J. La Placa, G.V. Chandrasheka, R.F. Boehme T M
Shaw, D.S. Yee, M.W. Shafer, and J.J. Cuomo "Superconductivity in Bi-Sr-Ca-Cu-O" j' AppI
Phys. Vol 64 1988. * v '
34. A.C Nunes, S.J. Pickart, L. Crow and Goyette (University of Rhode Island) T.R. McGuire
S. Shinde and T.M. Shaw (IBM) "Neutron depolarization by a High Tc Superconductor" To
be published J. Appl. Phys. Vol 64 1988.
35. R. Beyers and T.M. Shaw "The Structure of 123 and its Derivatives", Solid State Phys Vol
42 P. 135-212 1989. 3
36. T.M. Shaw S. Shinde, D. Dimos, R.F. Cook, P.R. Duncombe, and C. Kroll" "The Effect of
P248 256 C °9g^ Iicrostructure 311(1 Stress Relaxation in Polycrystalline 123", J. Mat. Res. Vol.4
37. D.R. Clarke, T.M. Shaw and D. Dimos "Issues in the Processing of Cuperate Ceramic
Superconductors" J. Amer. Ceram. Soc 72, 1103 (1989).
38. G. Burns, M. K. Crawford, F. H. Dacol, E. M. McCarron III, and T. M. Shaw, Phonons in
:f.CaCuO sub 2 ,:ef. Phys. Rev. B 40, 6717 (1989).
39. T.M. Shaw, D. Dimos, P.E. Batson, A.G. Schrott, D.R. Clarke and P.R. Duncombe "Carbon
Retention in :f/Y' < 'Ba' sub 2 > < 'Cu' sub 3 > 'O'sub < 7-delta > ':ef. and its Effect on the
Superconducting Transition," J. Mat. Res. 5(6), 1176 (1990).
40. S.L. Shinde and T.M. Shaw, "Considerations for Improved Polycrystalline Cuprate Super-
conductors," Page 579 in Superconductivity and Ceramic Superconductors, Eds. K.M Nair and
E.A. Giess, 13, Ceramics Trans., Published Amer. Ceram. Soc.
J.F. Bnngley, B.A. Scott, S.J. La Placa, R.F. Boehme, T.M. Shaw, M.W. McElfresh and S.S.
Trail, "Synthesis of :f.'LaCuO' sub < 3-delta > :ef. a new Defect Perovskite with Variable
Copper Valence from +2 to +3." Nature, 347, 263-265 (1990).
42. B.S. Berry, W.C. Pntchet and T.M. Shaw, "Anelastic Measurements of Atomic Mobility in
the Superconductor :f.'Y' <'Ba' sub 2> <'Cu' sub 3 > 'O'sub < 7-delta > ':ef.," Defect and
Diffusion Forum 1990.
43. M.K. Crawford, G. Burns, E.M. McCarron, G.V. Chandrashekhar, W.E. Farneth, and T.M.
Shaw, "Infrared and Raman Spectroscopy of Phonons in :f.(Nd/Pr) sub 2 CuO sub 4:ef. :f.(Ca
sub 0.86 Sr sub 0.14 )CaO sub 2:ef.," Materials Research Society Proceedings, 169, 1013
44. P.E. Batson, T.M. Shaw, D.Dimos and P.R. Duncombe "Participation of Carbon in the
Electronic-Structure of YBa2Cu307-Delta /, .Physical Review B-Condensed Matter 1991, Vol
43, Iss 7, pp 6236-6238
45. T.K. Worthington, E. Olsson, C.S. Nichols, T.M. Shaw and D.R. Clarke "Observation of a
Vortex-Glass Phase in Polyciystalline YBa2Cu307-X in a Magnetic-Field" Physical Review
B-Condensed Matter Vol 43, Iss 13, pp 538-543, (1991).
46. T.M. Shaw and P.R. Duncombe, "Forces Between Aluminum Oxide Grains in a Silicate Melt
and their Effect on Grain Boundary Wetting," J. Amer. Ceram. Soc, 74, P.2495, (1991).
47. "Synthesis and Processing of Ceramics: Scientific Issues," MRS Proceedings Vol. 249, Editors
W.E. Rhine, T.M. Shaw R.J Gottschall and Y. Chen. Published (1992).
48. M. D&ae.umling, L.E.Levine and T.M.Shaw, ":ef.T sub c:ef., :f.H sub c2:ef., and Oxygen
Ordering in Quenched Oxygen Deficient YBa&sub2.Cu&sub3.:f.O sub <7 -dlt>:ef. " Ad-
vances in Cryogenic Engineering (Materials), Published (1992).
