JP2011204545A - Dye for dye-sensitized solar cells, and dye-sensitized solar cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dye for a dye-sensitized solar cell excellent in an optical absorbing amount and a dye-sensitized solar cell using the same.SOLUTION: The dye for a dye-sensitized solar cell contains a carbonyl thiophene compound as expressed in a formula (1) and a phosphoryl thiophene compound as expressed in a formula (5). In the formula, R-Rand R-Rexpress a hydrogen atom or an alkyl group of a carbon number 1-20 each independently, and Z and Y are bivalent organic groups containing a thiophene or benzene ring.

Description

  The present invention relates to a dye for a dye-sensitized solar cell and a dye-sensitized solar cell using the dye.

In order to solve energy problems and global environmental problems that have been faced in recent years, various studies have been conducted on energy that can replace conventional fossil fuels.
Among them, solar cells that use solar energy have attracted a great deal of attention because they are not only infinite in resources but also environmentally friendly devices.
In particular, dye-sensitized solar cells have been researched for practical use since they were proposed by Gretzell et al. Because of the advantages such as the low cost of materials used and the use of vacuum equipment in the manufacturing process. It is actively done.

In this dye-sensitized solar cell, a semiconductor electrode having a light absorption effect in which a dye is adsorbed on a semiconductor electrode made of a porous metal oxide is used.
Since the photoelectric conversion efficiency of a solar cell is proportional to the amount of electrons generated by the absorption of sunlight, it is necessary to increase the dye adsorption amount on the semiconductor electrode in order to improve the conversion efficiency.
For this reason, it is calculated | required that the pigment | dye for dye-sensitized solar cells has high affinity and adhesiveness with respect to a metal oxide.

  Conventionally, in order to achieve high photoelectric conversion efficiency, it has been generally considered that a single kind of dye having high purity should be used. This is because when multiple types of dyes are mixed on one semiconductor layer, electrons are exchanged between the dyes or electron-hole recombination occurs, or the excited dyes are transferred to the semiconductor layer. When electrons are captured by another type of dye, the number of electrons that reach the transparent electrode from the excited photosensitizing dye decreases, and the ratio at which current is obtained from the absorbed photons, that is, the quantum yield decreases significantly. It is possible.

A co-adsorbent is also often used to prevent the association of dye molecules on the semiconductor layer. Typical coadsorbents include chenodeoxycholic acid, taurodeoxycholate, 1-decylphosphonic acid and the like.
The structural features of these molecules are that they have a carboxyl group or phosphono group as a functional group that is easily adsorbed to titanium oxide constituting the semiconductor layer, and intervene between the dye molecules to prevent interference between the dye molecules. Therefore, it may be formed by σ bond.

Furthermore, an example has been reported in which light of a wide wavelength range is absorbed by adsorbing two types of dyes having different absorption wavelengths to improve photoelectric conversion efficiency (see Patent Document 1).
However, in the dye-sensitized solar cell, most of the incident light (sunlight) is transmitted, increasing the amount of the dye to be adsorbed while suppressing the association of the dye molecules on the porous semiconductor. No attempt has been made to increase the amount of light absorption.

JP 2007-234580 A

  This invention is made | formed in view of such a situation, and it aims at providing the dye-sensitized solar cell dye excellent in the light absorption amount, and a dye-sensitized solar cell using the same.

  As a result of intensive studies to achieve the above object, the present inventors have found that a poly or oligothiophene compound having a carboxyl group or an alkoxycarbonyl (carboxylic ester) group and a poly or oligothiophene compound having a phosphoric acid (ester) group or The present inventors have found that a dye containing two different thiophene compounds called oligothiophene compounds has excellent light absorption and is useful as a dye for dye-sensitized solar cells, and completed the present invention.

〔（式中、Ｒ¹〜Ｒ⁶は、それぞれ独立して、水素原子または炭素数１〜２０アルキル基を表し、ｍ、ｎ、ｏおよびｐは、それぞれ独立して、０または１以上の整数を表し、１≦ｍ＋ｎ＋ｏ、かつ、２≦ｍ＋ｎ＋ｏ＋ｐ≦１，０００を満足し、Ｚは、下記式（２）〜（４）から選ばれる２価の有機基であり、

Ｒ⁷〜Ｒ¹⁶は、それぞれ独立して、水素原子または炭素数１〜２０アルキル基を表す。）

（式中、Ｒ¹⁷〜Ｒ²⁶は、それぞれ独立して、水素原子または炭素数１〜２０アルキル基を表し、ｍ’、ｎ’、ｏ’およびｐ’は、それぞれ独立して、０または１以上の整数を表し、１≦ｍ’＋ｎ’＋ｏ’、かつ、２≦ｍ’＋ｎ’＋ｏ’＋ｐ’≦１，０００を満足し、Ｙは、下記式（６）〜（８）から選ばれる２価の有機基であり、

Ｒ²⁷〜Ｒ³⁶は、それぞれ独立して、水素原子または炭素数１〜２０アルキル基を表す。）〕
２． １の色素増感太陽電池用色素を含むワニス、
３． １の色素増感太陽電池用色素を含む有機薄膜、
４． ２のワニスから作製される有機薄膜、
５． 光透過性を有する基板と、この基板に積層された透明導電膜と、この透明導電膜に積層された金属酸化物からなる多孔質半導体とを有し、前記多孔質半導体の表面には１の色素増感太陽電池用色素が吸着されていることを特徴とする半導体電極、
６． ２のワニスに多孔質半導体を有する基板を浸漬し、前記色素増感太陽電池用色素を前記多孔質半導体に吸着させてなる５の半導体電極、
７． ５の半導体電極と、対極と、これら半導体電極および対極間に介在する電解質と、を備えて構成される色素増感太陽電池
を提供する。 That is, the present invention
1. A dye for dye-sensitized solar cells, comprising a carbonylthiophene compound represented by the formula (1) and a phosphorylthiophene compound represented by the formula (5):

[Wherein, R ^{1 to} R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and m, n, o and p are each independently an integer of 0 or 1 or more. 1 ≦ m + n + o and 2 ≦ m + n + o + p ≦ 1,000 are satisfied, Z is a divalent organic group selected from the following formulas (2) to (4),

R ^{7 to} R ¹⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. )

(Wherein R ^{17 to} R ²⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and m ′, n ′, o ′ and p ′ each independently represent 0 or 1) Represents the above integer, satisfies 1 ≦ m ′ + n ′ + o ′ and 2 ≦ m ′ + n ′ + o ′ + p ′ ≦ 1,000, and Y is selected from the following formulas (6) to (8) A divalent organic group,

R ^{27 to} R ³⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. )]
2. A varnish comprising 1 dye-sensitized solar cell dye,
3. An organic thin film containing a dye for a dye-sensitized solar cell according to claim 1,
4). An organic thin film made from two varnishes,
5. A substrate having light transmissivity, a transparent conductive film laminated on the substrate, and a porous semiconductor made of a metal oxide laminated on the transparent conductive film, the surface of the porous semiconductor having 1 A semiconductor electrode, wherein a dye for a dye-sensitized solar cell is adsorbed;
6). 5 semiconductor electrodes obtained by immersing a substrate having a porous semiconductor in the varnish of 2 and adsorbing the dye for dye-sensitized solar cells to the porous semiconductor;
7). And a counter electrode, and an electrolyte interposed between the semiconductor electrode and the counter electrode.

