Manufacturing method for large-scale production of thin-film solar cells

• US 7,544,884 B2
• Filed: 10/25/2004
• Issued: 06/09/2009
• Est. Priority Date: 09/30/2002
• Status: Active Grant

• Current Assignee: Beijing Apollo Ding Rong Solar Technology Co., Ltd
• Original Assignee: MiaSole Incorporated (Wei Jun Li)
• Inventors: Hollars, Dennis R.
• Primary Examiner(s): Neckel; Alexa D
• Assistant Examiner(s): Mowla; Golam
• Application Number:
  US10/973,714
• Publication Number:
  US 20050109392A1
• Time in Patent Office: 1,688 Days
• Field of Search: 136/256, 136/244, 136/245, 136/251, 136/252, 136/262, 136/264, 136/265, 257/43, 257/431, 257/464, 257/433
• US Class Current: 136/256
• CPC Class Codes: C23C 14/0057 using reactive gases other than O2, H2O, N2, NH3 or CH4
• CPC Class Codes: C23C 14/3414 Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
• CPC Class Codes: C23C 14/352 using more than one target C23C14/56 takes precedence
• CPC Class Codes: C23C 14/562 for coating elongated substrates
• CPC Class Codes: H01L 31/022425 for solar cells
• 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 31/0336 in different semiconductor regions, e.g. Cu2X/CdX hetero- junctions, X being an element of Group VI of the Periodic Table
• CPC Class Codes: H01L 31/18 Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
• 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 method of manufacturing improved thin-film solar cells entirely by sputtering includes a high efficiency back contact/reflecting multi-layer containing at least one barrier layer consisting of a transition metal nitride. A copper indium gallium diselenide (Cu(In_xGa_1-x)Se₂) absorber layer (X ranging from 1 to approximately 0.7) is co-sputtered from specially prepared electrically conductive targets using dual cylindrical rotary magnetron technology. The band gap of the absorber layer can be graded by varying the gallium content, and by replacing the gallium partially or totally with aluminum. Alternately the absorber layer is reactively sputtered from metal alloy targets in the presence of hydrogen selenide gas. RF sputtering is used to deposit a non-cadmium containing window layer of ZnS. The top transparent electrode is reactively sputtered aluminum doped ZnO. A unique modular vacuum roll-to-roll sputtering machine is described. The machine is adapted to incorporate dual cylindrical rotary magnetron technology to manufacture the improved solar cell material in a single pass.

Claims

1. A method of manufacturing a solar cell, comprising:

passing a web substrate from an input module to an output module through a plurality of independently isolated, connected process modules at the same time such that the web substrate continuously extends from the input module to the output module while passing through the plurality of the independently isolated, connected process modules;

depositing a conductive film on a surface of the substrate;

depositing at least one p-type semiconductor absorber layer on the conductive film, wherein the p-type semiconductor absorber layer includes a copper indium diselenide (CIS) based alloy material, and wherein the deposition of the p-type semiconductor absorber layer includes sputtering the CIS based alloy material from a pair of conductive targets;

depositing an n-type semiconductor layer on the p-type semiconductor absorber layer to form a p-n junction; and

depositing a transparent electrically conductive top contact layer on the n-type semiconductor layer;

wherein each of the conductive film, the at least one p-type semiconductor absorber layer, the n-type semiconductor layer and the transparent electrically conductive top contact layer are deposited at the same time on the web substrate in a respective one of the plurality of the independently isolated, connected process modules.

2. The method of claim 1, wherein the pair of conductive targets comprises:

a first target comprising a mixture of copper and selenium; and

a second target comprising a mixture of indium, gallium, and selenium.

3. The method of claim 1, wherein the pair of conductive targets comprises:

a first target comprising a mixture of copper and selenium; and

a second target comprising a mixture of indium, aluminum, and selenium.

4. The method of claim 1, wherein the pair of conductive targets are disposed on dual cylindrical rotary magnetrons.

5. The method of claim 1, wherein the sputtering of the CIS based alloy material further comprises:

adjusting a power ratio between the first target and the second target so that the deposited p-type semiconductor absorber layer is slightly copper deficient.

6. The method of claim 1, wherein the sputtering of the CIS based alloy material from the pair of conductive targets includes:

sputtering the CIS material from two or more pairs of the conductive targets in a sequential manner, wherein the composition of each pair of conductive targets varies relative to the other pairs of conductive targets such that the deposited p-type semiconductor absorber layer has a graded bandgap.

