Methods of making highly conductive photoelectrochemical electrodes

• US 4,592,807 A
• Filed: 03/13/1985
• Issued: 06/03/1986
• Est. Priority Date: 05/19/1983
• Status: Expired due to Fees

• Current Assignee: Union Oil Company of California (Chevron Corp.)
• Original Assignee: Union Oil Company of California (Chevron Corp.)
• Inventors: Switzer, Jay A.
• Primary Examiner(s): Weisstuch, Aaron
• Application Number:
  US06/711,354
• Time in Patent Office: 447 Days
• Field of Search: 204/2.1, 204/86, 204/92, 204/DIG. 3, 204/290 R, 427/74, 427/86, 427/87, 427/443.1, 427/443.2, 429/111
• US Class Current: 205/91
• CPC Class Codes: C25B 1/55 Photoelectrolysis
• CPC Class Codes: C25B 11/077 the compound being a non-noble metal oxide
• CPC Class Codes: C25B 11/091 consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
• CPC Class Codes: H01G 9/20 Light-sensitive devices
• CPC Class Codes: Y02P 20/133 Renewable energy sources, e.g. sunlight
• CPC Class Codes: Y10S 204/03 Auxiliary internally generated electrical energy
• CPC Class Codes: Y10S 205/915 Electrolytic deposition of semiconductor

Abstract

A photoelectrode, containing a highly conductive coating material having a band gap greater than 0 to about 3.0 e.V. on a substrate containing a semiconductor material, is utilized in photovoltaic cells, photoelectrosynthesis and photoelectrocatalysis.

Claims

1. A method for preparation of a photoelectrode comprising the step of photoelectrochemical deposition of a conductive coating material having a band gap from greater than 0 to about 3.0 e.V. on a substrate consisting essentially of a semiconductor selected from the group consisting of n-type, p-type, and intrinsic semiconductors.

2. The method defined in claim 1 further comprising potentiostatic electrochemical deposition.

3. The method defined in claim 2 wherein said coating material comprises thallium (III) oxide and said substrate consists essentially of n-type silicon.

4. The method defined in claim 1 wherein said coating material has a band gap from greater than 0.5 to about 2.35 e.V.

5. The method defined in claim 1 wherein said substrate contains a layer of material having a bandgap greater than about 3.0 e.V. on the surface.

6. The method defined in claim 5 wherein said layer has an average thickness less than about 100 angstroms.

7. The method defined in claim 1 wherein said substrate is employed as an anode during said photoelectrochemical deposition.

8. The method defined in claim 1 wherein said substrate is employed as a cathode during said photoelectrochemical deposition.

9. The method defined in claim 1 wherein said substrate consists essentially of an n-type semiconductor.

10. The method defined in claim 1 wherein said substrate consists essesntially of a p-type semiconductor.

11. The method defined in claim 1 wherein said photoelectrochemical deposition is potentiostatic.

12. The method defined in claim 11 wherein said photoelectrochemical deposition process is stopped at such time that the photocurrent is within about 20 percent of its maximum value.

13. The method defined in claim 1 wherein an electrochemical cell employed in said step of photoelectrochemical deposition is biased with electrical energy from a source external to said electrochemical cell.

14. The method defined in claim 1 wherein said coating material has a resistivity less than about 10^-2 ohm-cm, measured at room temperature.

15. A method for the preparation of a photoelectrode comprising the step of electroless deposition of a conductive coating material onto a substrate, said substrate consisting essentially of a semiconductor selected from the group consisting of n-type, P-type, and intrinsic semiconductors and said coating material containing a semiconductor.

16. The method defined in claim 15 wherein said electroless deposition comprises photoelectroless deposition.

17. The method defined in claim 15 wherein said substrate contains a layer of material having a band gap greater than about 3.0 e.V. on the surface.

18. The method defined in claim 15 wherein said coating material has a band gap from greater than 0 to about 3.0 e.V.

19. The method defined in claim 15 wherein an electrochemical cell employed in said step of electroless deposition is biased with electrical energy from a source external to said electrochemical cell.

20. The method defined in claim 15 wherein said coating material has a resistivity less than about 10^-2 ohm-cm, measured at room temperature.