  ADVANTAGE OF THE INVENTION According to this invention, the pigment | dye for dye-sensitized solar cells excellent in the light absorption amount, and a dye-sensitized solar cell using the same can be provided.

1 is a schematic cross-sectional view of a dye-sensitized solar cell produced in Example 1. FIG. 3 is a diagram showing an IPCE spectrum of a dye-sensitized solar cell produced in Example 1. FIG. It is a figure which shows the IPCE spectrum of the dye-sensitized solar cell produced in Comparative Example 1. It is a figure which shows the IPCE spectrum of the dye-sensitized solar cell produced in Comparative Example 2.

Hereinafter, the present invention will be described in more detail.
In this specification, “n” is normal, “i” is iso, “s” is secondary, “t” is tertiary, “c” is cyclo, “o” is ortho, “M” means meta, “p” means para, “Me” means methyl group, “Et” means ethyl group, “Pr” means propyl group, “Bu” means butyl group, “Ph” "Means a phenyl group.

The pigment | dye for dye-sensitized solar cells in this invention contains the carbonyl (carboxy or alkoxycarbonyl) thiophene compound represented by the said Formula (1), and the phosphoryl thiophene compound represented by Formula (5).
In formulas (1) and (5), examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, ethyl group, n-propyl group, i-propyl group, c-propyl group, n-butyl group, i- Butyl group, s-butyl group, t-butyl group, c-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, c-pentyl group, 2-methyl-c-butyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 1, 1-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, c-hexyl group, 1-methyl-c-pentyl group, 1-ethyl-c -Butyl group, 1,2-dimethyl-c-butyl group, n-heptyl group n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, An n-octadecyl group, an n-nonadecyl group, an n-eicosyl group and the like can be mentioned.

In the dye for dye-sensitized solar cell of the present invention, as R ^{1 to} R ⁴ , in consideration of increasing the adsorptivity to the metal oxide constituting the semiconductor electrode and the solubility in the organic solvent during varnish preparation, A hydrogen atom and a C1-C10 alkyl group are preferable.
In addition, as R ^{17 to} R ^24, for the same reason as described above, in consideration of increasing the adsorptivity to the carbonylthiophene compound and the solubility in the organic solvent at the time of varnish preparation, a hydrogen atom and a carbon number of 1 to 10 Alkyl groups are preferred.
Furthermore, as the R ^5, R ^6, R ²⁵ and R ^26, a hydrogen atom, preferably a number of 1 to 10 alkyl group carbon atoms, and more preferably a hydrogen atom.

Z in the formula (1) is at least one divalent organic group selected from the above formulas (2) to (4), and a divalent organic group represented by the formula (2) is particularly preferable. In particular, an unsubstituted thiophenyl group in which R ⁷ and R ⁸ are both hydrogen atoms is preferred.
On the other hand, Y in formula (5) is at least one divalent organic group selected from the above formulas (6) to (8), and in particular, a divalent organic group represented by formula (6). In particular, an unsubstituted thiophenyl group in which R ²⁷ and R ²⁸ are both hydrogen atoms is preferable.

M, n, o, and p each independently represent an integer of 0 or 1 or more, and are integers that satisfy 1 ≦ m + n + o and 2 ≦ m + n + o + p ≦ 1,000, but 2 ≦ m + n + o + p ≦ 200 Is preferable, and 5 ≦ m + n + o + p ≦ 200 is more preferable. In particular, a compound in which any two of n, m, o, and p are 0, and a compound in which any two of n, m, and o are 0 are preferable.
This compound may be an oligomer satisfying 2 ≦ m + n + o + p ≦ 20 or a polymer satisfying 20 ≦ m + n + o + p ≦ 1,000.
The molecular weight of the carbonylthiophene compound is not particularly limited, but in the case of a polymer, the weight average molecular weight is preferably 1,000 to 100,000, more preferably 1,000 to 50,000.

M ′, n ′, o ′ and p ′ each independently represent 0 or an integer of 1 or more, 1 ≦ m ′ + n ′ + o ′, and 2 ≦ m ′ + n ′ + o ′ + p ′ ≦ Although it is an integer satisfying 1,000, 2 ≦ m ′ + n ′ + o ′ + p ′ ≦ 200 is preferable, and 5 ≦ m ′ + n ′ + o ′ + p ′ ≦ 200 is more preferable. In particular, a compound in which any two of m ′, n ′, o ′, and p ′ are 0, and a compound in which any two of m ′, n ′, and o ′ are 0 are preferable.
This compound may be an oligomer satisfying 2 ≦ m ′ + n ′ + o ′ + p ′ ≦ 20 or a polymer satisfying 20 ≦ m ′ + n ′ + o ′ + p ′ ≦ 1,000.
The molecular weight of the phosphorylthiophene compound is not particularly limited, but in the case of a polymer, the weight average molecular weight is preferably 1,000 to 100,000, more preferably 1,000 to 50,000.
In addition, the weight average molecular weight in this invention is a polystyrene conversion value by gel filtration chromatography.

  Both ends of the carbonylthiophene compound and phosphorylthiophene compound are independently of each other a hydrogen atom, a halogen atom, a C1-20 monoalkylamino group, a C1-20 dialkylamino group, a substituted or unsubstituted phenyl. Group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthranyl group, a C1-C10 trialkylstannyl group, a C1-C10 trialkylsilyl group and the like are preferable. preferable.