7. The method of claim 1, wherein the deposition of the n-type semiconductor layer includes RF sputtering from a stoichiometric zinc sulfide target in a magnetron configuration.

8. The method of claim 1, wherein the substrate comprises a thin metallic foil.

9. The method of claim 8, wherein the thin metallic foil is selected from stainless steel, copper, and aluminum.

10. The method of claim 1, wherein the CIS based alloy material is selected from copper indium diselenide, copper indium gallium diselenide and copper indium aluminum diselenide.

11. The method of claim 1, wherein the steps of depositing the conductive film, depositing the at least one p-type semiconductor absorber layer, depositing the n-type semiconductor layer, and depositing the transparent electrically conductive top contact layer are performed by sputtering.

12. The method of claim 11, wherein the steps of depositing the conductive film, depositing the at least one p-type semiconductor absorber layer, depositing the n-type semiconductor layer, and depositing the transparent electrically conductive top contact layer are performed by sputtering in a same sputtering apparatus.

13. The method of claim 12, wherein the steps of depositing the conductive film, depositing the at least one p-type semiconductor absorber layer, depositing the n-type semiconductor layer, and depositing the transparent electrically conductive top contact layer comprise passing a metallic web substrate from the input module to the output module though the plurality of process modules in which each of the conductive film, the p-type absorber layer, the n-type semiconductor layer and the transparent electrically conductive top contact layer are deposited over the substrate by sputtering.

23. The method of claim 1, further comprising cutting the web in the output module.

24. The method of claim 1, wherein the step of sputtering the CIS based alloy material from the pair of conductive targets comprises reactively sputtering the CIS based alloy material from the pair of targets, where each target comprises copper, indium and gallium, in a selenium containing ambient.

25. The method of claim 24, wherein an atomic ratio of copper to indium plus gallium in each target is less than one such that the CIS based alloy material comprises a copper deficient copper indium gallium diselenide material.

26. The method of claim 25, wherein the selenium containing ambient comprises hydrogen selenide gas provided into a sputtering system.

14. A method of manufacturing a solar cell, comprising:

passing a metallic web substrate from an input module to an output module through a plurality of independently isolated, connected process modules at the same time such that the web substrate continuously extends from the input module to the output module while passing though the plurality of the independently isolated, connected process modules;

sputtering a conductive film on a surface of the substrate in a first process module;

sputtering at least one p-type semiconductor absorber layer on the conductive film in a second process module, wherein the p-type semiconductor absorber layer includes a copper indium diselenide (CIS) based alloy material;

sputtering an n-type semiconductor layer on the p-type semiconductor absorber in a third process module layer to form a p-n junction; and

sputtering a transparent electrically conductive top contact layer on the n-type semiconductor layer in a fourth process module;

wherein each of the conductive film, the at least one p-type semiconductor absorber layer, the n-type semiconductor layer and the transparent electrically conductive top contact layer are deposited at the same time on the web substrate in a respective one of the plurality of the independently isolated, connected process modules.

15. The method of claim 14, wherein the steps of sputtering the conductive film, sputtering the at least one p-type semiconductor absorber layer, sputtering the n-type semiconductor layer, and sputtering the transparent electrically conductive top contact layer are performed in a sputtering apparatus without breaking

16. The method of claim 14, wherein the CIS based alloy material is selected from copper indium diselenide, copper indium gallium diselenide and copper indium aluminum diselenide.

17. The method of claim 14, wherein the sputtering of the p-type semiconductor absorber layer includes sputtering the CIS based alloy material from a pair of conductive targets.

18. The method of claim 14, wherein the metallic web substrate comprises a thin metallic foil web selected from stainless steel, copper, and aluminum web.

19. The method of claim 14, further comprising cutting the web in the output module.

20. The method of claim 14, wherein the step of sputtering at least one p-type semiconductor absorber layer comprises reactively sputtering the at least one p-type semiconductor absorber layer from a pair of targets, each target comprising copper, indium and gallium, in a selenium containing ambient.

21. The method of claim 20, wherein an atomic ratio of copper to indium plus gallium in each target is less than one such that the p-type semiconductor absorber layer comprises a copper deficient copper indium gallium diselenide material.

22. The method of claim 21, wherein the selenium containing ambient comprises hydrogen selenide gas provided into a sputtering system.