JP4982940B2 - Semiconductor for photoelectric conversion material, photoelectric conversion element and solar cell - Google Patents

Description

  The present invention relates to a semiconductor for a photoelectric conversion material, a photoelectric conversion element, and a solar cell.

  A photoelectric conversion material is a material that converts light energy into electrical energy using an electrochemical reaction between electrodes. When the photoelectric conversion material is irradiated with light, electrons are generated on one electrode side and move to the counter electrode. The electrons that have moved to the counter electrode move as ions in the electrolyte and return to one electrode.

  That is, the photoelectric conversion material is a material that can continuously extract light energy as electric energy, and is used in, for example, solar cells. There are several types of solar cells, but most of them are silicon solar cells that have been put to practical use in power generation panels for home installation, desk calculators, watches, portable game machines and the like.

  However, recently, dye-sensitized solar cells have attracted attention and are being studied for practical use. Dye-sensitized solar cells have been studied for a long time. Specifically, the basic structure is composed of a metal oxide semiconductor, a dye adsorbed thereon, an electrolyte solution, and a counter electrode. As the photoelectric conversion material in this case, a material obtained by adsorbing a spectral sensitizing dye having absorption in the visible light region on the semiconductor surface is used.

  For example, JP-A-1-220380 describes a solar cell having a spectral sensitizing dye layer such as a transition metal complex on the surface of a metal oxide semiconductor. JP-A-5-504023 describes a solar cell having a spectral sensitizing dye layer such as a transition metal complex on the surface of a titanium oxide semiconductor layer doped with metal ions.

On the other hand, as an oxide semiconductor electrode having photoelectric conversion ability, a semiconductor single crystal electrode has been used in the early days. The types include titanium oxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ), and the like.

  However, since the single crystal electrode has a small amount of dye adsorption, the efficiency is very low and the cost is high. Thus, a high surface area semiconductor electrode having a large number of pores formed by sintering fine particles has been devised. It has been reported by Tsubomura et al. That a porous zinc oxide electrode adsorbing an organic dye has very high performance (Nature, 261 (1976) p402).

Since then, the dyes have also been improved, and Graetzel et al. Have achieved the same performance as silicon solar cells by adsorbing ruthenium complex dyes on porous titanium oxide electrodes (J. Am. Chem. Soc. 115 (1993) 6382). However, for practical use replacing silicon solar cells, higher energy conversion efficiency, higher short-circuit current, open-circuit voltage, and form factor are required. At present, materials reported for porous semiconductor electrodes include ZnO, TiO ₂ , zirconium oxide (ZrO ₂ ), niobium oxide (Nb ₂ O ₅ ), and the like.

Dye-sensitized wet solar cells are much cheaper to manufacture than silicon solar cells, so in the future there is a possibility of replacing the silicon solar cells used in the above-mentioned various products. The characteristics of solar cells according to each product are important. There are various characteristics of solar cells,
1. Short circuit current 2. Open voltage Form factor 4. 4. Energy conversion efficiency The light absorption spectrum is important. The energy conversion efficiency of the solar cell is the biggest problem for solar cells, and its improvement has been strongly desired. As one of the technical problems affecting the efficiency, there is a demand for a sensitizing dye having the ability to efficiently transfer photoexcited electrons to a semiconductor. Of the various dyes studied so far, the ruthenium complex dyes are known to have relatively excellent characteristics, but the dyes are expensive and ruthenium, the central metal of the complex, is a rare element. Since there is concern about a stable supply in the future, an organic dye that is cheaper and can be stably supplied is more preferable.

  Many organic dyes have been studied so far because of such demands, but the photoelectric conversion efficiency is not yet sufficient, and there has been a demand for an organic dye that can constitute a photoelectric conversion element with higher conversion efficiency.

In addition to ruthenium complex dyes, various dyes have been studied, and polymethine dyes (particularly cyanine and merocyanine dyes) are one of them and have been studied conventionally. For example, odd-numbered methine dyes, even-numbered methine dyes, and the like are disclosed (for example, see Patent Documents 1 to 6). However, since none of the dyes yet has satisfactory performance, further development of dyes having strong adsorptive power and high efficiency up to a long wavelength region is desired.
JP-A-11-167937 Japanese Patent Laid-Open No. 11-214730 Japanese Patent Laid-Open No. 11-163378 Japanese Patent Laid-Open No. 11-214731 JP 2000-106224 A JP 2001-76775 A

  An object of the present invention is to provide an inexpensive semiconductor for a photoelectric conversion material and a photoelectric conversion element that achieve both excellent photoelectric conversion efficiency and stability. Furthermore, it is providing the solar cell using this semiconductor for photoelectric conversion materials, and a photoelectric conversion element.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention with a semiconductor for a photoelectric conversion material sensitized with a compound having a specific structure.

