Bulk sulfide species treatment of thin film photovoltaic cell and manufacturing method

• US 8,435,826 B1
• Filed: 09/25/2009
• Issued: 05/07/2013
• Est. Priority Date: 10/06/2008
• Status: Expired due to Fees

• Current Assignee: Stion Corporation
• Original Assignee: Stion Corporation
• Inventors: Lee, Howard W. H.
• Primary Examiner(s): Yang, Minchul
• Application Number:
  US12/567,704
• Time in Patent Office: 1,320 Days
• Field of Search: 438/85, 257/E21.466, 257/467, 257/483, 257/485, 257/497
• US Class Current: 438/85
• 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 31/0749 including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
• CPC Class Codes: Y02E 10/541 CuInSe2 material PV cells

Abstract

A method for forming a thin film photovoltaic device. The method includes providing a transparent substrate comprising a surface region and forming a first electrode layer overlying the surface region. The method forms a bulk copper indium disulfide material from a multi-layered structure comprising a copper species, an indium species, and a sulfur species overlying the first electrode layer. The bulk copper indium disulfide material comprises one or more portions of a copper poor copper indium disulfide material, a copper poor surface regions, and one or more portions of a sulfur deficient copper indium disulfide material characterized by at least a CuInS_2-x species, where 0<x<2. The copper poor surface and one or more portions of the copper poor copper indium disulfide material are subjected to a sodium species derived from a sodium sulfide material to convert the copper poor surface from an n-type characteristic to a p-type characteristic. The method also subjects the one or more portions of the sulfur deficient copper indium disulfide material to a sulfur species derived form the sodium sulfide material to improve a conversion efficiency characteristic of the photovoltaic device. A window layer is formed overlying the copper indium disulfide material.

Claims

1. A method for forming a thin film photovoltaic device, the method comprising:

providing a transparent substrate comprising a surface region;

forming a first electrode layer overlying the surface region;

forming a copper layer overlying the first electrode layer;

forming an indium layer overlying the copper layer to form a multi-layered structure;

subjecting at least the multi-layered structure to a thermal treatment process in an environment containing a sulfur bearing species;

forming a bulk copper indium disulfide material from at least the treatment process of the multi-layered structure, the bulk copper indium disulfide material comprising one or more portions of copper poor copper indium disulfide material characterized by a copper-to-indium atomic ratio of less than about 0.95;

1 and the bulk copper indium disulfide material having a surface region characterized by a copper poor surface comprising a copper to indium atomic ratio of less than about 0.95;

1, the bulk copper indium disulfide material comprising one or more portions of a sulfur deficient copper indium disulfide material characterized by at least a CuInS_2-x species, where 0<

x<

2, and the bulk copper indium disulfide material having a sulfur deficient surface region characterized by the CuInS_2-x, species, where 0<

x<

2, from at least the heat treatment process;

subjecting the copper poor surface, one or more portions of the copper poor copper indium disulfide material to a sodium species derived from a sodium sulfide material to convert the copper poor surface from an n-type characteristic to a p-type characteristic, to convert any of the one or more portions of the copper poor copper indium disulfide material having the copper-to-indium atomic ratio of less than about 0.95;

1 from an n-type characteristic to a p-type characteristic;

subjecting the one or more portions of the sulfur deficient copper indium disulfide material and the sulfur deficient surface region to a sulfur species derived form the sodium sulfide material to improve a conversion efficiency characteristic; and

forming a window layer overlying the copper indium disulfide material;

whereupon the subjecting of the copper poor surface, the sulfur deficient surface, the one or more portions of the copper poor copper indium disulfide material, and the sulfur deficient copper indium disulfide material is performed during at least a thermal treatment process for a time period.

2. The method of claim 1 wherein the sulfur deficient copper indium disulfide material and the sulfur deficient surface are characterized by a low conversion efficiency.

3. The method of claim 1 wherein the subjecting to the sodium species derived from the sodium sulfide material is provided by at least one process selected from spin coating, spraying, spray pyrolysis, pyrolysis, dipping, deposition, sputtering, or electrolysis.

4. The method of claim 1 wherein the sodium species comprises sodium ions.

5. The method of claim 1 wherein the sulfur species comprises sulfide ions (S_2-).

6. The method of claim 1 wherein the sulfur deficient copper indium disulfide material has a interstitial sulfur deficient region.

7. The method of claim 1 wherein the bulk copper indium disulfide comprising a thickness of copper sulfide material, the thickness of copper sulfide material being selectively removed using a solution of potassium cyanide.

8. The method of claim 1 wherein the window layer is selected from a group consisting of a cadmium sulfide, a zinc sulfide, zinc selinium, zinc oxide, or zinc magnesium oxide.

9. The method of claim 1 wherein the thermal treatment process of the copper poor surface and the sulfur deficient surface comprises a temperature ranging from about 100 Degrees Celsius to about 500 Degrees Celsius.

10. The method of claim 1 wherein the forming of the copper layer is provided by a sputtering process or plating process.

11. The method of claim 1 wherein the sodium species derived from the sodium sulfide material compensates for any missing copper in the copper poor surface.

12. The method of claim 1 wherein the sulfide compensated surface and the sulfur.

13. The method of claim 1 wherein the fanning of the indium layer is provided by a sputtering process.

14. The method of claim 1 wherein the forming of the indium layer is provided by a plating, process.

15. The method of claim 1 wherein the bulk copper indium disulfide comprises p-type semiconductor characteristic.

16. The method of claim 1 wherein the window layer comprises an n⁺-type semiconductor characteristic.

17. The method of claim 1 further comprising introducing an indium species in the window layer to cause formation of an n⁺-type semiconductor characteristic.

18. The method of claim 1 wherein the bulk copper indium disulfide is mixed with a copper indium aluminum disulfide or copper indium gallium disulfide.

19. The method of claim 1 wherein the sulfur bearing species comprise hydrogen sulfide in fluid phase.

20. A method for forming a thin film photovoltaic device, the method comprising:

providing a transparent substrate comprising a surface region;

forming a first electrode layer overlying the surface region;

forming a chalcopyrite material overlying the electrode layer, the chalcopyrite material comprises a copper poor copper indium disulfide region and a sulfur deficient copper indium disulfide region, the copper poor copper indium disulfide region having an atomic ratio of Cu;

In of about 0.99 and less, the sulfur deficient copper indium disulfide region comprising a CuInS_2-x, species, where 2>

x>

0;

compensating the copper poor copper indium disulfide region using a sodium species to change in characteristic from an n-type to a p-type

compensating the sulfur deficient copper indium disulfide region using a sulfide species to improve a characteristic of conversion efficiency;

forming a window layer overlying the chalcopyrite material; and

forming a second electrode layer overlying the window layer.

21. A method for forming a thin film photovoltaic device, the method comprising:

providing a transparent substrate comprising a surface region;

forming a first electrode layer overlying the surface region;

forming a copper containing layer overlying the first electrode layer;

forming an indium containing layer overlying the copper containing layer to form a multi-layered structure;

subjecting at least the multi-layered structure to a thermal treatment process in an environment containing a sulfur bearing species;

forming a bulk copper indium disulfide containing material from at least the thermal treatment process of the multi-layered structure, the bulk copper indium disulfide containing material comprising one or more portions of a sulfur deficient copper indium disulfide containing material characterized by at least a CuInS_2-x species, where 0<

x<

2;

subjecting the one or more portions of the sulfur deficient copper indium disulfide containing material to a sulfur species derived from a sulfur bearing material to improve a device characteristic from a first value to a second value; and

forming a window layer overlying the copper indium disulfide material.