Method of manufacturing a compound semiconductor thin film for a photoelectric or solar cell device

• US 5,714,391 A
• Filed: 05/16/1996
• Issued: 02/03/1998
• Est. Priority Date: 05/17/1995
• Status: Expired due to Fees

• Current Assignee: New Energy and Industrial Technology Development Organizatio, Matsushita Battery Industrial Company, Limited (Panasonic Holdings Corporation)
• Original Assignee: Matsushita Electric Industrial Company Limited (Panasonic Holdings Corporation)
• Inventors: Shibutani, Satoshi, Nishio, Tsuyoshi, Kondoh, Shigeo, Murozono, Mikio, Omura, Kuniyoshi, Hanafusa, Akira, Oyama, Hideaki
• Primary Examiner(s): Weisstuch, Aaron
• Application Number:
  US08/648,544
• Time in Patent Office: 628 Days
• Field of Search: 136/260, 136/264, 136/265, 257/184, 437/5, 437/234, 437/102, 427/74, 427/226, 427/248.1, 427/255.2, 427/372.2
• US Class Current: 438/99
• CPC Class Codes: C23C 16/305 Sulfides, selenides, or tellurides
• CPC Class Codes: C23C 16/306 AII BVI compounds, where A is Zn, Cd or Hg and B is S, Se or Te
• CPC Class Codes: C23C 16/4485 by evaporation without using carrier gas in contact with the source material C23C16/4486 takes precedence
• CPC Class Codes: H01L 31/073 comprising only AIIBVI compound semiconductors, e.g. CdS/CdTe solar cells
• CPC Class Codes: H01L 31/0749 including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
• CPC Class Codes: H01L 31/1828 the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
• CPC Class Codes: H01L 31/1836 comprising a growth substrate not being an AIIBVI compound
• CPC Class Codes: Y02E 10/541 CuInSe2 material PV cells
• 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

This invention relates to a manufacturing method of a compound semiconductor thin film derived from a metal sulfide produced by thermal decomposition of a sulfur-containing metal organic compound, the compound containing at least one functional group having at least one metal atom selected from the group consisting of copper, zinc, cadmium, mercury, and lead, and the functional group also containing at least one sulfur atom. Since the obtained metal sulfides are of high-purity and dense, they can be utilized in various photoelectric devices. Particularly, the photoelectric conversion efficiency of a CdS/CdTe system thin film compound semiconductor solar cell can be improved remarkably by employing a layer made of a CdS thin film as a window of the solar cell.

Claims

1. A method of forming a compound semiconductor thin film on a thin film forming substrate, comprising the step of:

thermally decomposing a sulfur-containing metal organic compound at a temperature above 300°

C., said compound containing at least one functional group having at least one metal atom selected from the group consisting of copper, zinc, cadmium, mercury, and lead, said functional group also containing at least one sulfur atom.

2. A method according to claim 1, wherein said functional group also contains carbon, nitrogen, or carbon and nitrogen.

3. A method according to claim 1, wherein said metal organic compound is selected from the group consisting of mercaptide, thioate, dithioate, thiocarbonate, dithiocarbonate, trithiocarbonate, thiocarbamate, and dithiocarbamate of at least one metal element selected from the group consisting of copper, zinc, cadmium, mercury, and lead.

4. A method of forming a metal sulfide compound semiconductor thin film on a thin film forming substrate, comprising the steps of:

volatizing a metal organic compound containing sulfur at a temperature above 300°

C. from a metal organic compound supplying substrate by thermal evaporation, said metal organic compound supplying substrate having a face coated with said metal organic compound,

depositing said metal organic compound onto said thin film forming substrate,

thermally decomposing said deposited metal organic compound at a temperature higher than a temperature at which said thermal evaporation is performed, and

crystallizing a thin film of said metal sulfide compound semiconductor on said thin film forming substrate.

5. A method according to claim 4, wherein at least one cadmium organic compound selected from the group consisting of cadmium mercaptide, cadmium thioate, cadmium dithioate, cadmium thiocarbonate, cadmium dithiocarbonate, cadmium trithiocarbonate, cadmium thiocarbamate, and cadmium dithiocarbamate is used as said metal organic compound.

