Thin films of mixed metal compounds

• US 4,523,051 A
• Filed: 09/27/1983
• Issued: 06/11/1985
• Est. Priority Date: 09/27/1983
• Status: Expired due to Term

• Current Assignee: The Boeing Co.
• Original Assignee: The Boeing Co.
• Inventors: Chen, Wen S., Mickelsen, Reid A.
• Primary Examiner(s): Weisstuch, Aaron
• Application Number:
  US06/536,395
• Time in Patent Office: 623 Days
• Field of Search: 136/258 PC, 136/260, 136/264, 136/265, 357/11, 357/16, 357/30, 357/59, 357/61, 29/572, 427/74, 427/76, 427/87, 427/255.2, 148/174, 148/175
• US Class Current: 136/260
• CPC Class Codes: H01L 31/022425 for solar cells
• CPC Class Codes: H01L 31/0322 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
• CPC Class Codes: H01L 31/072 the potential barriers being only of the PN heterojunction type
• CPC Class Codes: H01L 31/0749 including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
• CPC Class Codes: Y02E 10/541 CuInSe2 material PV cells

Abstract

A compositionally uniform thin film of a mixed metal compound is formed by simultaneously evaporating a first metal compound and a second metal compound from independent sources. The mean free path between the vapor particles is reduced by a gas and the mixed vapors are deposited uniformly. The invention finds particular utility in forming thin film heterojunction solar cells.

Claims

1. A method for forming a uniform composition thin film of a polycrystalline mixed metal compound on a substrate, said method consisting essentially of the steps of:

(a) introducing a vapor of a first metal compound to a vessel containing said substrate from a first vapor source while simultaneously introducing a vapor of a second metal compound from a second vapor source to said vessel to form a vapor mixture comprised of metal compounds, said first and second metals comprising the metal components of said mixed metal compound;

(b) independently controlling the vaporization rate of said first and second vapor sources;

(c) reducing the mean free path between vapor particles of said mixture in said vessel by including a gas within said vessel, said gas being present in an amount sufficient to induce homogeneity of said vapor mixture; and

(d) depositing said homogeneous vapor mixture on said substrate to form a uniform composition polycrystalline film of said first and second metal compounds thereon.

2. The method of claim 1 wherein said first metal is an element from Group IIB of the Periodic Table.

3. The method of claim 1 wherein said second metal is an element from Group IIB of the Periodic Table.

4. The method of claim 1 wherein said substrate is a I-III-VI₂ chalcopyrite material.

5. The method of claim 1 wherein said mixed metal compound is a sulfide.

6. The method of claim 5 wherein said gas is hydrogen.

7. The method of claim 6 wherein hydrogen in said vessel is present in an amount to provide a pressure in the range of from 1-3×

10^-4 torr.

8. A method of making a thin film heterojunction solar cell according to the method of claim 5 wherein said mixed metal compound is Zn_x Cd_1-x S and said compound is about 20% Zn, said substrate being CuInSe₂.

9. The method of claim 1 wherein said mixed metal compound is Zn_x Cd_1-x S, wherein said mixture contains from 10 to 30% Zn.

10. A method of making a thin film heterojunction solar cell comprised of a substrate of a I-III-VI₂ chalcopyrite having a thin film of a uniform composition mixed metal compound deposited thereon, said method consisting essentially of the steps of:

(a) introducing a vapor of a first metal compound to a vessel from a first vapor source while simultaneously introducing a vapor of a second metal compound from a second vapor source to said vessel thereby forming a vapor comprised of said first metal compound and said second metal compound, said first and second metals comprising the mixed metal compound;

having a common electronegative element;

(b) independently controlling the vaporization rate of said first and second vapor sources; and

(c) reducing the mean free path between vapor particle in said vessel by including a gas within said vessel, said gas being present in an amount sufficient to induce homogeneity of said vapor mixture and thereby produce a uniform composition thin film of a polycrystalline mixed metal compound comprised of said first and second metals and said common electronegative element on said substrate.

11. The method of claim 10 wherein said gas is hydrogen in an amount sufficiently to provide a pressure in said vessel of from 1-3×

10^-4 torr.

12. The method of claim 10 wherein said mixed metal compound is Zn_x Cd_1-x S and Zn comprises from 10 to 30% of said mixed metal compound.

13. The method of claim 12 wherein said mixed metal compound is Zn_x Cd_1-x S and Zn comprises about 20% of said mixed metal compound.

14. A thin film heterojunction solar cell, said heterojunction comprising a p-type I-III-IV₂ chalcopyrite substrate and an overlying layer of an n-type ternary mixed metal compound wherein said ternary mixed metal compound is applied to said substrate by introducing the vapor of a first metal compound to a vessel containing said substrate from a first vapor source while simultaneously introducing a vapor of a second metal compound from a second vapor source of said vessel, said first and second metals comprising the metal components of said mixed metal compound;

independently controlling the vaporization rate of said first and second vapor sources;

reducing the mean free path between vapor particles in said vessel, said gas being present in an amount sufficient to induce homogeneity of said vapor mixture; and

depositing said mixed metal compound on said substrate in the form of a uniform composition polycrystalline mixed metal compound.

15. The solar cell of claim 14 wherein said mixed metal compound is Zn_x Cd_1-x S and said compound is from 10 to 30% Zn.

16. The solar cell of claim 15 wherein said Zn_x Cd_1-x S is about 20% Zn.

17. The solar cell of claim 15 wherein said substrate is CuInSe₂.

18. The solar cell of claim 17 wherein the ratio of Cu to In is adjusted during deposition of said substrate of CuInSe₂ such that the ratio of Cu to In is not uniform within said substrate upon its formation.