Process for fabricating polycrystalline semiconductor thin-film solar cells, and cells produced thereby

• US 6,137,048 A
• Filed: 12/22/1998
• Issued: 10/24/2000
• Est. Priority Date: 11/07/1996
• Status: Expired due to Term

• Current Assignee: Alliance For Sustainable Energy LLC
• Original Assignee: Midwest Research Institute
• Inventors: Sheldon, Peter, Wu, Xuanzhi
• Primary Examiner(s): CHAPMAN, MARK A
• Application Number:
  US09/218,206
• Time in Patent Office: 672 Days
• Field of Search: 136/260, 136/265, 136/256, 438/487
• US Class Current: 136/260
• CPC Class Codes: H01L 31/073 comprising only AIIBVI compound semiconductors, e.g. CdS/CdTe solar cells
• CPC Class Codes: H01L 31/1828 the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
• CPC Class Codes: H01L 31/1884 Manufacture of transparent electrodes, e.g. TCO, ITO
• CPC Class Codes: Y02E 10/543 Solar cells from Group II-VI materials
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

A novel, simplified method for fabricating a thin-film semiconductor heterojunction photovoltaic device includes initial steps of depositing a layer of cadmium stannate and a layer of zinc stannate on a transparent substrate, both by radio frequency sputtering at ambient temperature, followed by the depositing of dissimilar layers of semiconductors such as cadmium sulfide and cadmium telluride, and heat treatment to convert the cadmium stannate to a substantially single-phase material of a spinel crystal structure. Preferably, the cadmium sulfide layer is also deposited by radio frequency sputtering at ambient temperature, and the cadmium telluride layer is deposited by close space sublimation at an elevated temperature effective to convert the amorphous cadmium stannate to the polycrystalline cadmium stannate with single-phase spinel structure.

Claims

1. Method of fabricating a thin-film semiconductor heterojunction photovoltaic device, comprising the steps of:

a) depositing a layer of cadmium stannate on a transparent substrate by radio frequency sputtering at ambient temperature to act as a transparent conductive oxide (TCO) layer forming a front contact;

b) depositing a zinc stannate layer on said TCO layer by radio frequency sputtering at ambient temperature to form a buffer layer;

c) depositing a first semiconductor window layer upon said buffer layer;

d) depositing a second semiconductor layer upon said window layer to form a heterojunction; and

e) heat treating the device formed by steps (a)-(d) to convert said cadmium stannate layer to a substantially single-phase material with a spinel crystal structure.

2. The method of claim 1, wherein said first and second semiconductor layers are cadmium sulfide and cadmium telluride, respectively.

3. The method of claim 1, wherein said layers of cadmium stannate and zinc stannate are applied in amorphous form.

4. The method of claim 1 which further comprises treatment with cadmium chloride at elevated temperature and the depositing of a thin electrically conductive film upon said cadmium telluride layer to serve as a rear electrical contact.

5. The method of claim 1, wherein said window layer is deposited by radio frequency sputtering at ambient temperature and said cadmium telluride is deposited by close space sublimation at a temperature of at least about 500°

C., which temperature is effective to convert said cadmium stannate to a single-phase spinel crystal structure.

6. The method of claim 1, wherein said second semiconductor layer is deposited at a temperature in the range of from ambient temperature to about 550°

C., followed by heat treatment of the device at a temperature in the range of from about 500°

to about 630°

C.

7. The method of claim 6 wherein said second semiconductor layer is deposited by electrodeposition, screen printing, sputtering, spraying or physical vapor deposition (PVD).

8. The method of claim 1 wherein said window layer is applied by close space sublimation followed by the depositing of said second semiconductor layer by close space sublimation.

9. The method of claim 8, wherein the close space sublimation of said window layer is carried out at a temperature in the range of from about 500°

C. to about 600°

C. and the close space sublimation of said second semiconductor layer is carried out at a temperature in the range of from about 500°

C. to about 630°

C.

10. A thin-film photovoltaic device prepared by the method of claim 1.

11. A thin-film photovoltaic device prepared by the method of claim 5.

12. A thin-film photovoltaic device prepared by the method of claim 6.

13. A thin-film photovoltaic device prepared by the method of claim 8.

18. The method of claim 11, wherein the first three layers of cadmium stannate, zinc stannate and cadmium sulfide are annealed in hydrogen at a temperature in the range of from about 300°

C. to about 450°

C. before said cadmium telluride layer is deposited.

14. A method of fabricating a thin-film CdS/CdTe heterojunction photovoltaic device, comprising the steps of:

a) depositing a layer of cadmium stannate on a transparent substrate by radio frequency sputtering at ambient temperature to act as a TCO layer forming a front contact;

b) depositing a zinc stannate layer on said TCO layer by radio frequency sputtering at ambient temperature to form a buffer layer;

c) depositing a cadmium sulfide window layer upon said buffer layer by radio frequency splattering at ambient temperature; and

d) depositing a layer of cadmium telluride upon said window layer by close space sublimination at elevated temperature, thus forming a heterojunction, wherein the temperature profile for the close space sublimation of said cadmium telluride is effective to convert said cadmium stannate layer to a substantially single-phase material with a spinel crystal structure.

15. The method of claim 14, wherein said layers of cadmium stannate and zinc stannate are applied in amorphous form.

16. The method of claim 14, wherein said layer of cadmium telluride is applied at a temperature in the range of from about 500°

C. to about 630°

C.

17. The method of claim 14, further comprising the steps of cadmium chloride treatment at elevated temperature, which temperature is lower than that in claim 14 (d), and the depositing of a thin electrically conducting film upon said cadmium telluride layer to serve as a rear electrical contact.