Here, examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.
Specific examples of the C 1-20 monoalkylamino group carbon, NHMe, NHEt, NHPr-n , NHPr-i, NHBu-n, NHBu-i, NHBu-s, NHBu-t, NHPen-n, NHCHEt 2, NHHex-n, NHHep-n, NHOct-n, NHDec-n, and the like can be given.
Examples of C20 dialkylamino group _{carbon, NMe 2, NEt 2, N} (Pr-n) 2, N (Pr-i) 2, N (Bu-n) 2, N (Bu-i) ₂ , N (Bu-s) ₂ , N (Bu-t) ₂ , N (Pen-n) ₂ , N (CHEt ₂ ) ₂ , N (Hex-n) ₂ , N (Hep-n) ₂ , N (Oct-n) ₂ , N (Dec-n) ₂ , N (Me) (Bu-n), N (Me) (Pen-n), N (Me) (Hex-n), N (Me) ( Hep-n), N (Me) (Oct-n), N (Me) (Dec-n) and the like.
Specific examples of the C 1 -C 10 trialkyl stannyl group _{carbon, SnMe 3, SnEt 3, Sn} (Pr-n) 3, Sn (Pr-i) 3, Sn (Bu-n) 3, Sn (Bu- i) ₃ , Sn (Bu-s) ₃ , Sn (Bu-t) _{3 and the} like.
Specific examples of the C 1 -C 10 trialkylsilyl group having a _{carbon, SiMe 3, SiEt 3, Si} (Pr-n) 3, Si (Pr-i) 3, Si (Bu-n) 3, Si (Bu-i ) ₃ , Si (Bu-s) ₃ , Si (Bu-t) _{3 and the} like.

  Specific examples of the substituted or unsubstituted phenyl group include phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-trifluoromethylphenyl, m-trifluoromethylphenyl, and p-trifluoromethylphenyl. P-ethylphenyl, pi-propylphenyl, pt-butylphenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-bromophenyl, m-bromophenyl, p-bromophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, o-trifluoromethoxyphenyl, p-trifluoromethoxyphenyl, o-nitrophenyl, m-nitrophenyl, p -Nitrophenyl, o-dimethylaminophenyl m-dimethylaminophenyl, p-dimethylaminophenyl, p-cyanophenyl, 3,5-dimethylphenyl, 3,5-bistrifluoromethylphenyl, 3,5-dimethoxyphenyl, 3,5-bistrifluoromethoxyphenyl, 3 , 5-diethylphenyl, 3,5-di-i-propylphenyl, 3,5-dichlorophenyl, 3,5-dibromophenyl, 3,5-difluorophenyl, 3,5-dinitrophenyl, 3,5- Dicyanophenyl, 2,4,6-trimethylphenyl, 2,4,6-tristrifluoromethylphenyl, 2,4,6-trimethoxyphenyl, 2,4,6-tristrifluoromethoxyphenyl, 2,4 6-trichlorophenyl, 2,4,6-tribromophenyl, 2,4,6-trifluorophenyl, o Biphenylyl, m- biphenylyl, p- biphenylyl and the like.

  Specific examples of the substituted or unsubstituted naphthyl group include 1-naphthyl, 2-naphthyl, 2-butyl-1-naphthyl, 3-butyl-1-naphthyl, 4-butyl-1-naphthyl, and 5-butyl-1. -Naphthyl, 6-butyl-1-naphthyl, 7-butyl-1-naphthyl, 8-butyl-1-naphthyl, 1-butyl-2-naphthyl, 3-butyl-2-naphthyl, 4-butyl-2-naphthyl 5-butyl-2-naphthyl, 6-butyl-2-naphthyl, 7-butyl-2-naphthyl, 8-butyl-2-naphthyl, 2-hexyl-1-naphthyl, 3-hexyl-1-naphthyl, 4 -Hexyl-1-naphthyl, 5-hexyl-1-naphthyl, 6-hexyl-1-naphthyl, 7-hexyl-1-naphthyl, 8-hexyl-1-naphthyl, 1-hexyl-2-naphthyl, 3- Xyl-2-naphthyl, 4-hexyl-2-naphthyl, 5-hexyl-2-naphthyl, 6-hexyl-2-naphthyl, 7-hexyl-2-naphthyl, 8-hexyl-2-naphthyl, 2-octyl- 1-naphthyl, 3-octyl-1-naphthyl, 4-octyl-1-naphthyl, 5-octyl-1-naphthyl, 6-octyl-1-naphthyl, 7-octyl-1-naphthyl, 8-octyl-1- Naphthyl, 1-octyl-2-naphthyl, 3-octyl-2-naphthyl, 4-octyl-2-naphthyl, 5-octyl-2-naphthyl, 6-octyl-2-naphthyl, 7-octyl-2-naphthyl, 8-octyl-2-naphthyl, 2-phenyl-1-naphthyl, 3-phenyl-1-naphthyl, 4-phenyl-1-naphthyl, 5-phenyl-1-naphthyl 6-phenyl-1-naphthyl, 7-phenyl-1-naphthyl, 8-phenyl-1-naphthyl, 1-phenyl-2-naphthyl, 3-phenyl-2-naphthyl, 4-phenyl-2-naphthyl, 5- Phenyl-2-naphthyl, 6-phenyl-2-naphthyl, 7-phenyl-2-naphthyl, 8-phenyl-2-naphthyl, 2-methoxy-1-naphthyl, 3-methoxy-1-naphthyl, 4-methoxy- 1-naphthyl, 5-methoxy-1-naphthyl, 6-methoxy-1-naphthyl, 7-methoxy-1-naphthyl, 8-methoxy-1-naphthyl, 1-methoxy-2-naphthyl, 3-methoxy-2- Naphthyl, 4-methoxy-2-naphthyl, 5-methoxy-2-naphthyl, 6-methoxy-2-naphthyl, 7-methoxy-2-naphthyl, 8-methoxy-2-naphth Til, 2-ethoxy-1-naphthyl, 3-ethoxy-1-naphthyl, 4-ethoxy-1-naphthyl, 5-ethoxy-1-naphthyl, 6-ethoxy-1-naphthyl, 7-ethoxy-1-naphthyl, 8-ethoxy-1-naphthyl, 1-ethoxy-2-naphthyl, 3-ethoxy-2-naphthyl, 4-ethoxy-2-naphthyl, 5-ethoxy-2-naphthyl, 6-ethoxy-2-naphthyl, 7- Ethoxy-2-naphthyl, 8-ethoxy-2-naphthyl, 2-butoxy-1-naphthyl, 3-butoxy-1-naphthyl, 4-butoxy-1-naphthyl, 5-butoxy-1-naphthyl, 6-butoxy- 1-naphthyl, 7-butoxy-1-naphthyl, 8-butoxy-1-naphthyl, 1-butoxy-2-naphthyl, 3-butoxy-2-naphthyl, 4-butoxy-2 Naphthyl, 5-butoxy-2-naphthyl, 6-butoxy-2-naphthyl, 7-butoxy-2-naphthyl, 8-butoxy-2-naphthyl, 2-amino-1-naphthyl, 3-amino-1-naphthyl, 4-amino-1-naphthyl, 5-amino-1-naphthyl, 6-amino-1-naphthyl, 7-amino-1-naphthyl, 8-amino-1-naphthyl, 1-amino-2-naphthyl, 3- Amino-2-naphthyl, 4-amino-2-naphthyl, 5-amino-2-naphthyl, 6-amino-2-naphthyl, 7-amino-2-naphthyl, 8-amino-2-naphthyl, 2- (N , N-dimethylamino) -1-naphthyl, 3- (N, N-dimethylamino) -1-naphthyl, 4- (N, N-dimethylamino) -1-naphthyl, 5- (N, N-dimethylamino) ) -1-Naph 6- (N, N-dimethylamino) -1-naphthyl, 7- (N, N-dimethylamino) -1-naphthyl, 8- (N, N-dimethylamino) -1-naphthyl, 1- ( N, N-dimethylamino) -2-naphthyl, 3- (N, N-dimethylamino) -2-naphthyl, 4- (N, N-dimethylamino) -2-naphthyl, 5- (N, N-dimethyl) Amino) -2-naphthyl, 6- (N, N-dimethylamino) -2-naphthyl, 7- (N, N-dimethylamino) -2-naphthyl, 8- (N, N-dimethylamino) -2- Naphthyl, 2- (N, N-diphenylamino) -1-naphthyl, 3- (N, N-diphenylamino) -1-naphthyl, 4- (N, N-diphenylamino) -1-naphthyl, 5- ( N, N-diphenylamino) -1-naphthyl, 6- (N, N-diphenylamino) -1-naphthyl, 7- (N, N-diphenylamino) -1-naphthyl, 8- (N, N-diphenylamino) -1-naphthyl, 1- (N, N-diphenylamino) 2-naphthyl, 3- (N, N-diphenylamino) -2-naphthyl, 4- (N, N-diphenylamino) -2-naphthyl, 5- (N, N-diphenylamino) -2-naphthyl, Examples include 6- (N, N-diphenylamino) -2-naphthyl, 7- (N, N-diphenylamino) -2-naphthyl, and 8- (N, N-diphenylamino) -2-naphthyl.