21. A method for the preparation of an electrode, said method comprising the step of photoelectroless deposition of a coating material onto a substrate consisting essentially of a semiconductor selected from the group consiting of n-type, p-type, and intrinsic semiconductors.

22. The method defined in claim 21 wherein said coating material is conductive.

23. The method defined in claim 21 wherein an electrochemical cell employed in said step of photoelectroless deposition is partially biased with electrical energy from a source external to said electrochemical cell.

24. The method defined in claim 21 wherein said coating material is deposited on said substrate from an electrochemical cell comprising a redox-couple containing the coating material precursor.

25. A method for the preparation of a photoelectrode, said method comprising the step of electrochemical deposition of a conductive coating material having a band gap in the range from greater than about 0.5 to about 2.35 e.V. onto a substrate containing a semiconductor material, said photoelectrode further comprising a layer of material having a bandgap greater than about 3.0 e.V. between said substrate and said coating material, and said layer having an average thickness less than about 100 angstroms.

26. The method defined in claim 25 wherein said coating material has a resistivity less than said substrate.

27. The method defined in claim 25 wherein said semiconductor has a band gap from about 0.5 to about 4.0 e.V.

28. The method defined in claim 25 wherein said coating material has a resistivity less than about 10^-2 ohm-cm, measured at room temperature.

29. The method defined in claim 25 wherein said coating material has a band gap greater than the band gap of said semiconductor material in said substrate.

30. The method defined in claim 25 wherein said semiconductor in said substrate compises n-type or p-type material.

31. The method defined in claim 25 wherein said coating material is doped to degeneracy.

32. The method defined in claim 25 wherein said layer has an average thickness from about 1 to about 20 angstroms.

33. The method defined in claim 25 wherein said coating material is naturally degenerate.

34. The method defined in claim 25 wherein said coating material comprises a combination of components selected from the group consisting of elements and compounds.

35. The method defined in claim 25 wherein said coating material has a resistivity less than about 10^-3 ohm-cm, measured at room temperature.

36. The method defined in claim 25 wherein said coating material is selected from the group consisting of Tl₂ O₃, CdO, PbO₂, Cr₂ O₃, RuS₂, PtCoO₂, PdRhO₂ and PdCrO₂.

37. The method defined in claim 25 wherein said layer has a band gap greater than about 4.0 e.V.

38. The method defined in claim 25 wherein said coating material has a resistivity less than about 10^-4 ohm-cm, measured at room temperature.

39. The method defined in claim 25 wherein said electrochemical deposition comprises photoelectrochemical deposition.

40. The method defined in claim 25 further comprising potentiostatic electrochemical deposition.

41. A method for the preparation of a phototelectrode, said method comprising the step of electrochemical deposition of a coating material contining thallium (III) oxide onto a substrate containing a semiconductor.

42. The method defined in claim 41 wherein said substrate is selected from the group consisting of GaAs, InP, CdSe, GaP, and Si.

43. The method defined in claim 41 wherein said substrate comprises a material having a band gap greater than 0 and less than about 4.0 e.V.

44. The method defined in claim 41 wherein said semiconductor has a band gap from about 0.7 to about 2.5 e.V.

45. The method defined in claim 41 wherein said semiconductor comprises n-type silicon.

46. The method defined in claim 45 further comprising a layer comprising an oxide of silicon having an average thickness of less than about 50 angstroms and located between said n-type silicon and said thallium (III) oxide.

47. The method defined in claim 41 wherein said thallium (III) oxide is dispersed on said substrate to an average thickness of less than 10⁵ angstroms.

48. The method defined in claim 41 wherein said substrate has a band gap less than the band gap of said thallium (III) oxide.

49. A method for the preparation of a photoelectrode, useful in a semiconductor liquid junction photovoltaic cell, said method comprising the step of photoelectrochemical deposition of a coating material containing an inorganic semiconductor having a resistivity less than about 10^-2 ohm-cm onto a substrate comprising a semiconductor.

50. The method defined in claim 49 wherein said photoelectrochemical deposition comprises photoelectroless deposition.

51. The method defined in claim 49 wherein said substrate is employed as an anode during said photoelectrochemical deposition.