Solar cell with chalcopyrite absorber layer

• US 5,626,688 A
• Filed: 12/01/1995
• Issued: 05/06/1997
• Est. Priority Date: 12/01/1994
• Status: Expired due to Term

• Current Assignee: Saint-Gobain Glass France (Compagnie De Saint-Gobain)
• Original Assignee: Siemens AG
• Inventors: Harms, Hauke, Rimmasch, Joerk, Probst, Volker
• Primary Examiner(s): Weisstuch, Aaron
• Application Number:
  US08/565,978
• Time in Patent Office: 522 Days
• Field of Search: 136/264, 136/265, 437/5, 437/81-82, 427/76, 257/184, 257/607, 257/613, 204/192.25
• US Class Current: 136/265
• 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 31/03923 including AIBIIICVI compound materials, e.g. CIS, CIGS
• 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 substrate-independent manufacturing method for a solar cell with chalcopyrite absorber layer (4, 5) is proposed wherein a desired alkali content is obtained in the finished absorber layer by dosed addition of Na, K, or Li during the manufacturing process. An additional drive-in of alkali ions from a potentially alkali-containing substrate (1) is prevented by providing a diffusion barrier layer (2) between substrate and absorber layer.

Claims

1. A solar cell comprising a chalcopyrite absorber layer including a controlled amount of a dopant selected from alkali metals and alkali metal compounds of from about 10¹⁴ to about 10¹⁷ alkali metal atoms per square centimeter of said chalcopyrite absorber layer.

2. A solar cell comprising:

a substrate having a surface;

a diffusion barrier layer disposed on said surface sufficient to prevent diffusion of alkali metal ions from the substrate across said diffusion barrier layer;

a back electrode layer disposed on said diffusion barrier layer;

a chalcopyrite absorber layer disposed on said back electrode layer, a lower portion of said chalcopyrite absorber layer adjacent said back electrode layer including a controlled amount of dopant selected from alkali metals and alkali metal compounds;

a window layer disposed on the chalcopyrite absorber layer; and

a front electrode disposed on said window layer.

3. A solar cell as defined in claim 2, wherein said substrate includes alkali metal or alkaline earth metal contaminants.

4. A solar cell as defined in claim 2, wherein said substrate comprises glass.

5. A solar cell as defined in claim 2, wherein said diffusion barrier layer comprises TiN, Al₂ O₃, SiO₂, Si₃ N₄, ZrO₂, or TiO₂.

6. A solar cell as defined in claim 2, wherein said diffusion barrier layer has a thickness of from about 20 to about 100 nm.

7. A solar cell as defined in claim 2, wherein said back electrode layer comprises molybdenum, titanium, palladium, platinum, or compounds of any of the foregoing elements.

8. A solar cell as defined in claim 2, wherein said chalcopyrite absorber layer comprises CuInSe₂ (CIS) or CuIn(Ga)Se₂ (S₂)(=CIGS).

9. A solar cell as defined in claim 2, wherein said window layer comprises cadmium sulfide.

10. A solar cell as defined in claim 2, wherein said front electrode layer comprises a transparent conductive oxide.

11. A solar cell comprising:

an alkali-free substrate having a surface;

a back electrode disposed on said surface;

a chalcopyrite absorber layer disposed on said back electrode, a lower portion of said chalcopyrite absorber layer adjacent said back electrode layer including a controlled amount of a dopant selected from alkali metals and alkali metal compounds;

a window layer disposed on said chalcopyrite absorber layer; and

a front electrode layer disposed on said window layer.

12. A solar cell as defined in claim 11, further comprising a diffusion barrier layer disposed intermediate said back electrode layer and said chalcopyrite absorber layer.

