Liquid junction photoelectrodes using amorphous silicon-based thin film semiconductor

• US 4,656,103 A
• Filed: 05/20/1985
• Issued: 04/07/1987
• Est. Priority Date: 02/18/1983
• Status: Expired due to Term

• Current Assignee: Energy Conversion Devices
• Original Assignee: Energy Conversion Devices
• Inventors: Liang, Gao, Reichman, Benjamin, Sapru, Krishna
• Primary Examiner(s): Weisstuch, Aaron
• Application Number:
  US06/736,433
• Time in Patent Office: 687 Days
• Field of Search: 204/290 R, 204/266, 204/DIG. 3, 204/129, 429/111, 136/258 AM, 136/259
• US Class Current: 429/111
• CPC Class Codes: C25B 1/55 Photoelectrolysis
• CPC Class Codes: H01G 9/20 Light-sensitive devices
• CPC Class Codes: Y02E 60/36 Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
• CPC Class Codes: Y02P 20/133 Renewable energy sources, e.g. sunlight
• CPC Class Codes: Y10S 204/03 Auxiliary internally generated electrical energy

Abstract

An amorphous silicon semiconductor alloy having multiple layers is used to form a photoelectrode (either a photoanode or a photocathode) for use in a photoelectrochemical cell for the photoelectrolysis of water to produce hydrogen or the conversion of solar energy into electrical energy. Each layer of the semiconductor alloy has a different dopant concentration ranging from no dopant to a heavy dopant concentration. The photoelectrochemical cell can utilize a photocathode and a conventional metal anode, a photoanode or both a photocathode and a photoanode according to the present invention. The semiconductor alloy of the photoelectrode is a-Si:F:H or a-Si:H_x deposited on a reflective layer of aluminum or molybdenum which is deposited on a substrate of glass or stainless steel. A tunnelable oxide layer can be deposited or intrinsically formed to cover and protect the top surface of the semiconductor alloy body. The photoanode is of an n-type configuration while the photocathodes can be either a p-type or a P-I-N type configuration.

Claims

1. A photoelectrochemical cell for the conversion of sunlight into electrical energy for the production of hydrogen gas comprising:

a cell having an interior space therein, said space divided by a membrane positioned in said space to form an anode compartment and a cathode compartment within said cell;

an electrolyte without an added redox couple in said anode compartment and in said cathode compartment;

a photocathode positioned in said cathode compartment with at least a portion in contact with said electrolyte;

an electrode positioned in said anode compartment with at least a portion in contact with said electrolyte;

said photocathode being a photoelectrode and including a substrate having a deposition surface, an electrically conductive lead, and a thin film amorphous silicon semiconductor alloy body deposited on the substrate having at least a first and a second layer, the first layer being adjacent the substrate being p+ type and including a p type dopant at a concentration of about 10²³ atoms/cm³ and adapted to be coupled to the electrically conductive lead, said semiconductor alloy body having enhanced resistance to photocorrosion while operating in the absence of an added redox coupled in said electrolyte; and

means for impinging photons upon said photoelectrode wherein sunlight will be converted into energy usable as electricity or a fuel.

2. The cell as defined in claim 1, wherein said cell further includes an electrical power source electrically coupled to said electrodes wherein photoassisted electrolysis will occur.

3. The cell as defined in claim 1, wherein said cell further includes an electrical load electrically coupled to said electrodes wherein sunlight is converted into electrical energy.

4. The cell as defined in claim 1, wherein said substrate of said photoelectrode is a material selected from a group consisting of glass and stainless steel.

5. The cell as defined in claim 1, wherein said semiconductor alloy of said photoelectrode is a-Si:

H_x.

6. The cell as defined in claim 1, wherein said semiconductor alloy of said photoelectrode is a-Si:

F;

H.

7. The cell as defined in claim 1, wherein said photoelectrode further comprises a reflective layer deposited on the deposition surface of said substrate, said reflective layer interposed between said substrate and said first layer.

8. The cell as defined in claim 7, wherein said reflective layer of said photoelectrode is a material selected from a group consisting of aluminum and molybdenum.

9. The cell as defined in claim 1, wherein the second layer of said photoelectrode is substantially intrinsic.

10. The cell as defined in claim 1, wherein said first and second layer of said photoelectrode are each doped with said dopant in different concentrations.

11. The cell of claim 10 wherein said dopant is boron and said second layer is doped to a concentration of about 10¹⁷ atoms/cm³.

12. The cell as defined in claim 1, wherein said p type dopant is boron.

13. A cell as defined in claim 1, wherein said second layer is a substantially intrinsic amorphous silicon semiconductor alloy, said semiconductor alloy body further including a third layer of an n+ type amorphous silicon semiconductor alloy overlying said second layer.

14. A cell as defined in claim 13, wherein said first layer of said photoelectrode is doped with boron and said third layer is doped with phosphorus to a concentration of about 10²⁷ atoms/cm³.

15. A cell as defined in claim 1, wherein said photoelectrode further includes a thin film oxide layer deposited to cover said semiconductor body.

16. A cell as defined in claim 15 wherein said oxide layer is an amorphous silicon based oxide or Nb₂ O₅.