49. T. Frey, C.C. Chi, C.C.Tsuei, T.M. Shaw and G. Trafas, "RHEED-controlled Unit-Cell by
Unit-Cell Layer-Growth of High-Tc Cuperate Films with Laser Ablation Technique,"MRS
Proceedings, Vol.275 P. 61, (1992).
50. C.C.Tsuei, T. Frey, C.C. Chi, T.M. Shaw, D.T. Shaw and M.K. Wu, 'The Making of
High-Tc Layered Superconductors," Proceedings of the Buffalo conference on
Superconductivity and its Applications (1992).
51. M.Y. Chern, A. Gupta, B.W. Hussey and T.M. Shaw, "RHEED Intensity Monitored
Homoepitaxial Growth of :f/SrTiO' sub 3:ef. Buffer Layer by Pulsed Laser Deposition," J.
Vac. Sci. Technol. A. 11, 637 (1993).
52. M. Daumling, P.R. Duncombe, K.H. Kelleher, R.A. Figat and T.M. Shaw, "upper Critical-
Field of Gold-Doped YBa&sub2.Cu&sub3.:f.O sub < 7 -dlt > :ef.," Phys. Rev. B 47, P. 6177,
53. T.M. Shaw "A Model for the Effect of Powder Packing on the Driving Force For Liquid Phase
Sintering," J. Amer. Ceram. Soc 76, P.664, (1993).
54. D.R. Clarke T.M. Shaw, A.P. Philipse and R.G. Horn "On a possible Electrical Double layer
Contribution to the Equilibrium Thickness of Intergranular Glass Phases in Polycrystalline
Ceramics" to be published, Journal of the American Ceramics Society (1993).
55. T. Frey, C.C. Chi, C.C.Tsuei, T.M. Shaw and F. Bozso "THe Effect of Atomic Oxygen on
the Initial Growth Mode in Thin Epitaxial Cuprate Films", Phys. Rev. B.49,P. 3483,(1994).
56. A.Gupta, B.W. Hussey, T.M. Shaw, R.F. Saraf, J.F. Bringley and B.A. Scott, "Growth of
Thin Films Of the Defect Perovskite :f.'LaCuO' sub <3-delta>:ef. by Pulsed Laser
Ablation",Solid State Commu.,108, P.202, (1994).
57. A.D. Kent, T.M. Shaw and S. von Molnar, "Growth of High Aspect Ratio Nanometer Scale
Magnets Using Chemical Vapor Deposition and Scanning Tunneling Microscope Techniques/'
Science, 262, P. 1249 (1993).
58. A. Gupta, B. W. Hussey, T. M. Shaw, A. M. Guloy, M. Y. Chern, R. F. Saraf, and B. A.
Scott, "Layer-by- Layer Growth of Thin Films of the Infinite-Layer Compounds: &sco. and
&cco.", J. Solid State Chem. 112, P. 113, (1994).
59. T.M. Shaw, A. Gupta, B.W. Hussey, P.E. Batson, B.A. Scott and R.B. Laibowitz, * Atomic
Scale Oxide Superlattices Grown by RHEED Controlled Pulsed Laser Deposition/' , J. Mat.
60. A. Gupta, T.M. Shaw, M.Y. Chern, B.W. Hussey, A.M. Guloy and B.A. Scott, * Reflection
High-Energy Electron Diffraction Monitored Growth of Infinite-Layer &cco./&sco. Thin Film
Heteostructures" To be published Phys. Rev. B.
61. J. Drennan, D. R. Clarke, R.H.J. Hannink and T.M. Shaw, "Effect of Oxygen Partial Pressure
on the Microstructure of Mg^PSZ with Strontia and Silica Additions", J. Amer. Ceram. Soc.
77, P.2001, (1994).
62. A.Grill, W. Kane, D. Beach, R. Laibowitz and T.M. Shaw., "Preparation of Strontium
Titanate Films by MOCVD", To be published J. Integrated ferroelectrics (1994).
63. D.B. Beach, R.B. Laibowitz, T.M. Shaw, A. Grill, and W.F. Kane, "Thickness Dependent
Dielectric Properties of Sol Gel prepared Lead- Lanthanum TiTanate Films. To Be published,
Journal of Integrated Ferroelectrics.
64. J.R. Kirtley, P. Chaudhari, M.B. Ketchen, N. Khare, S.Y. Lin and T.M. Shaw, "Scannning
SQUID TEST of the Symmetry of the High-Tc Superconducting Order Parameter" To be
65. C.C. Tsuei, J.R. Kirtley, C.C. Chi, L.S. Yu-Jahnes, A. Gupta, T.M. Shaw, J.Z. Sun and M.B.
Ketchen, Pairing Symmetry and Flux Quantization in a Tri-Crytal Superconducting Ring of
YBa&sub2.Cu&sub3.:f.O sub < 7 -dlt > :ef.", To be published.... (1994).