Organic dye-sensitized metal oxide semiconductor electrode and its manufacturing method, and organic dye-sensitized solar cell

• US 7,118,936 B2
• Filed: 10/11/2002
• Issued: 10/10/2006
• Est. Priority Date: 10/11/2001
• Status: Expired due to Fees

• Current Assignee: Bridgestone Corporation
• Original Assignee: Bridgestone Corporation
• Inventors: Tanuma, Itsuo, Yoshikawa, Masato, Kobayashi, Taichi, Iwabuchi, Yoshinori, Oono, Shingo
• Primary Examiner(s): Geyer, Scott B.
• Application Number:
  US10/492,162
• Publication Number:
  US 20040248394A1
• Time in Patent Office: 1,460 Days
• Field of Search: 438/99, 438/104, 257/40, 257/43
• US Class Current: 438/99
• CPC Class Codes: C23C 14/08 Oxides C23C14/10 takes precedence
• CPC Class Codes: H01G 9/2031 comprising titanium oxide, e.g. TiO2 H01G9/2036 takes precedence
• CPC Class Codes: H01G 9/2059 comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
• 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

Abstract

The present invention provides a semiconductor electrode of organic dye-sensitized metal oxide having a semiconductor layer of metal oxide that can be easily prepared, and an organic dye-sensitized solar cell. The semiconductor electrode of organic dye-sensitized metal oxide comprises a substrate having a transparent electrode thereon, a semiconductor layer of metal oxide provided on the electrode and an organic dye absorbed on a surface of the semiconductor layer, the semiconductor layer being formed by a vapor deposition process.

Claims

1. A semiconductor electrode of organic dye-sensitized metal oxide comprising a substrate having a transparent electrode thereon, a semiconductor layer of metal oxide provided on the electrode and an organic dye absorbed on a surface of the semiconductor layer, wherein the semiconductor layer is formed by an opposite target type diode sputtering process or a dual cathode type magnetron sputtering process, and the transparent electrode includes a laminated layer comprising a metal compound layer and a metal layer which are superposed alternatively.

2. A semiconductor electrode of organic dye-sensitized metal oxide as defined in claim 1, wherein the sputtering process is a reactive sputtering process.

3. A semiconductor electrode of organic dye-sensitized metal oxide as defined in claim 1 or 2, wherein the dual cathode type magnetron sputtering process is a bipolar type dual magnetron sputtering process or a unipolar type dual magnetron sputtering process.

4. A semiconductor electrode of organic dye-sensitized metal oxide as defined in claim 1 or 2, wherein the semiconductor layer of metal oxide comprises at least one compound selected from titanium oxide, zinc oxide, tin oxide, antimony oxide, niobium oxide, tungsten oxide or indium oxide, or the metal oxide doped by other metal or metal oxide.

5. A semiconductor electrode of organic dye-sensitized metal oxide as defined in claim 1 or 2, wherein the semiconductor layer of metal oxide comprises titanium oxide.

6. A semiconductor electrode of organic dye-sensitized metal oxide as defined in claim 1 or 2, wherein the semiconductor layer of metal oxide comprises anatase-form titanium oxide.

7. A semiconductor electrode of organic dye-sensitized metal oxide as defined claim 1 or 2, wherein a thickness of the semiconductor layer of metal oxide is not less than 10 nm.

8. A semiconductor electrode of organic dye-sensitized metal oxide as defined in claim 1 or 2, wherein the semiconductor layer has surface roughness Ra of not less than 2 nm, the Ra being defined as centerline average height, and void volume of not less than 25%.

9. A semiconductor electrode of organic dye-sensitized metal oxide as defined in claim 1 or 2, wherein the transparent electrode includes a metal layer having a number of holes.

10. A semiconductor electrode of organic dye-sensitized metal oxide as defined in claim 1 or 2, wherein an antireflective layer is provided on a surface having no transparent electrode of the substrate.

11. An organic dye-sensitized solar cell comprising the semiconductor electrode of organic dye-sensitized metal oxide as defined in claim 1 or 2, an electrode couple provided opposite the semiconductor electrode, and redox electrolyte injected between the electrode and the electrode couple.

12. A process for the preparation of a semiconductor electrode of organic dye-sensitized metal oxide comprising the steps of:

subjecting a transparent electrode of a substrate having the transparent electrode thereon to an opposite target type diode sputtering process or a dual cathode type magnetron sputtering process using a metal and/or metal oxide as a target to form a semiconductor layer of metal oxide, and

adsorbing an organic dye on a surface of the semiconductor layer.

13. A process as defined in claim 12, wherein the sputtering process is a reactive sputtering process.

14. A process as defined in claim 12 or 13, wherein the dual cathode type magnetron sputtering process is a bipolar type dual magnetron sputtering process or a unipolar type dual magnetron sputtering process.

15. A process as defined in claim 12 or 13, wherein the metal as the target is titanium, zinc, tin, antimony, niobium, tungsten or indium, or a mixture of the metals, and the metal oxide as the target is titanium oxide, zinc oxide, tin oxide, antimony oxide, niobium oxide, tungsten oxide or indium oxide, or the metal oxide doped by other metal or metal oxide.

16. A process as defined in claim 12 or 13, wherein the semiconductor layer of metal oxide comprises at least one compound selected from titanium oxide, zinc oxide, tin oxide, antimony oxide, niobium oxide, tungsten oxide or indium oxide, or the metal oxide doped by other metal or metal oxide.

17. A process as defined in claim 12 or 13, wherein the semiconductor layer of metal oxide comprises titanium oxide.

18. A process as defined in claim 12 or 13, wherein the semiconductor layer of metal oxide comprises anatase-form titanium oxide.

19. A process as defined in claim 12 or 13, wherein a thickness of the semiconductor layer of metal oxide is not less than 10 nm.