Photoresponsive amorphous semiconductor materials, methods of making the same, and photoanodes made therewith

• US 4,511,638 A
• Filed: 06/01/1983
• Issued: 04/16/1985
• Est. Priority Date: 06/01/1983
• Status: Expired due to Term

• Current Assignee: Xylon LLC (Intellectual Ventures LLC)
• Original Assignee: Energy Conversion Devices
• Inventors: Reichman, Benjamin, Sapru, Krishna, Liang, Gao
• Primary Examiner(s): Weisstuch, Aaron
• Application Number:
  US06/499,900
• Time in Patent Office: 685 Days
• Field of Search: 204/37 R, 204/130, 204/140, 204/192 S, 204/192 P, 204/290 R, 204/242, 204/DIG. 3, 252/62.3 R, 252/62.3 E, 252/62.3 ZT, 252/62.3 V, 252/62.3 BT, 252/501.1, 429/111
• US Class Current: 429/111
• CPC Class Codes: C25B 1/55 Photoelectrolysis
• CPC Class Codes: H01G 9/20 Light-sensitive devices
• CPC Class Codes: H01L 31/20 such devices or parts thereof comprising amorphous semiconductor materials
• CPC Class Codes: H01M 14/005 Photoelectrochemical storage cells light sensitive devices H01G9/20, semiconductors sensitive to light H01L31/00
• CPC Class Codes: Y02E 10/542 Dye sensitized solar cells
• CPC Class Codes: Y02P 20/133 Renewable energy sources, e.g. sunlight
• CPC Class Codes: Y10S 204/03 Auxiliary internally generated electrical energy

Abstract

A photoresponsive amorphous semiconductor material is modified by incorporating at least one compensating agent selected from a group consisting of hydrogen, lithium, fluorine, beryllium, aluminum, boron, magnesium, other Group I elements, and compounds of these elements. The semiconductor material is cathodically treated either simultaneously with or subsequent to this modification. The semiconductor material may be additionally modified by incorporating a second modifying agent selected from a group consisting of silicon, the transition elements, the lanthanides, and compounds of these elements. The semiconductor material also may be subjected to heat treatment in an inert atmosphere before the cathodic treatment.

A photoanode utilizing the above described semiconductor material further includes a substrate to support a film of said material. The photoanode may additionally include a second semiconductor film having a small band gap inserted between said substrate and said first semiconductor film. These photoanodes may be used in an electrochemical cell for the conversion of light into electrical energy or energy stored in a fuel.

Claims

1. A method of making a photoresponsive amorphous semiconductor material comprising the steps of:

forming an amorphous semiconductor;

cathodically treating said amorphous semiconductor so that a compensating agent modifies the semiconductor to eliminate or compensate the localized states and enhance the photoresponse of the semiconductor.

2. A method as defined in claim 1, wherein said method further includes incorporating in said semiconductor a second compensating agent selected from the group consisting of hydrogen, lithium, fluorine, beryllium, aluminum, boron, magnesium, other Group I elements, and compounds of these elements, prior to said cathodically treating step.

3. A method as defined in claim 1, wherein said cathodically treating step includes:

placing said semiconductor in electrical contact with an electrolyte; and

subsequently,

applying an electrical bias to said semiconductor.

4. A method as defined in claim 3, wherein said electrolyte is selected from the group consisting of potassium hydroxide, sodium hydroxide, and lithium hydroxide.

5. A method as defined in claim 3, wherein said electrical bias of the applying step is between about -1.2 to 2.0 volts for approximately 5 to 10 minutes.

6. A method as defined in claim 1, wherein said method further includes the step of heating said semiconductor prior to said cathodically treating step so that the photoresponse of the semiconductor is enhanced.

7. A method as defined in claim 6, wherein said semiconductor is heated in the range of approximately 200°

C. to 400°

C.

8. A method as defined in claim 1, wherein said semiconductor is selected from the group consisting of the oxides, sulfides, selenides, and phosphides of the transition elements.

9. A method as defined in claim 1, wherein said semiconductor is selected from the group consisting of TiO₂, Fe₂ O₃, SrTiO₂, WO₃, and Si:

F;

H alloys.

10. A method as defined in claim 1, wherein the forming step further includes reactively sputtering said semiconductor on a substrate in an atmosphere of about 2.5% oxygen/argon, with sputtering power between about 0.5 and 2 watts/cm² and the temperature of said substrate between about 20°

C. and 80°

C.

11. A method as defined in claim 1, wherein said compensating agent is present in an amount of about 1 atomic percent.

12. A method as defined in claim 1, wherein said method further includes the step of incorporating in said semiconductor a modifying agent selected from the group consisting of silicon, transition elements, lanthanides, and compounds of these elements, prior to said treating step.

13. A method as defined in claim 12, wherein said modifying agent is selected from the group consisting of chromium, iron, niobium, silicon, and praseodymium.

14. A method as defined in claim 12, wherein said modifying agent is present in an amount of not more than about 20 atomic percent.

15. A method as defined in claim 12, wherein said incorporating step comprises reactively co-sputtering said modifying agent with the semiconductor during the forming step.

16. A method as defined in claim 12, wherein said incorporating step comprises soaking the semiconductor in a solution containing the modifying agent, prior to the treating step.

17. A photoresponsive amorphous semiconductor material for use in the conversion of light to electrical energy or fuel produced in accordance with the method defined in claim 1.

18. A photoanode having enhanced photoresponse for use in the conversion of light to electrical energy or fuel comprising:

a substrate including a deposition surface; and

an amorphous semiconductor film in electrical contact with said deposition surface, said semiconductor incorporating a compensating agent selected from the group consisting of hydrogen, lithium, fluorine, beryllium, aluminum, boron, magnesium, other Group I elements, and compounds of these elements, said semiconductor film being cathodically treated to enhance its photoresponse.

19. A photoanode as defined in claim 18, wherein said photoelectrode further includes a second semiconductor film in electrical contact with said deposition surface and positioned between said first semiconductor film and said deposition surface, so that said first semiconductor film provides a coating over said second semiconductor film.

20. A photoanode as defined in claim 19, wherein said second semiconductor film comprises a smaller band gap semiconductor.

21. A photoanode as defined in claim 20, wherein said smaller band gap semiconductor is selected from the group consisting of CdS, CdSe, and compounds thereof.

22. A photoanode as defined in claim 18, wherein said semiconductor film is annealed prior to said cathodic treatment to enhance its photoresponse.

23. A photoanode as defined in claim 18, wherein said semiconductor is selected from the group consisting of the oxides, sulfides, selenides, and phosphides of the transition elements.

24. A photoanode as defined in claim 18, wherein said semiconductor is selected from the group consisting of TiO₂, Fe₂ O₃, SrTiO₂, WO₃ and Si:

F;

H alloys.

25. A photoanode as defined in claim 18, wherein said compensating agent is present in an amount of about 1 atomic percent.

26. A photoanode as defined in claim 18, wherein said semiconductor further includes a modifying agent selected from the group consisting of silicon, transition elements, lanthanides, and compounds of these elements.

27. A photoanode as defined in claim 26, wherein said modifying agent is selected from the group consisting of chromium, iron, niobium, silicon, and praseodymium.

28. A photoanode as defined in claim 26, wherein said modifying agent is present in an amount of not more than about 20 atomic percent.

29. A photoanode as defined in claim 18, wherein said substrate is a material selected from the group consisting of titanium, stainless steel, nickel, and NESA glass.

30. A photoelectrochemical cell for the conversion of light into electrical energy or energy stored in a fuel 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 counter electrode compartment within said cell,

an electrolyte in said anode compartment and in said counter electrode compartment;

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

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

said photoanode including a substrate having a deposition surface, and an amorphous semiconductor film in electrical contact with said deposition surface, said semiconductor film including a compensating agent selected from the group consisting of hydrogen, lithium, fluorine, beryllium, aluminum, boron, magnesium, other Group I elements, and compounds of these elements, said semiconductor film being cathodically treated to enhance its photoresponse; and

means for allowing light to enter the cell and illuminate said photoelectrode wherein the light will be converted into energy usable as electricity or a fuel.

31. A cell as defined in claim 30, wherein said cell further includes an electrical load electrically coupled to said photoanode and counter electrode, whereby the light is converted into electrical energy.

32. A cell as defined in claim 30, wherein said cell further includes an electrical power source electrically coupled to said photoanode and counter electrode, whereby photoassisted electrolysis will occur.

33. A cell as defined in claim 30, wherein said semiconductor film is further annealed prior to said cathodic treatment to enhance its photoresponse.

34. A cell as defined in claim 30, wherein said semiconductor is selected from the group consisting of the oxides, sulfides, selenides, and phosphides of the transition elements.

35. A cell as defined in claim 30, wherein said semiconductor is selected from the group consisting of TiO₂, Fe₂ O₃, SrTiO₂, WO₃ and a-Si:

F;

H alloys.

36. A cell as defined in claim 30, wherein said compensating agent is present in an amount of about 1 atomic percent.

37. A cell as defined in claim 30, wherein said amorphous semiconductor film further includes a modifying agent selected from the group consisting of silicon, transition elements, lanthanides, and compounds of these elements.

38. A cell as defined in claim 37, wherein said modifying agent is selected from the group consisting of chromium, iron, niobium, silicon, and praseodymium.

39. A cell as defined in claim 37, wherein said modifying agent is present in an amount of not more than about 20 atomic percent.

40. A cell as defined in claim 30, wherein said photoanode further includes a second semiconductor film in electrical contact with said deposition surface and positioned between said first semiconductor film and said deposition surface, so that said first semiconductor film provides a coating over said second semiconductor film.

41. A cell as defined in claim 40, wherein said second semiconductor film comprises a smaller band gap semiconductor.

42. A cell as defined in claim 41, wherein said smaller band gap semiconductor is selected from the group consisting of CdS, CdSe, and compounds thereof.