［式中、Ｒ _１ 、Ｒ _２ は各々、独立に水素原子、置換されていてもよい脂肪族基、置換されていてもよい芳香族基、置換されていてもよい複素環基を表し、また、Ｒ _１ とＲ _２ 間で結合して、（非金属原子群による）含窒素複素環を形成してもよい。Ｃｐは、５員または６員の芳香族炭素環基または複素環基で、少なくとも１つのカルボキシル基を置換基として有する化合物を有する原子団を表わす。Ｌ _１ 〜Ｌ_３は各々、置換されていてもよいメチン基を表わし、Ｚ _１ 及びＺ _２ は各々、酸素原子、硫黄原子、＞Ｎ−Ｒａ基を表し、ＲａはＲ _１ 並びにＲ _２ と同義であり、Ｒ _３ 〜Ｒ _６ は各々、水素原子、置換基を表す。また、Ｒ _３ とＲ _４ の間、或いはＲ _５ とＲ _６ の間は互いに結合して縮合環を形成してもよい。ｐは０又は１の整数を、ｑは１の整数を表す。］
２．前記一般式（２）のＣｐがＣｐ−６で表されることを特徴とする前記１に記載の光電変換材料用半導体。

［式中、Ｂ _１ は窒素原子或いは＝Ｃ−Ｒ _２３ 基、Ｂ _２ は窒素原子或いは＝Ｃ−Ｒ _２４ 基、Ｂ _３ は窒素原子或いは＝Ｃ−Ｒ _２５ 基、Ｂ _４ は窒素原子或いは＝Ｃ−Ｒ _２６ を表す。Ｒ _２３ 〜Ｒ _２６ は各々、水素原子、アルキル基、アルケニル基、アリール基、複素環基、アシルアミノ基、アルカンもしくはアリールスルホニルアミノ基、アミノ基、アルキルチオ基、アリールチオ基、アルコキシ基、アリールオキシ基、ウレイド基、アルコキシカルボニルアミノ基、カルバモイル基、スルファモイル基、シアノ基、カルボキシル基、アシル基、アリールオキシカルボニル基またはアルコキシカルボニル基を表す。］
３．下記一般式（４）又は（５）で表される化合物の少なくとも１種が半導体表面に吸着されていることを特徴とする光電変換材料用半導体。

［式中、Ｒ _１ 、Ｒ _２ は各々、独立に水素原子、置換されていてもよい脂肪族基、置換されていてもよい芳香族基、置換されていてもよい複素環基を表し、また、Ｒ _１ とＲ _２ 間で結合して、（非金属原子群による）含窒素複素環を形成してもよい。Ｒ _１０３ 〜Ｒ _１０８ は各々、水素原子、置換基を表し、Ｒ _１ 又はＲ _２ とＲ _１０３ 又はＲ _１０６ の間、Ｒ _１０３ とＲ _１０４ の間、またＲ _１０５ とＲ _１０６ の間は互いに結合して縮合環を形成してもよく、Ｒ _１０９ は、アルキル基、アリール基、複素環基、アシルアミノ基、アミノ基、シアノ基、カルボキシル基、アルコキシカルボニル基、カルバモイル基、アルコキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、ウレイド基またはアルコキシカルボニルアミノ基を表し、Ｒ _１１０ 、Ｒ _１１１ は置換されていてもよい脂肪族基、置換されていてもよい芳香族基、置換されていてもよい複素環基またはアシル基である。］
４．前記半導体表面が、金属酸化物もしくは金属硫化物半導体の表面であることを特徴とする前記１〜３のいずれか１項に記載の光電変換材料用半導体。
５．導電性支持体上に、前記１〜４のいずれか１項に記載の光電変換材料用半導体が設けられていることを特徴とする光電変換素子。
６．導電性支持体上に、前記１〜４のいずれか１項に記載の光電変換材料用半導体を含有する層が設けられた光電変換素子、電荷移動層及び対向電極を有することを特徴とする太陽電池。
なお、以下（１）〜（１２）については参考とされる構成である。 That is, the above object of the present invention is achieved by the following configurations 1 to 6 .
1. A compound for photoelectric conversion material, wherein a compound represented by the following general formula ( 2 ) is adsorbed on a semiconductor surface.

