Production of thin, stable, solid electrolyte films of high ionic conductivity

• US 4,105,807 A
• Filed: 07/28/1975
• Issued: 08/08/1978
• Est. Priority Date: 07/28/1975
• Status: Expired due to Term

• Current Assignee: Unican Electrochemical Products Limited
• Original Assignee: Unican Electrochemical Products Limited
• Inventors: Arora, Mulk R.
• Primary Examiner(s): Esposito, Michael F.
• Application Number:
  US05/599,897
• Time in Patent Office: 1,107 Days
• Field of Search: 204/192 C, 204/192 SP, 427/126, 427/255, 427/248 R, 136/62, 429/191
• US Class Current: 427/126.1
• CPC Class Codes: H01L 2224/32225 the item being non-metallic, e.g. insulating substrate with or without metallisation
• CPC Class Codes: H01L 2224/45144 Gold (Au) as principal constituent
• CPC Class Codes: H01L 2224/48227 connecting the wire to a bond pad of the item
• CPC Class Codes: H01L 2224/48472 the other connecting portion not on the bonding area also being a wedge bond, i.e. wedge-to-wedge
• CPC Class Codes: H01L 2224/73265 Layer and wire connectors
• CPC Class Codes: H01L 23/58 Structural electrical arrangements for semiconductor devices not otherwise provided for , e.g. in combination with batteries H01L23/49593, H01L23/49596 take precedence
• CPC Class Codes: H01L 2924/00 Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
• CPC Class Codes: H01M 6/18 with solid electrolyte

Abstract

Production of thin stable films of oxy-anion-substituted silver iodide solid electrolytes, such as Ag₁₉ I₁₅ P₂ O₇, on a substrate, such films having good ionic conductivity at room temperature, by vaporizing such oxy-anion-substituted silver iodide elecytrolyte material, or a mixture of the components thereof in stoichiometric proportions, by flash evaporation of such electrolyte material at high temperature, preferably ranging from about 1,400° to about 1,600° C., or by RF sputtering, preferably at electrode potentials ranging from about 700 to about 900 volts, and maintaining the substrate on which the solid electrolyte film is deposited, at certain elevated temperatures, preferably ranging from about 140° to about 150° C., to permit recombination and deposition of the vaporized constituents of the electrolyte material on the substrate, to form a thin film of the solid electrolyte such that the solid electrolyte film thus formed is neither iodine-rich nor iodine-poor, relative to the proper stoichiometry for such solid electrolyte.

Claims

1. A process for depositing thin films of complex silver iodo solid electrolytes on a substrate, said electrolytes having good ionic conductivity at room temperature, which comprises evaporating an electrolyte material selected from the group consisting of (a) a stoichiometric complex silver iodo solid electrolyte material and (b) a mixture of the components in stoichiometric proportions of said solid electrolyte material, by flash evaporation, and wherein the vaporized products include silver-containing and iodine-containing constituents, and depositing said constituents on a heated substrate while maintaining the temperature of said heated substrate at a sufficiently elevated temperature to maintain the original stoichiometric ratio of said constituents as they recombine and deposit on said substrate to form the original solid electrolyte material.

2. The process as defined in claim 1, said evaporation of said solid electrolyte material or said mixture of said components thereof being carried out by flash evaporation at high temperatures.

3. The process as defined in claim 1, wherein said electrolyte material is a mixture of the components of said electrolyte material in stoichiometric proportions.

4. The process as defined in claim 1, wherein said electrolyte material is an oxy-anion-substituted silver iodide solid electrolyte.

5. The process as defined in claim 1, wherein said electrolyte material is a mixture of powders comprising the components of an oxy-anion-substituted silver iodide electrolyte, in stoichiometric proportions.

6. The process as defined in claim 1, wherein said electrolyte material is a cation substituted silver iodide solid electrolyte.

7. The process as defined in claim 1, wherein said electrolyte material is an anion and cation substituted silver iodide solid electrolyte.

8. The process as defined in claim 6, wherein said solid electrolyte is RbAg₄ I₅, said electrolyte is vaporized at temperature ranging from about 900°

to about 1100°

C and said substrate is maintained at temperature ranging from 60°

to about 80°

C.

9. A process for fabricating stable thin films of oxy-anion-substituted silver iodide solid electrolytes having high ionic conductivity at room temperature, on a substrate, which comprises vaporizing an electrolyte material selected from the group consisting of (a) an oxy-anion-substituted silver iodide solid electrolyte and (b) a mixture of the components in stoichiometric proportions of said last mentioned solid electrolyte, by flash evaporation, and wherein the vaporized decomposition products of said electrolyte material include silver-containing iodine-containing and oxy-anion-containing constituents, and depositing said vaporized constituents on a substrate which is maintained at a high temperature such that the net condensation of the vapors of said constituents on said substrate is in proper stoichiometric proportions to form a thin film of said oxy-anion-substituted silver iodide solid electrolyte, said solid electrolyte film being neither iodine-poor nor iodine-rich with respect to the stoichiometric proportion of iodine in said solid electrolyte.

10. The process as defined in claim 9, wherein said solid electrolyte is Ag₁₉ I₁₅ P₂ O₇, or a mixture of AgI and Ag₄ P₂ O₇ in stoichiometric proportions to form Ag₁₉ I₁₅ P₂ O₇, said substrate being maintained at a temperature ranging from about 130°

to about 155°

C.

11. The process as defined in claim 9, said oxy-anion-substituted silver iodide selected from the group consisting of Ag₆ I₄ WO₄, Ag₇ I₄ AsO₄, Ag₇ I₄ VO₄, Ag₇ I₄ PO₄ and Ag₁₉ I₁₅ P₂ O₇.

12. The process as defined in claim 11, said substrate being maintained at a temperature ranging from about 130°

to about 155°

C.

13. The process as defined in claim 11, wherein said solid electrolyte is Ag₁₉ I₁₅ P₂ O₇, or a mixture of AgI and Ag₄ P₂ O₇ in stoichiometric proportions to form Ag₁₉ I₁₅ P₂ O₇.

14. The process as defined in claim 12, said vaporizing said electrolyte material being carried out by flash evaporation of said electrolyte material at temperature ranging from about 1250°

to about 1600°

C.

15. The process as defined in claim 13, said vaporizing said electrolyte material being carried out by flash evaporation of said electrolyte material at temperature ranging from about 1400°

to about 1600°

C, and said substrate being maintained at a temperature ranging from about 140°

to about 150°

C.

16. The process as defined in claim 12, wherein said film of solid electrolyte is deposited on said substrate at a rate ranging from about 15 to about 60 A/sec., and wherein said film is deposited to a thickness of about 5,000 to about 50,000 A.

17. The process as defined in claim 15, wherein said film of solid electrolyte is deposited on said substrate at a rate ranging from about 20 to about 50 A/sec., and wherein said film is deposited to a thickness of about 25,000 to about 50,000 A.

18. The process as defined in claim 12, said substrate being a ceramic or metallic substrate.

19. A process for depositing thin films of complex silver iodo solid electrolytes on a substrate, said electrolytes having good ionic conductivity at room temperature, which comprises evaporating an electrolyte material selected from the group consisting of (a) a complex silver iodo solid electrolyte material and (b) a mixture of the components in stoichiometric proportions of said solid electrolyte material and wherein the vaporized products include silver-containing and iodine-containing constitutents, and depositing said constituents on a substrate while maintaining the temperature of said substrate at a sufficiently elevated temperature to maintain the original stoichiometric ratio of said constituents as they recombine and deposit on said substrate to form the original solid electrolyte material, said evaporation of said components thereof being carried out by RF sputtering at electrode potentials producing good adherence of the deposited solid electrolyte on said substrate, in the form of a film of substantially uniform thickness.

20. A process for fabricating stable thin films of oxy-anion-substituted silver iodide solid electrolytes having high ionic conductivity at room temperature, on a substrate, which comprises vaporizing an electolyte material selected from the group consisting of (a) an oxy-anion-substituted silver iodide solid electrolyte and (b) a mixture of the components in stoichiometric proportions of said last-mentioned solid electrolyte, by RF sputtering at potentials across the electrodes ranging from about 700 to about 900 volts, said electrolyte material maintained at a temperature below about 200°

C, and wherein the vaporized decomposition products of said electrolyte material include silver-containing, iodine-containing and oxy-anion containing constituents, and depositing said vaporized constituents on a substrate which is maintained at a high temperature such that the net condensation of the vapors of said constituents on said substrate is in proper stoichiometric proportions to form a thin film of said oxy-anion-substituted silver iodide solid electrolyte, said solid electrolyte film being neither iodine-poor nor iodine-rich with respect to the stoichiometric proportion of iodine in said solid electrolyte, and wherein said solid electrolyte is Ag₁₉ I₁₅ P₂ O₇, or a mixture of AgI and Ag₄ P₂ O₇ in stoichiometric proportions to form Ag₁₉ I₁₅ P₂ O₇.

21. A process for fabricating stable thin films of oxy-anion-substituted silver iodide solid electrolytes having high ionic conductivity at room temperature, on a substrate, which comprises vaporizing an electrolyte material selected from the group consisting of (a) an oxy-anion-substituted silver iodide solid electrolyte and (b) a mixture of the components in stoichiometric proportions of said last-mentioned solid electrolyte, by RF sputtering at potentials across the electrodes ranging from about 700 to about 900 volts, and wherein the vaporized decomposition products of said electrolyte material include silver-containing, iodine-containing and oxy-anion-containing constituents, and depositing said vaporized constituents on a substrate which is maintained at a high temperature such that the net condensation of the vapors of said constituents on said substrate is in proper stoichiometric proportions to form a thin film of said oxy-anion-substituted silver iodide solid electrolyte, said solid electrolyte film being neither iodine-poor nor iodine-rich with respect to the stoichiometric proportion of iodine in said solid electrolyte, said oxy-anion-substituted silver iodide selected from the group consisting of Ag₆ I₄ WO₄, Ag₇ I₄ AsO₄, Ag₇ I₄ VO₄, Ag₇ I₄ PO₄ and Ag₁₉ I₁₅ P₂ O₇, said substrate being maintained at a temperature ranging from about 130°

L to about 155°

C.

22. The process as defined in claim 21, wherein said film of solid electrolyte is deposited on said substrate at a rate ranging from about 20 to about 50 A/sec., and wherein the film is deposited to a thickness of about 5,000 to about 50,000 A.