Process for producing chalcopyrite type compound thin film

• US 5,567,469 A
• Filed: 06/01/1995
• Issued: 10/22/1996
• Est. Priority Date: 10/30/1992
• Status: Expired due to Fees

• Current Assignee: New Energy and Industrial Technology Development Organizatio
• Original Assignee: Matsuhita Electric
• Inventors: Wada, Takahiro, Nishitani, Mikihiko, Negami, Takayuki
• Primary Examiner(s): Beck, Shrive
• Assistant Examiner(s): Talbot, Brian K.
• Application Number:
  US08/458,015
• Time in Patent Office: 509 Days
• Field of Search: 427/74, 427/76, 427/248.1, 427/255.2, 423/508, 423/511, 136/260
• US Class Current: 427/74
• CPC Class Codes: H01L 21/02422 Non-crystalline insulating materials, e.g. glass, polymers
• CPC Class Codes: H01L 21/02491 Conductive materials
• CPC Class Codes: H01L 21/02568 Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
• CPC Class Codes: H01L 21/02614 Transformation of metal, e.g. oxidation, nitridation
• CPC Class Codes: H01L 21/02631 Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
• 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: Y02E 10/541 CuInSe2 material PV cells
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

A chalcopyrite compound, for instance, CuInS₂ or CuInSe₂, is prepared by subjecting a thin film containing copper metal, indium metal, and an indium compound or a compound which contains both indium and copper, selected from the group consisting of oxides, sulfides and selenides, with heat under a reducing atmosphere containing at least one of the Group VIb element or under an atmosphere containing a reducing compound of at least one of the Group VIb element, thereby converting said thin film into a chalcopyrite compound.

Claims

1. A process for producing a Cu-In-Group VI chalcopyrite film, which comprises:

treating a film containing (1) copper metal, (2) indium metal, and (3) an indium compound selected from the group consisting of oxides, sulfides and selenides, with heat under a reducing atmosphere containing at least one of a Group VIb element or under an atmosphere containing a reducing compound of at least one of a Group VIb element, wherein an atomic ratio In/Cu of indium metal to copper metal in said film prior to heating is In/Cu≦

9/11, thereby converting said film into a Cu-In-Group VI chalcopyrite compound.

3. The process of claim 1 or claim 2, wherein copper metal and indium metal are present as an alloy of copper and indium.

4. The process of claim 3, wherein said alloy is a Cu₁₁ In₉ alloy.

5. The process of claim 1, wherein said indium compound is noncrystalline.

8. The process of any one of claim 1 or 2, wherein said reducing compound of the Group VIb element is at least one selected from the group consisting of H₂ S, CS₂, H₂ Se, (CH₃)₂ Se and (C₂ HS)₂ Se.

9. The process of any one of claim 1 or 2, wherein said Group VIb element is at least one selected from the group consisting of S and Se.

10. The process of any one of claim 1 or 2, wherein said heat treatment is performed at a temperature of 250°

C. to 700°

C.

11. The process of claim 10, wherein said heat treatment is performed at a temperature of 400°

C. to 600°

C.

2. A process of producing a Cu-In-Group VI chalcopyrite film, which comprises:

treating a film containing (1) copper metal, (2) indium metal, and (3) a compound containing copper and indium selected from the group consisting of oxides, sulfides and selenides, with heat under a reducing atmosphere containing at least one of a Group VIb element or under an atmosphere containing a reducing compound of at least one of a Group VIb element, wherein an atomic ratio In/Cu of indium metal to copper metal in said film prior to heating is In/Cu≦

9/11, thereby converting said film into a Cu-In-Group VI chalcopyrite compound.

6. The process of claim 2, wherein said compound containing copper and indium is noncrystalline.

7. A process of producing a Cu-In-Group VI chalcopyrite film, which comprises:

treating a film containing (1) copper metal, (2) indium metal, and (3) a mixture of (3a) a compound containing copper and indium selected from the group consisting of oxides, sulfides and selenides, and of (3b) an indium compound selected from the group consisting of oxides, sulfides and selenides, with heat under a reducing atmosphere containing at least one of a Group VIb element or under an atmosphere containing a reducing compound of at least one of a Group VIb element, thereby converting said film into a Cu-In-Group VI chalcopyrite compound.

12. The process of claim 7, wherein copper metal and indium metal are present as an alloy of copper and indium.

13. The process of claim 7, wherein said compound containing copper and indium is noncrystalline.