  Specific examples of the substituted or unsubstituted anthranyl group include 1-anthranyl, 2-anthranyl, 9-anthranyl, 2-butyl-1-anthranyl, 3-butyl-1-anthranyl, 4-butyl-1-anthranyl, 5 -Butyl-1-anthranyl, 6-butyl-1-anthranyl, 7-butyl-1-anthranyl, 8-butyl-1-anthranyl, 9-butyl-1-anthranyl, 10-butyl-1-anthranyl, 1-butyl 2-anthranyl, 3-butyl-2-anthranyl, 4-butyl-2-anthranyl, 5-butyl-2-anthranyl, 6-butyl-2-anthranyl, 7-butyl-2-anthranyl, 8-butyl-2 -Anthranyl, 9-butyl-2-anthranyl, 10-butyl-2-anthranyl, 1-butyl-9-a Tranyl, 2-butyl-9-anthranyl, 3-butyl-9-anthranyl, 4-butyl-9-anthranyl, 10-butyl-9-anthranyl, 2-hexyl-1-anthranyl, 3-hexyl-1-anthranyl, 4-hexyl-1-anthranyl, 5-hexyl-1-anthranyl, 6-hexyl-1-anthranyl, 7-hexyl-1-anthranyl, 8-hexyl-1-anthranyl, 9-hexyl-1-anthranyl, 10- Hexyl-1-anthranyl, 1-hexyl-2-anthranyl, 3-hexyl-2-anthranyl, 4-hexyl-2-anthranyl, 5-hexyl-2-anthranyl, 6-hexyl-2-anthranyl, 7-hexyl- 2-anthranyl, 8-hexyl-2-anthranyl, 9-hexyl-2- Ntranyl, 10-hexyl-2-anthranyl, 1-hexyl-9-anthranyl, 2-hexyl-9-anthranyl, 3-hexyl-9-anthranyl, 4-hexyl-9-anthranyl, 10-hexyl-9-anthranyl 2-octyl-1-anthranyl, 3-octyl-1-anthranyl, 4-octyl-1-anthranyl, 5-octyl-1-anthranyl, 6-octyl-1-anthranyl, 7-octyl-1-anthranyl, 8- Octyl-1-anthranyl, 9-octyl-1-anthranyl, 10-octyl-1-anthranyl, 1-octyl-2-anthranyl, 3-octyl-2-anthranyl, 4-octyl-2-anthranyl, 5-octyl- 2-anthranyl, 6-octyl-2-anthranyl, 7-oct Tyl-2-anthranyl, 8-octyl-2-anthranyl, 9-octyl-2-anthranyl, 10-octyl-2-anthranyl, 1-octyl-9-anthranyl, 2-octyl-9-anthranyl, 3-octyl- 9-anthranyl, 4-octyl-9-anthranyl, 10-octyl-9-anthranyl, 2-phenyl-1-anthranyl, 3-phenyl-1-anthranyl, 4-phenyl-1-anthranyl, 5-phenyl-1- Anthranyl, 6-phenyl-1-anthranyl, 7-phenyl-1-anthranyl, 8-phenyl-1-anthranyl, 9-phenyl-1-anthranyl, 10-phenyl-1-anthranyl, 1-phenyl-2-anthranyl, 3-phenyl-2-anthranyl, 4-phenyl-2-anthrani 5-phenyl-2-anthranyl, 6-phenyl-2-anthranyl, 7-phenyl-2-anthranyl, 8-phenyl-2-anthranyl, 9-phenyl-2-anthranyl, 10-phenyl-2-anthranyl, 1 -Phenyl-9-anthranyl, 2-phenyl-9-anthranyl, 3-phenyl-9-anthranyl, 4-phenyl-9-anthranyl, 10-phenyl-9-anthranyl, 2-methoxy-1-anthranyl, 3-methoxy -1-anthranyl, 4-methoxy-1-anthranyl, 5-methoxy-1-anthranyl, 6-methoxy-1-anthranyl, 7-methoxy-1-anthranyl, 8-methoxy-1-anthranyl, 9-methoxy-1 -Anthranyl, 10-methoxy-1-anthranyl, 1-methoxy-2 Anthranyl, 3-methoxy-2-anthranyl, 4-methoxy-2-anthranyl, 5-methoxy-2-anthranyl, 6-methoxy-2-anthranyl, 7-methoxy-2-anthranyl, 8-methoxy-2-anthranyl, 9-methoxy-2-anthranyl, 10-methoxy-2-anthranyl, 1-methoxy-9-anthranyl, 2-methoxy-9-anthranyl, 3-methoxy-9-anthranyl, 4-methoxy-9-anthranyl, 10- Methoxy-9-anthranyl, 2-ethoxy-1-anthranyl, 3-ethoxy-1-anthranyl, 4-ethoxy-1-anthranyl, 5-ethoxy-1-anthranyl, 6-ethoxy-1-anthranyl, 7-ethoxy- 1-anthranyl, 8-ethoxy-1-anthranyl, 9-eth Xyl-1-anthranyl, 10-ethoxy-1-anthranyl, 1-ethoxy-2-anthranyl, 3-ethoxy-2-anthranyl, 4-ethoxy-2-anthranyl, 5-ethoxy-2-anthranyl, 6-ethoxy- 2-anthranyl, 7-ethoxy-2-anthranyl, 