Sodium species surface treatment of thin film photovoltaic cell and manufacturing method

• US 8,476,104 B1
• Filed: 09/18/2009
• Issued: 07/02/2013
• Est. Priority Date: 09/29/2008
• 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:
  US12/563,064
• Time in Patent Office: 1,383 Days
• Field of Search: 438/85, 257E21466-E21467, 257/E21.483, 257/E21.485, 257/E21.497
• 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, forming a first electrode layer overlying the surface region, forming a copper layer overlying the first electrode layer and forming an indium layer overlying the copper layer to form a multi-layered structure. The multi-layered structure is subjected to a thermal treatment process in an environment containing a sulfur bearing species to forming a copper indium disulfide material. The copper indium disulfide material comprising a copper-to-indium atomic ratio ranging from about 1.2:1 to about 2:1 and a thickness of substantially copper sulfide material having a copper sulfide surface region. The thickness of the copper sulfide material is selectively removed to expose a surface region having a copper poor surface comprising a copper to indium atomic ratio of less than about 0.95:1. The method subjects the copper poor surface to a sodium species to convert the copper poor surface from an n-type semiconductor characteristic to a p-type semiconductor characteristic. 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 copper indium disulfide material from at least the thermal treatment process of the multi-layered structure, the copper indium disulfide material comprising a copper-to-indium atomic ratio ranging from about 1.2;

1 to about 2;

1 and a thickness of substantially copper sulfide material having a copper sulfide surface region, wherein the formed copper indium disulfide is mixed with a copper indium aluminum disulfide or copper indium gallium disulfide;

removing the thickness of the copper sulfide material to expose a surface region having a copper poor surface comprising a copper to indium atomic ratio of less than about 0.95;

1;

subjecting the copper poor surface to a sodium species to convert the copper poor surface from an n-type semiconductor characteristic to a p-type semiconductor characteristic;

subjecting the copper poor surface to a treatment process during a time period associated with the subjecting of the copper poor surface with the sodium species; and

forming a window layer overlying the copper indium disulfide material.

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

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

4. The method of claim 1 wherein the removing comprises using a solution of potassium cyanide to selectively remove the thickness of copper sulfide material.

5. 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.

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

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

8. The method of claim 1 wherein the sodium species compensates for any missing copper in the copper poor surface.

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

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

11. The method of claim 1 wherein the copper indium disulfide has a p-type semiconductor characteristic.

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

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

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

15. 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 comprising at least a copper poor copper indium disulfide material including a copper poor copper indium disulfide material surface, the copper poor copper indium disulfide surface having an atomic ratio of Cu;

In of about 0.99 and less, wherein the chalcopyrite material is mixed with a copper indium aluminum gallium disulfide;

compensating the copper poor copper indium disulfide material using a sodium species to change in characteristic from an n-type to a p-type, wherein the sodium species is incorporated subsequently to the formation of the copper-poor, copper indium disulfide material;

forming a window layer overlying the chalcopyrite material; and

forming a second electrode layer overlying the window layer.