13. A solar cell as defined in claim 12, wherein said diffusion barrier layer is electrically conductive.

14. A method for making a solar cell, comprising the steps of:

providing a substrate having a surface;

depositing a diffusion barrier layer on the surface of the substrate capable of preventing diffusion of alkali metal ions from the substrate across said diffusion barrier layer;

depositing a back electrode layer on said diffusion barrier layer;

forming a chalcopyrite absorber layer including a controlled amount of a dopant selected from alkali metals and alkali metal compounds on said back electrode layer;

depositing a window layer on the chalcopyrite absorber layer; and

depositing a front electrode layer on said window layer.

15. A method as defined in claim 14, wherein said chalcopyrite absorber layer comprises a compound semiconductor of CuInSe₂ (CIS) or CuIn(Ga)Se₂ (S₂)(=CIGS) and said forming step further includes the steps of sputtering targets to form a sputter deposited layer generally having appropriate stoichiometric amounts of each element, said targets being selected from the group consisting of copper, indium, gallium, selenium, sulfur, an alkali metal selected from sodium, potassium, lithium, and binary compounds of any of the foregoing to form said sputter deposited layer;

and

thereafter, heating the sputter deposited layer to temperatures above about 500°

C. to convert the sputtered elements into said compound semiconductor chalcopyrite absorber layer.

16. A method as defined in claim 14, wherein said chalcopyrite absorber layer comprises a compound semiconductor of CuInSe₂ (CIS) or CuIn(Ga)Se₂ (S₂) (=CIGS) and said foxing step further includes the steps of vapor depositing generally appropriate stoichiometric amounts of elements selected from the group consisting of copper, indium, gallium, selenium, sulfur, an alkali metal selected from sodium, potassium, lithium, and binary compounds of any of the foregoing elements to form a vapor-deposited layer;

and

thereafter, heating said vapor-deposited layer to a temperature above about 500°

C. to convert the vapor-deposited elements into said compound semiconductor chalcopyrite absorber layer.

17. A method as defined in claim 14, wherein said chalcopyrite absorber layer comprises a compound semiconductor of CuInSe₂ (CIS)) or CuIn(Ga)Se₂ (S₂) (=CIGS) and said forming step further includes the steps of sputtering or vapor depositing generally appropriate stoichiometric amounts of elements selected from Cu, In, Ga, Se, S, an alkali metal selected from the group consisting of Na, K, and Li, and binary compounds of any of the foregoing and wherein said stoichiometric amounts of Se or S are at least partially introduced by performing said sputtering or vapor depositing in an atmosphere comprising Se or S, respectively, to form a precursor layer;

and

thereafter, heating said precursor layer to temperatures above about 500°

C. to convert the sputtered or vapor-deposited elements into said composite semiconductor chalcopyrite absorber layer.

18. A method as defined in claim 14, wherein said chalcopyrite absorber layer comprises a compound semiconductor of CuInSe₂ (CIS) or CuIn(Ga)Se₂ (S₂) (=CIGS) and said forming step further includes the steps of depositing said controlled amount of dopant by sputtering or vapor depositing an alkali metal selected from the group consisting of Na, K, Li, and binary compounds of any of the foregoing with Se or S to form a first layer on said back electrode layer;

sputtering or vapor depositing generally appropriate stoichiometric amounts of elements selected from the group consisting of;

Cu, In, Ga, Se, S, and binary compounds of any of the foregoing onto said first layer to form a second layer; and

thereafter, heating to a temperature above about 500°

C. to convert the first and second layers into said compound semiconductor chalcopyrite absorber layer.

19. A method for making a solar cell, comprising the steps of:

providing an alkali-free substrate having a surface;

depositing a back electrode layer on said surface;

forming a chalcopyrite absorber layer including a controlled amount of dopant selected from alkali metals and alkali metal compounds on said back electrode layer;

depositing a window layer on said chalcopyrite absorber layer; and

depositing a front electrode layer on said window layer.

20. A method for making a solar cell as defined in claim 19, further comprising the step of depositing an electrically conductive diffusion barrier on said back electrode prior to said forming step.