Skip to main content

Full text of "USPTO Patents Application 08479810"

See other formats



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 



Sir: 

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

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

I have worked as a postdoctoral researcher in the Material Science Department of 
Cornell University from 1981-1982. I worked at Rockwell International Science Center 
in Thousand Oaks, California from 1 982-1984 as a ceramic scientist. I have worked as 
a research staff member in Ceramics Science at the Thomas J. Watson Research 

YO987-074BZ 1 




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 



YO987-074BZ 



2 



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

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

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

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

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

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

An exemplary list of articles applying their general 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. 



YO987-074BZ 



3 



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 
No.01P04935290 
r?« ah,,ed ,n Westchester County , 
commission Expires July 5, 



YO987-074BZ 



4 



PUBLICATIONS T.M.SHAW 



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 
1431-1435 (1983). 



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. 



1 




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, 
P.4032(1987). 



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). 



2 



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. 



41. 



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 



3 



sub 0.86 Sr sub 0.14 )CaO sub 2:ef.," Materials Research Society Proceedings, 169, 1013 
(1990). 

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, 
(1993). 

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). 



4 



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. 
Res.,9,P.2566, (1994). 

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 
published (1994) 

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). 



5