Wherein each R _1, R ₂ represent independently a hydrogen atom, an optionally substituted aliphatic group, an optionally substituted aromatic group, a heterocyclic group which may be substituted, also , R ₁ and R ₂ may be combined to form a nitrogen-containing heterocycle (due to the nonmetallic atom group). Cp is a 5-membered or 6-membered aromatic carbocyclic group or a heterocyclic group, to Table Wa an atomic group having a compound having at least one carboxyl group as a substituent. Each L ₁ ~ L ₃ represents a methine group which may be substituted, _{Z 1} and _{Z 2} are each an oxygen atom, a sulfur atom,> N-Ra group, Ra is _{R 1} and _{R 2} as defined And R _{3 to} R ₆ each represent a hydrogen atom or a substituent. Further, R ₃ and R ₄ or R ₅ and R ₆ may be bonded to each other to form a condensed ring. p represents an integer of 0 or 1, and q represents an integer of 1. ]
2. The photoelectric conversion material for semiconductor according to the 1, wherein Cp in formula (2), characterized in Rukoto represented by Cp-6.

[In the formula, B ₁ is a nitrogen atom or = CR ₂₃ group, B ₂ is a nitrogen atom or = CR ₂₄ group, B ₃ is a nitrogen atom or = CR ₂₅ group, B ₄ is a nitrogen atom or = It represents a _{C-R 26.} R _{23 to} R ₂₆ are each a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, acylamino group, alkane or arylsulfonylamino group, amino group, alkylthio group, arylthio group, alkoxy group, aryloxy group, It represents a ureido group, alkoxycarbonylamino group, carbamoyl group, sulfamoyl group, cyano group, carboxyl group, acyl group, aryloxycarbonyl group or alkoxycarbonyl group. ]
3. Under following general formula (4) or (5) at least one semiconductor for a photoelectric conversion material you characterized that you have been adsorbed on the semiconductor surface of the compound represented by.

Wherein each R _1, R ₂ represent independently a hydrogen atom, an optionally substituted aliphatic group, an optionally substituted aromatic group, a heterocyclic group which may be substituted, also , R ₁ and R ₂ may be combined to form a nitrogen-containing heterocycle (due to the nonmetallic atom group). R _{103 to} R ₁₀₈ each represent a hydrogen atom or a substituent , and are bonded to each other between R ₁ or R ₂ and R ₁₀₃ or R ₁₀₆ , between R ₁₀₃ and R ₁₀₄ , and between R ₁₀₅ and R _106. R ₁₀₉ may be an alkyl group, aryl group, heterocyclic group, acylamino group, amino group, cyano group, carboxyl group, alkoxycarbonyl group, carbamoyl group, alkoxy group, aryloxy group, Represents an alkylthio group, an arylthio group, a ureido group or an alkoxycarbonylamino group, and R ₁₁₀ and R ₁₁₁ are an optionally substituted aliphatic group, an optionally substituted aromatic group, and an optionally substituted heterocyclic ring. Group or an acyl group. ]
4). 4. The semiconductor for a photoelectric conversion material according to any one of 1 to 3 , wherein the semiconductor surface is a surface of a metal oxide or metal sulfide semiconductor.
5. 5. A photoelectric conversion element, wherein the semiconductor for a photoelectric conversion material according to any one of 1 to 4 is provided on a conductive support .
6). A solar comprising a photoelectric conversion element, a charge transfer layer, and a counter electrode provided with a layer containing the semiconductor for a photoelectric conversion material according to any one of 1 to 4 above on a conductive support. Battery .
In addition, the following (1) to (12) are configurations to be referred to.

(1 )
A compound for photoelectric conversion material, wherein a compound represented by the following general formula (1) is adsorbed on a semiconductor surface.

[Wherein, Ar ₁ and Ar ₂ each independently represent a divalent 5-membered or 6-membered aromatic carbocyclic group or heterocyclic group, and Cp has at least one carboxyl group as a substituent. The compound represented by the general formula (1) represents an atomic group capable of imparting absorption ability in the visible region or near infrared region, and R ₁ and R ₂ are each independently a hydrogen atom or an optionally substituted aliphatic group. A group, an aromatic group which may be substituted, and a heterocyclic group which may be substituted; Bonded between R ