Batteries: thermoelectric and photoelectric – Photoelectric – Cells
Reexamination Certificate
2002-12-12
2004-11-23
Diamond, Alan (Department: 1753)
Batteries: thermoelectric and photoelectric
Photoelectric
Cells
C136S252000, C136S256000, C257S040000, C257S043000, C257S431000
Reexamination Certificate
active
06822159
ABSTRACT:
TECHNICAL FIELD
The present invention relates to semiconductor fine particles sensitized with dye(s), photoelectric conversion devices sensitized with dye(s) and solar cell sensitized with a dye, and in particular to a semiconductor fine particle sensitized with azo dye(s), a photoelectric conversion device sensitized with azo dye(s) and a solar cell utilizing the same.
BACKGROUND OF THE INVENTION
A solar cell utilizing sunlight as an alternative energy source to a fossil fuel such as petroleum, coal or the like has been in the spotlight. Today, developments and studies are being conducted on enhancement of efficiency and the like of a silicon solar cell which uses crystalline or amorphous silicon, a compound semiconductor solar cell which uses gallium, arsenic or the like. However, since much energy is required for producing these solar cells and the cost of them is high, there is a problem that it is difficult to put them to general use. Further, a photoelectric conversion device which uses semiconductor fine particles sensitized with dye(s) and a solar cell which uses this device have been known whereupon materials for use in producing them and techniques for producing them have been disclosed. (B. O'Regan and M. Gratzel Nature, 353, 737 (1991), M. K. Nazeeruddin, A. Kay, I. Rodicio, R. Humphry-Baker, E. Muller, P. Liska, N. Vlachopoulos, M. Gratzel, J. Am. Chem. Soc., 115, 6382 (1993) e.t.c.). This photoelectric conversion device is produced by using a comparatively low-cost oxide semiconductor such as titanium oxide or the like. Since there is a possibility that a photoelectric conversion device can be obtained in low cost compared with a solar cell which uses a conventional silicon or the like, this device has been remarked. However, in order to obtain a device having high conversion efficiency, a ruthenium-type complex is used as a sensitizing dye wherein the dye itself is high in cost and there also is a problem in supply thereof. Further, although it has already been attempted to use an organic dye as a sensitizing dye, it is a present situation that, due to low conversion efficiency and the like, it has not yet been used practically.
A development of a photoelectric conversion device, using an organic dye-sensitized semiconductor, which has high conversion efficiency as well as high practicability has been required.
DISCLOSURE OF THE INVENTION
The present inventors have made an extensive effort to solve the above-described problems and, as a result, have found that a photoelectric conversion device having high conversion efficiency can be obtained by sensitizing semiconductor particles with a specified azo-type dye and, then, producing a photoelectric conversion device to achieve the present invention.
Namely, the present invention relates to
(1) a photoelectric conversion device, comprising an oxide semiconductor fine particles sensitized with at least one azo dye represented by the following formula (1):
wherein Ar 1 represents an aromatic group having at least one substituent selected from the group consisting of a carboxylic acid group, a hydroxyl group, a phosphoric acid group, a phosphoric acid ester group and a mercapto group either directly or via a cross-linking group; and Ar 2 represents an aromatic group having at least one electron-donating group as a substituent, and wherein Ar 1 and Ar 2 may have other substituents than those defined above,
(2) the photoelectric conversion device of the above-described (1), wherein Ar 1 of the azo dye mentioned in the above-described (1) has at least 2 substituents selected from the group consisting of a carboxylic acid group, a hydroxyl group, a phosphoric acid group, aphosphoric acid ester group and a mercapto group,
(3) the photoelectric conversion device of the above-described (2), characterized in that at least 2 of substituents on Ar 1 of the azo dye mentioned in the above-described (1) are groups selected from the group consisting of a carboxylic acid group and a hydroxyl group,
(4) the photoelectric conversion device mentioned in the above-described (2) or (3), wherein at least 2 of substituents on Ar 1 of the azo dye mentioned in the above-described (1) are substituted at any two adjacent positions within a same aromatic ring,
(5) the photoelectric conversion device mentioned in any one of the above-described (1) to (4) wherein the electron-donating groups in Ar 2 of the azo dye mentioned in the above-described (1) are one, or two or more substituents, which may further be substituted, selected from the group consisting of an amino group, a hydroxyl group and an alkoxyl group,
(6) the photoelectric conversion device mentioned in any one of the above-described (1) to (5), comprising oxide semiconductor fine particles sensitized with the azo dye mentioned in at least one of the above-described (1) to (5) and another metal complex and/or another organic dye,
(7) the photoelectric conversion device mentioned in any one of the above-described (1) to (6), wherein the oxide semiconductor fine particles contain titanium dioxide as an essential component,
(8) the photoelectric conversion device mentioned in any one of the above-described (1) to (6), wherein a dye is absorbed on the oxide semiconductor fine particles in the presence of an inclusion compound,
(9) a solar cell, characterized by comprising using the photoelectric conversion device mentioned in any one of the above-described (1) to (8), and
(10) a photoelectric conversion device, comprising a semiconductor thin film which adsorbs thereon at least one azo dye represented by the following formula (1):
wherein Ar 1 represents an aromatic group having at least one substituent selected from the group consisting of a carboxylic acid group, a hydroxyl group, a phosphoric acid group, a phosphoric acid ester group and a mercapto group either directly or via a cross-linking group; and Ar 2 represents an aromatic group having at least one electron-donating group as a substituent,
said semiconductor thin film being formed from oxide semiconductor fine particles.
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention will be described in detail below. A photoelectric conversion device according to the present invention uses an oxide semiconductor sensitized with an azo dye. The azo dye to be used in the present invention is characterized by being represented by the following general formula (1):
General formula (1):
wherein Ar 1 represents an aromatic group having at least one substituent selected from the group consisting of a carboxyl group, a hydroxyl group, a phosphoric acid group, a phosphoric ester group and a mercapto group either directly or via a cross-linking group; and Ar 2 represents an aromatic group having at least one electron-donating group as a substituent.
In the general formula (1), Ar 1 shows an aromatic group which has at least one substituent selected from the group consisting of a carboxyl group, a hydroxyl group, a phosphoric acid group, a phosphoric ester group and a mercapto group either directly or via a cross-linking group and, further, may have another substituent, and Ar 2 shows an aromatic group which has at least one electron-donating group as a substituent. Further, Ar 1 and Ar 2 may further have other substituents than those defined above.
Further, the term “aromatic group” used herein means a group which is a substituted or non-substituted aromatic ring deprived of one hydrogen atom therefrom; on this occasion, as such aromatic rings, mentioned are monocyclic or condensed polycyclic aromatic rings such as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, an indene ring, an azulene ring, a fluorene ring and the like. As a preferable aromatic group, mentioned is a phenyl group or a naphthyl group.
An essential substituent in Ar 1 is selected from the group consisting of a carboxyl group, a hydroxyl group, a phosphoric acid group, a phosphoric ester group and a mercapto group. As a preferable group, mentioned are the carboxyl group and the hydroxyl group. Further, a cross-linking g
Ikeda Masaaki
Inoue Teruhisa
Shigaki Koichiro
Yanagida Shozo
Diamond Alan
Nields & Lemack
Nippon Kayaku Kabushiki Kaisha
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