8-ethoxy-2-anthranyl, 9-ethoxy-2-anthranyl, 10-ethoxy-2-anthranyl, 1-ethoxy-9-anthranyl, 2-ethoxy-9- Anthranyl, 3-ethoxy-9-anthranyl, 4-ethoxy-9-anthranyl, 10-ethoxy-9-anthranyl, 2-butoxy-1-anthranyl, 3-butoxy-1-anthranyl, 4-butoxy-1-anthranyl, 5-butoxy-1-anthranyl, 6-butoxy-1-anthrani 7-butoxy-1-anthranyl, 8-butoxy-1-anthranyl, 9-butoxy-1-anthranyl, 10-butoxy-1-anthranyl, 1-butoxy-2-anthranyl, 3-butoxy-2-anthranyl, 4 -Butoxy-2-anthranyl, 5-butoxy-2-anthranyl, 6-butoxy-2-anthranyl, 7-butoxy-2-anthranyl, 8-butoxy-2-anthranyl, 9-butoxy-2-anthranyl, 10-butoxy 2-anthranyl, 1-butoxy-9-anthranyl, 2-butoxy-9-anthranyl, 3-butoxy-9-anthranyl, 4-butoxy-9-anthranyl, 10-butoxy-9-anthranyl, 2-amino-1 -Anthranyl, 3-amino-1-anthranyl, 4-amino-1-an Ranyl, 5-amino-1-anthranyl, 6-amino-1-anthranyl, 7-amino-1-anthranyl, 8-amino-1-anthranyl, 9-amino-1-anthranyl, 10-amino-1-anthranyl, 1-amino-2-anthranyl, 3-amino-2-anthranyl, 4-amino-2-anthranyl, 5-amino-2-anthranyl, 6-amino-2-anthranyl, 7-amino-2-anthranyl, 8- Amino-2-anthranyl, 9-amino-2-anthranyl, 10-amino-2-anthranyl, 1-amino-9-anthranyl, 2-amino-9-anthranyl, 3-amino-9-anthranyl, 4-amino- 9-anthranyl, 10-amino-9-anthranyl, 2- (N, N-dimethylamino) -1-anthranyl, 3 -(N, N-dimethylamino) -1-anthranyl, 4- (N, N-dimethylamino) -1-anthranyl, 5- (N, N-dimethylamino) -1-anthranyl, 6- (N, N -Dimethylamino) -1-anthranyl, 7- (N, N-dimethylamino) -1-anthranyl, 8- (N, N-dimethylamino) -1-anthranyl, 9- (N, N-dimethylamino)- 1-anthranyl, 10- (N, N-dimethylamino) -1-anthranyl, 1- (N, N-dimethylamino) -2-anthranyl, 3- (N, N-dimethylamino) -2-anthranyl, 4 -(N, N-dimethylamino) -2-anthranyl, 5- (N, N-dimethylamino) -2-anthranyl, 6- (N, N-dimethylamino) -2-anthranyl, 7- (N, N - Tilamino) -2-anthranyl, 8- (N, N-dimethylamino) -2-anthranyl, 9- (N, N-dimethylamino) -2-anthranyl, 10- (N, N-dimethylamino) -2- Anthranyl, 1- (N, N-dimethylamino) -9-anthranyl, 2- (N, N-dimethylamino) -9-anthranyl, 3- (N, N-dimethylamino) -9-anthranyl, 4- ( N, N-dimethylamino) -9-anthranyl, 10- (N, N-dimethylamino) -9-anthranyl, 2- (N, N-diphenylamino) -1-anthranyl, 3- (N, N-diphenyl) Amino) -1-anthranyl, 4- (N, N-diphenylamino) -1-anthranyl, 5- (N, N-diphenylamino) -1-anthranyl, 6- (N, N-diphe) Ruamino) -1-anthranyl, 7- (N, N-diphenylamino) -1-anthranyl, 8- (N, N-diphenylamino) -1-anthranyl, 9- (N, N-diphenylamino) -1- Anthranyl, 10- (N, N-diphenylamino) -1-anthranyl, 1- (N, N-diphenylamino) -2-anthranyl, 3- (N, N-diphenylamino) -2-anthranyl, 4- ( N, N-diphenylamino) -2-anthranyl, 5- (N, N-diphenylamino) -2-anthranyl, 6- (N, N-diphenylamino) -2-anthranyl, 7- (N, N-diphenyl) Amino) -2-anthranyl, 8- (N, N-diphenylamino) -2-anthranyl, 9- (N, N-diphenylamino) -2-anthranyl, 10- (N , N-diphenylamino) -2-anthranyl, 1- (N, N-diphenylamino) -9-anthranyl, 2- (N, N-diphenylamino) -9-anthranyl, 3- (N, N-diphenylamino) ) -9-anthranyl, 4- (N, N-diphenylamino) -9-anthranyl, 10- (N, N-diphenylamino) -9-anthranyl and the like.

