Method and device for cadmium-free solar cells

• US 8,628,997 B2
• Filed: 09/19/2011
• Issued: 01/14/2014
• Est. Priority Date: 10/01/2010
• Status: Expired due to Fees

• Current Assignee: Stion Corporation
• Original Assignee: Stion Corporation
• Inventors: Ramanathan, Kannan, Wieting, Robert D.
• Primary Examiner(s): Vu, David
• Assistant Examiner(s): TAYLOR, EARL N
• Application Number:
  US13/236,286
• Publication Number:
  US 20120240989A1
• Time in Patent Office: 848 Days
• Field of Search: 438/84, 438/85, 438/95, 438/104
• 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 31/0323 characterised by the doping material
• CPC Class Codes: H01L 31/0682 back-junction, i.e. rearside emitter, solar cells, e.g. interdigitated base-emitter regions back-junction cells
• 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
• CPC Class Codes: Y02E 10/547 Monocrystalline silicon PV cells

Abstract

A method for fabricating a thin film photovoltaic device is provided. The method includes providing a substrate comprising a thin film photovoltaic absorber which has a surface including copper, indium, gallium, selenium, and sulfur. The method further includes subjecting the surface to a material containing at least a zinc species substantially free of any cadmium. The surface is heated to cause formation of a zinc doped material. The zinc doped material is free from cadmium. Furthermore the method includes forming a zinc oxide material overlying the zinc doped material and forming a transparent conductive material overlying the zinc oxide material.

Claims

1. A method for fabricating a thin film photovoltaic device free from cadmium comprising:

providing a substrate having a thin film photovoltaic absorber with a surface region including a copper species, an indium species, a gallium species, a selenium species, and a sulfur species;

subjecting the surface region to a material containing at least a zinc species which is substantially free of cadmium;

heating at least the surface region to cause formation of zinc doped material at the surface region, wherein the heating comprises using a lamp heater to cause the surface region and adjacent regions to increase from room temperature to about 150 degrees Fahrenheit while keeping the majority of the absorber material substantially at room temperature;

forming zinc oxide over the zinc doped material; and

forming a transparent conductive material overlying the zinc oxide material.

2. The method of claim 1 wherein the thin-film photovoltaic absorber comprises a compound material selected from CuInSe₂, CuInGaSe₂, CuInGa(SeS)₂, and a combination thereof.

3. The method of claim 1 wherein the step of subjecting the surface region comprises immersing the surface at substantially room temperature in a liquid electrolyte solution which includes the zinc species.

4. The method of claim 3 wherein the liquid electrolyte solution comprises at least one of zinc chloride and zinc sulfate, each having a concentration of zinc ranging from 0.0001 Mol to 0.1 Mol, and the liquid electrolyte solution further comprises ammonium hydroxide having a concentration of ammonium hydroxide ranging from 0.1 Mol to 5 Mol, and water.

5. The method of claim 1 wherein the step of subjecting the surface region to the material comprises placing a solid film comprising volatile zinc species in proximity to the surface region.

6. The method of claim 5 wherein the solid film comprises zinc chloride film coated on a substrate disposed above the surface region at a distance ranging between 1 millimeter and 5 millimeters.

7. The method of claim 1 wherein the depth of the zinc doped material comprises less than about one tenth of a total thickness of the thin-film photovoltaic absorber and zinc has an atomic concentration of about 1020 cm⁻

3.

8. The method of claim 1 wherein the step of forming zinc oxide comprises using a MOCVD process at a temperature between 150°

C. and 250°

C. without introducing dopant gas.

9. The method of claim 8 wherein the MOCVD process comprises using a work gas including water vapor and diethylzinc, with a water-to-diethylzinc ratio greater than 1:

4.

12. The method of claim 1 wherein the step of forming a transparent conductive material comprises depositing a second zinc oxide material in a MOCVD process using at least diethylzinc gas combined with a diborane gas, with a ratio of diborane-to-diethylzinc gas from about one percent to about five percent.

13. The method of claim 1, wherein the lamp heater has an elongated shape to cover the substrate.

14. The method of claim 1, wherein the lamp heater is configured to scan either the length or width of the substrate.

10. A method for fabricating a thin film photovoltaic device free from cadmium comprising:

providing a substrate having a thin film photovoltaic absorber with a surface region including a copper species, an indium species, a gallium species, a selenium species, and a sulfur species;

subjecting the surface region to a material containing at least a zinc species which is substantially free of cadmium;

heating at least the surface region to cause formation of zinc doped material at the surface region;

forming zinc oxide over the zinc doped material, wherein formation comprises using a MOCVD process at a temperature between 150°

C. and 250°

C. without introducing dopant gas, and wherein the MOCVD process comprises using a work gas including water vapor, diethylzinc, and hydrogen sulfide to form a ZnO_1-xS_x material overlying the zinc-doped material; and

forming a transparent conductive material overlying the zinc oxide material.

11. The method of claim 10 wherein the step forming zinc oxide material further comprises annealing the zinc oxide material deposited by the MOCVD process, causing the depth of the zinc doped material to shift and resulting in a zinc doping level ranging from 1015 cm-3 to 1018 cm-3.

15. The method of claim 10, wherein the water-to-diethylzinc ratio is greater than 1:

4.

16. The method of claim 10, wherein the thin-film photovoltaic absorber comprises a compound material selected from CuInSe₂, CuInGaSe₂, CuInGa(SeS)₂, and a combination thereof.

17. The method of claim 10, wherein the step of subjecting the surface region comprises immersing the surface at substantially room temperature in a liquid electrolyte solution which includes the zinc species.

18. The method of claim 17, wherein the liquid electrolyte comprises at least one of zinc chloride and zinc sulfate, each having a concentration of zinc ranging from 0.0001 Mol to 0.1 Mol, and the liquid electrolyte solution further comprises ammonium hydroxide having a concentration of ammonium hydroxide ranging from 0.1 Mol to 5 Mol, and water.

19. The method of claim 10, wherein the step of subjecting the surface region to the material comprises placing a solid film comprising volatile zinc species in proximity to the surface region.