6. A method of forming a metal sulfide compound semiconductor thin film on a thin film forming substrate, comprising the steps of:

disposing a sulfur containing metal organic compound supplying substrate having a face coated with a sulfur containing metal organic compound at a close distance facing said thin film forming substrate,

heating said metal organic compound supplying substrate to at least the volatization temperature of said metal organic compound to volatize and thermally evaporate said metal organic compound from said metal organic compound supplying substrate,

depositing said metal organic compound onto said thin film forming substrate,

thermally decomposing said deposited metal organic compound by maintaining said thin film forming substrate at least at a thermal decomposition temperature of said metal organic compound, and

crystallizing a thin film of said metal sulfide compound semiconductor on said thin film forming substrate.

7. A method of forming a compound semiconductor thin film, comprising the steps of:

providing a substrate,

forming a solution by dissolving in an organic solvent at least one metal organic compound selected from the group consisting of mercaptide, thioate, dithioate, thiocarbonate, dithiocarbonate, trithiocarbonate, thiocarbamate and dithiocarbamate of a metal element selected from the group consisting of copper, zinc, cadmium, mercury, and lead,

coating said substrate with a layer of said solution using a printing method,

drying said layer on said substrate, and

thermally decomposing said layer at a temperature above 300°

C. to form said compound semiconductor thin film on said substrate.

8. A method according to claim 7, wherein at least one cadmium organic compound selected from the group consisting of mercaptide, thioate, dithioate, thiocarbonate, dithiocarbonate, trithiocarbonate, thiocarbamate, and dithiocarbamate of cadmium is used as said metal organic compound.

9. A method according to claim 7, wherein said metal organic compound dissolved in said organic solvent to form said solution is a cadmium organic compound, and the viscosity of said solution is maintained in a range of 5-100 centipoise by regulating the concentration of said cadmium organic compound in said solution within a range of 0.2-2.0 mol/l.

10. A method of manufacturing photoelectric device, comprising the steps of depositing a first electrode on an electrically insulating sheet selected from the group consisting of ceramic, glass, and resin,

forming a first compound semiconductor thin film of metal sulfide on the surface of said electrode by thermally decomposing a sulfur-containing metal organic compound at a temperature above 300°

C., said compound containing at least one functional group having at least one metal atom selected from the group consisting of copper, zinc, cadmium, mercury, and lead, said functional group also containing at least one sulfur atom,

forming a second compound semiconductor thin film on the surface of said metal sulfide thin film using a proximity sublimation method, wherein said second compound semiconductor thin film is segmented to expose portions of said first compound semiconductor thin film,

forming a second electrode of carbon on said second compound semiconductor thin film, and

forming a third electrode which contacts both said first compound semiconductor thin film and said second electrode of an adjacent segment of said second compound semiconductor thin film.

11. A method according to claim 10, wherein said first and third electrodes are made from a material selected from the group consisting of copper, silver, gold, platinum, palladium, molybdenum, carbon, tin oxide, and indium-tin oxide.

12. A method of forming a compound semiconductor solar cell provided with a p-n junction, comprising the steps of:

forming a transparent conductive electrode made of indium oxide or indium-tin oxide on a transparent and electrically insulating sheet of soda-lime glass or polyamide resin,

forming an n-type semiconductor window layer on the surface of said transparent conductive electrode, said n-type semiconductor window layer being a metal sulfide thin film formed by thermally decomposing a sulfur-containing metal organic compound at a temperature above 300°

C., said compound containing at least one functional group having at least one metal atom selected from the group consisting of copper, zinc, cadmium, mercury, and lead, said functional group also containing at least one sulfur atom, and

forming a p-type semiconductor thin film layer of cadmium telluride on said n-type semiconductor window layer.

13. A method of forming a compound semiconductor solar cell according to claim 12, wherein said metal sulfide thin film is a cadmium sulfide thin film having a thickness less than 700 nm.

14. A method of forming a compound semiconductor solar cell provided with a p-n junction, comprising the steps of:

depositing an n-type semiconductor window layer by thermally decomposing a sulfur-containing metal organic compound at a temperature above 300°

C., said compound containing at least one functional group having at least one metal atom selected-from the group consisting of copper, zinc, cadmium, mercury, and lead, said functional group also containing at least one sulfur atom, onto a p-type semiconductor layer consisting of cadmium telluride or copper-indium selenide,

said p-type semiconductor deposited on a surface of a metal sheet selected from the group consisting of copper, copper plated with silver, platinum, or molybdenum, iron plated with copper, silver, platinum, or molybdenum, stainless steel plated with copper, silver, platinum, or molybdenum, and an electro-insulating sheet with a conductive electrode.

15. A method of forming a compound semiconductor solar cell according to claim 14, wherein said window layer is a cadmium sulfide thin film having a thickness less than 700 nm.