The carbonylthiophene compound represented by the formula (1) used as the dye for the dye-sensitized solar cell of the present invention is obtained by halogenating a commercially available alkyl thiophene-3-carboxylate with a halogenating reagent such as N-halosuccinimide. The obtained carbonylthiophene monomer compound can be produced by coupling or polymerization by an appropriate method.
On the other hand, the phosphorylthiophene compound represented by the formula (5) can be synthesized by the method described in International Publication No. 2009/119428.
The coupling method is not particularly limited, and for example, biaryl coupling, Stille coupling, Suzuki coupling, Ullmann coupling, Heck reaction, Sonogashira coupling, Grignard reaction and the like can be used.
The polymerization method is not particularly limited as long as it is a method capable of polymerizing a carbonylthiophene compound, and may be appropriately selected from known polymerization methods such as chemical oxidation polymerization, electrolytic oxidation polymerization, and catalytic polymerization. In the invention, catalytic polymerization is preferred.

Catalytic polymerization is a method in which a carbonylthiophene monomer compound and a monomer corresponding to Z used as necessary are reacted in the presence of a metal catalyst to obtain a carbonylthiophene oligomer or polymer compound represented by the formula (1). It is.
As the carbonylthiophene monomer compound used for catalytic polymerization and the monomer that gives Z, a carbonylthiophene compound having a halogen atom at the terminal (polymerization site) substituent is preferred. Of these, those having a bromine atom at the end are preferred.

  Examples of the metal catalyst include nickel complexes, and specific examples include nickel (0) represented by bis (1,5-cyclooctadiene) nickel (0), tetrakis (triphenylphosphine) nickel (0), and the like. ) Complex, or nickel chloride, bis (triphenylphosphine) nickel (II) dichloride, [1,2-bis (diphenylphosphino) ethane] nickel (II) dichloride, [1,3-bis (diphenylphosphino) propane ] Nickel (II) complexes represented by nickel (II) dichloride, tris (2,2'-bipyridyl) nickel (II) dibromide and the like, 1,5-cyclooctadiene, 2,2'-bipyridine, triphenyl Examples include combinations with various ligands represented by phosphine. Among these, in consideration of increasing the polymerization degree of the obtained polymer, a combination of bis (1,5-cyclooctadiene) nickel, 1,5-cyclooctadiene and 2,2'-bipyridine is preferable.

The amount of the metal catalyst used is preferably 0.05 to 2.0 moles, particularly preferably 0.5 to 0.8 moles, relative to the halogen atoms contained in all monomer compounds of the substrate.
The amount of the ligand used is preferably 0.05 to 2.0 moles, and particularly preferably 0.5 to 0.8 moles, relative to the halogen atoms contained in all monomer compounds of the substrate.
Examples of the reaction solvent include amide compounds such as N, N-dimethylformamide and N, N-dimethylacetamide; aromatic hydrocarbons such as benzene, toluene and xylene; tetrahydrofuran (THF), 1,4-dioxane, Ether compounds such as 1,2-dimethoxyethane and diethylene glycol dimethyl ether are preferred. Especially, it is suitable at the point that the polymerization degree of the polymer which 1, 4- dioxane produced | generated is high.
The reaction temperature should just be below the boiling point of a use solvent, and is about 20-200 degreeC normally.
The reaction time is not particularly limited, but is usually about 1 to 48 hours.

The dye-sensitized solar cell according to the present invention uses both the carbonylthiophene compound represented by the above-described formula (1) and the phosphorylthiophene compound represented by the formula (5) as dyes. Specifically, Has a light-transmitting substrate, a transparent conductive film laminated on the substrate, and a porous semiconductor made of a metal oxide laminated on the transparent conductive film. The semiconductor electrode to which the dye for dye-sensitized solar cells is adsorbed, a counter electrode, and an electrolyte interposed between these electrodes are configured.
In this case, the use ratio of the carbonylthiophene compound represented by the formula (1) and the phosphorylthiophene compound represented by the formula (5) is not particularly limited. The ruthiophene compound can be about 10: 1 to 1:10, preferably 5: 1 to 1: 5, and more preferably 2: 1 to 1: 2.

The dye-sensitized solar cell of the present invention is characterized by using a dye in which the carbonylthiophene compound represented by the above formula (1) and the phosphorylthiophene compound represented by the formula (5) are used in combination. Therefore, the other solar cell constituent members are not particularly limited and can be appropriately selected from known ones.
For example, the light-transmitting substrate is not particularly limited as long as it has a light-transmitting property and can be a conductive layer substrate, and includes a glass substrate, a transparent polymer film, and a laminate thereof. Etc. can be used.
Examples of the material for the transparent polymer film include triacetyl cellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), and polyarylate. Polysulfone, polyester sulfone (PES), polyimide (PI), polyetherimide (PEI), cyclic polyolefin, brominated phenoxy, and the like can be used.

  As a material constituting the transparent conductive film, for example, platinum, gold, silver, copper, zinc, titanium, aluminum, indium, alloys such as these alloys, indium-tin composite oxide, tin oxide doped with fluorine or antimony However, it is particularly preferable to use tin dioxide or indium-tin oxide doped with fluorine or antimony. This transparent conductive layer can be formed by applying or vapor-depositing on the surface of the transparent substrate.

Examples of the metal oxide constituting the semiconductor include TiO ₂ , SnO ₂ , Fe ₂ O ₃ , WO ₃ , ZnO, Nb ₂ O _{5 and the} like.
The counter electrode is not particularly limited as long as it acts as a positive electrode of the dye-sensitized solar cell. For example, at least selected from platinum, gold, silver, copper, aluminum, and magnesium on a glass substrate or a plastic film. Examples thereof include an electrode on which one kind of metal is applied or deposited.

Examples of the electrolyte include electrolyte salts such as metal iodides such as LiI, NaI, KI, CsI, and CaI ₂ , quaternary pyridinium or imidazolium compound iodine salts, tetraalkylammonium compound iodine salts, and the like I ⁻ And an organic solvent containing iodine capable of forming a redox pair.
Organic solvents include carbonates such as ethylene carbonate and propylene carbonate; ethers such as dioxane, diethyl ether, ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, and polypropylene glycol dialkyl ether; methanol, ethanol, ethylene glycol Monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, alcohols such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin; acetonitrile, propionitrile, benzonitrile, etc. Nitrile And the like.
In addition, the dye-sensitized solar cell of the present invention may be provided with a functional layer such as a protective layer or an antireflection layer at an appropriate position.

As a method for adsorbing the dye-sensitized solar cell dye of the present invention on the surface of the porous semiconductor, a solution (varnish) containing the above two kinds of dyes is prepared, and a substrate having the porous semiconductor is immersed in the solution. For example, a method of applying a solution (varnish) containing two kinds of pigments to a substrate having a porous semiconductor can be used.
The solvent for preparing the solution (varnish) containing the dye is not particularly limited as long as it has the ability to dissolve the dye, and examples thereof include methanol, ethanol, dimethyl sulfoxide (DMSO), and chloroform.
The total pigment concentration in the solution (varnish) is not particularly limited, but can be about 0.01 to 10 mmol / L.
The total adsorption amount of the dye can be, for example, about 0.01 to 100 mmol per unit surface area (1 m ² ) of the semiconductor.

In the dye-sensitized solar cell of the present invention, known dyes such as metal complex dyes, methine dyes, porphyrin dyes, and phthalocyanine dyes may be used in combination with the dye of the present invention.
Among these, ruthenium-bipyridine complex, among them cis-di (thiocyanato) -N, N′-bis (2,) because of its high optical activity and excellent adsorption to semiconductor and durability. 2'-bipyridyl-4,4'-dicarboxylic acid) ruthenium (II) is preferred.

Hereinafter, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
In addition, the analyzers and conditions used in the examples are as follows.

[1] ¹ H-NMR
Model: JNM-A500 (JEOL Ltd.) or AVANCE 400S (Bruker)
[2] Gel filtration chromatography (GPC)
Model: TOSOH: HLC-8220GPC, column: SHODEX GPC KF-804L + GPC KF-805L, column temperature: 40 ° C., detector: UV detector (254 nm) and RI detector, eluent: THF, column flow rate: 1.0 ml / Min.
[3] IPCE (incident-photon conversion efficiency) spectrum Using a spectroscope (SM-250, manufactured by Spectrometer Co., Ltd.) with a 500 W Xe lamp, spectrally radiates in the range of 300 nm to 1100 nm and irradiates monochromatic light at intervals of 10 nm Then, the photocurrent from the cell was detected by an ammeter (6487, manufactured by Keithley), and the photocurrent spectrum was measured by correcting the spectrum measured by the reference silicon light receiving element with the spectral sensitivity.
[4] Current-Voltage Measurement Using a solar simulator (YSS-80, manufactured by Yamashita Denso Co., Ltd.), a simulated solar light source (AM1.5, 100 mW / cm ² ) was irradiated to measure the current-voltage characteristics (HSV- 100, manufactured by HOKUTO DENKO).

[Synthesis Example 1] Production of polythiophene derivative PT-P-Et

0.756 g (2.00 mmol) of 2,5-dibromo-3-diethoxyphosphorylthiophene and 0.937 g (6.00 mmol) of 2,2′-bipyridyl synthesized by the method described in International Publication No. 2006/109895 pamphlet 1.2 equivalents), and the reaction vessel was purged with nitrogen, and then 0.75 g (3.00 mmol) 2,5-dibromothiophene and 0.541 g (5.00 mmol) 1,5-cyclooctadiene. , 1.0 eq.), And 50 ml of 1,4-dioxane were added via syringe. Subsequently, 1.650 g (6.00 mmol, 1.2 equivalents) of bis (1,5-cyclooctadiene) nickel (0) was added, and the mixture was heated and stirred at 60 ° C. for 5 hours.
After completion of the reaction, the reaction solution was filtered through celite, and the residue was washed with chloroform. The filtrate was washed once with a 10% by mass aqueous hydrochloric acid solution and three times with 10% by mass brine, dried over anhydrous sodium sulfate to the organic layer, filtered, and then the solvent was distilled off. Chloroform was added to the residue after distillation to dissolve it, and the mixture was added dropwise to n-hexane. The precipitated solid was collected by filtration and washed with n-hexane. This was dried under reduced pressure with a vacuum pump to obtain 0.351 g of a red solid.
Mw (GPC): 9,232
¹ H-NMR (CDCl ₃ ): 1.29-1.35 (br), 4.11-4.21 (br), 7.13-7.22 (br), 7.50-7.83 ( br)

[Synthesis Example 2] Production of polythiophene derivative PT-P

0.070 g of the polythiophene derivative PT-P-Et obtained in Synthesis Example 1 was put into a reaction vessel and dissolved in a nitrogen atmosphere by adding 7 ml of methylene chloride and 5 ml of acetonitrile. Then, 0.096 g of iodotrimethylsilane was slowly added. It was dripped. After completion of dropping, the mixture was stirred at room temperature for 1 hour. After the reaction, water was added, the mixture was stirred at room temperature for 30 minutes, 28 mass% aqueous ammonia was added to dissolve the crude product, and the mixture was washed 5 times with chloroform. Water was distilled off from the aqueous layer. Water was added to the residue after distillation to dissolve it, and the mixture was added dropwise to acetone. The precipitated solid was collected by filtration and washed with acetone. This was dried under reduced pressure with a vacuum pump to obtain 0.055 g of a red solid.
¹ H-NMR (CD ₃ OD): 1.14-1.32 (br), 3.82-4.16 (br), 7.22-7.78 (br)

[Synthesis Example 3] Production of methyl 2,5-dibromothiophene-3-carboxylate

Commercially available methyl thiophene-3-carboxylate, N, N-dimethylformamide, and acetic acid were charged into the reaction vessel, and the temperature was raised to 75 ° C. N-bromosuccinimide was added there, and it heated at 75 degreeC for 2.5 hours. After completion of the reaction, the reaction mixture was extracted with ethyl acetate, and the organic layer was washed successively with 10% by mass aqueous sodium thiosulfate solution and water, and the solvent was distilled off. The obtained crude product was purified with a silica gel column (ethyl acetate / hexane = 1/10 → 1/6) to obtain a white solid.
¹ H-NMR (CDCl ₃ ): 3.87 (s, 3H), 7.35 (s, 1H)

[Synthesis Example 4] Production of polythiophene derivative PT-C-Me

Methyl 2,5-dibromothiophene-3-carboxylate and 2,5-dibromothiophene obtained in Synthesis Example 3, 2,2′-bipyridyl (1.2 equivalents), 1,5-cyclooctadiene (1. 0 equivalents) and bis (1,5-cyclooctadiene) nickel (0) (1.2 equivalents) were added to the reaction vessel, N, N-dimethylformamide was added under a nitrogen atmosphere, and the mixture was heated at 60 ° C. for 4 hours. Heated. After completion of the reaction, the reaction solution was filtered through celite, and the residue was washed with chloroform. The filtrate was washed with 14% aqueous ammonia, 2M aqueous hydrochloric acid and water, dried over anhydrous sodium sulfate to the organic layer, and the solvent was distilled off. This was purified with a silica gel column (chloroform / methanol = 100/0 → 95/5) to obtain a dark red solid.
Mw (GPC): 2,700

[Synthesis Example 5] Production of polythiophene derivative PT-C

The polythiophene derivative PT-C-Me and N, N-dimethylformamide obtained in Synthesis Example 4 were put into a reaction vessel and heated to 100 ° C. 20 mass% sodium hydroxide aqueous solution (12 equivalent) was dripped here, and it heated at 100 degreeC for 2 hours. After completion of the reaction, 2M aqueous hydrochloric acid solution was added, and the mixture was dried. The resulting solid was washed with water and filtered to give a dark red solid.
Mw (GPC): 2,700

[Example 1]
[1] Production of photoelectric conversion electrode As shown in FIG. 1, titania paste (Ti) on a glass substrate 11 (size: 15 mm × 25 mm) with an FTO (F: SnO ₂ ) film 12 having a surface resistance of 10 Ω / sq. -Nanoxide T / S, manufactured by SOLARONIXS) was applied by screen printing, dried at 120 ° C. for 3 minutes, and then baked at 500 ° C. for 30 minutes to form a titania semiconductor layer 13. When the film thickness of the titania semiconductor layer 13 after firing was measured with a stylus type film thickness meter (model number: ET4000A, manufactured by Kosaka Laboratory Ltd.), it was 8 μm.
Next, the fired substrate is immersed in a methanol solution (concentration: 0.1 mM) of the polythiophene derivative PT-P obtained in Synthesis Example 2 and the polythiophene derivative PT-C obtained in Synthesis Example 5 to obtain polythiophene. The derivative PT-P and the polythiophene derivative PT-C (pigment) (not shown) were simultaneously adsorbed on the titania semiconductor layer 13 to produce the photoelectric conversion electrode 10.

[2] Fabrication of Solar Cell Ethylene- around the counter electrode 20 in which a Pt layer 14 was formed (film thickness: 1 nm) on a glass substrate 15 with an FTO film having two electrolyte injection holes having a diameter of 0.7 mm. A methacrylic acid copolymer ionomer resin film (High Milan, manufactured by Mitsui DuPont Polychemical Co., Ltd.) (film thickness: 30 nm) was placed and bonded to the photoelectric conversion electrode 10 obtained above. Thereafter, an electrolyte 30 made of an acetonitrile solution containing 0.5 mol / L of N, N, N, N-tetrabutylammonium iodide and 0.05 mol / L of iodine is injected from the electrolyte injection hole, and dye sensitization is performed. A solar battery cell 1 was produced.

About the photovoltaic cell obtained in Example 1, IPCE was measured in the range of 300 to 800 nm. The obtained IPCE spectrum is shown in FIG. As shown in FIG. 2, it can be seen that IPCE is obtained in a region corresponding to light absorption from ultraviolet to 650 nm.
Moreover, the current-voltage characteristic of the obtained photovoltaic cell was measured. The result and IPCE at 450 nm are shown together in Table 1. As shown in Table 1, although there is some variation in data depending on the measurement time, a photoelectric conversion efficiency of 1.39% is obtained, and it can be seen that IPCE at 450 nm is 68.1%.

[Comparative Example 1]
A photoelectric conversion electrode and a solar battery cell were produced in the same manner as in Example 1 except that the dye adsorbed on the titania semiconductor layer 13 was changed to only the polythiophene derivative PT-P.
About the photovoltaic cell obtained in Comparative Example 1, IPCE was measured in the range of 300 to 800 nm. The obtained IPCE spectrum is shown in FIG. As shown in FIG. 3, it can be seen that IPCE is obtained in a region corresponding to light absorption from ultraviolet to 600 nm.
Moreover, the current-voltage characteristic of the obtained photovoltaic cell was measured. The result and IPCE at 450 nm are shown together in Table 1. As shown in Table 1, a photoelectric conversion efficiency of 1.04% is obtained, and it can be seen that IPCE at 450 nm is 54.8%.

[Comparative Example 2]
A photoelectric conversion electrode and a solar battery cell were produced in the same manner as in Example 1 except that the dye adsorbed on the titania semiconductor layer 13 was changed to only the polythiophene derivative PT-C.
About the photovoltaic cell obtained in Comparative Example 2, IPCE was measured in the range of 300 to 800 nm. The obtained IPCE spectrum is shown in FIG. As shown in FIG. 4, it can be seen that IPCE is obtained in a region corresponding to light absorption from ultraviolet to 650 nm.
Moreover, the current-voltage characteristic of the obtained photovoltaic cell was measured. The result and IPCE at 450 nm are shown together in Table 1. As shown in Table 1, a photoelectric conversion efficiency of 1.46% is obtained, and it can be seen that IPCE at 450 nm is 56.1%.

1 Solar cell (Dye-sensitized solar cell)
10 Photoelectric conversion electrode 11 Glass substrate (substrate having optical transparency)
12 FTO film (transparent conductive film)
13 Titania semiconductor layer adsorbed with photosensitizing dye (porous semiconductor)
14 Pt layer 15 Glass substrate 20 Counter electrode 30 Electrolyte

Claims (7)

A dye for a dye-sensitized solar cell, comprising a carbonylthiophene compound represented by formula (1) and a phosphorylthiophene compound represented by formula (5).

[In the formula, R ^{1 to} R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
m, n, o and p each independently represent an integer of 0 or 1 and satisfy 1 ≦ m + n + o and 2 ≦ m + n + o + p ≦ 1,000;
Z is a divalent organic group selected from the following formulas (2) to (4),

R ^{7 to} R ¹⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. )

(Wherein R ^{17 to} R ²⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
m ′, n ′, o ′ and p ′ each independently represent 0 or an integer of 1 or more, 1 ≦ m ′ + n ′ + o ′, and 2 ≦ m ′ + n ′ + o ′ + p ′ ≦ 1. , 000,
Y is a divalent organic group selected from the following formulas (6) to (8),

R ^{27 to} R ³⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. )]   A varnish comprising the dye-sensitized solar cell dye according to claim 1.   The organic thin film containing the pigment | dye for dye-sensitized solar cells of Claim 1.   The organic thin film produced from the varnish of Claim 2. A substrate having optical transparency, a transparent conductive film laminated on the substrate, and a porous semiconductor made of a metal oxide laminated on the transparent conductive film,
A semiconductor electrode, wherein the dye for a dye-sensitized solar cell according to claim 1 is adsorbed on a surface of the porous semiconductor.   The semiconductor electrode according to claim 5, wherein a substrate having a porous semiconductor is immersed in the varnish according to claim 2, and the dye for dye-sensitized solar cell is adsorbed to the porous semiconductor.   A dye-sensitized solar cell comprising the semiconductor electrode according to claim 5, a counter electrode, and an electrolyte interposed between the semiconductor electrode and the counter electrode.

Images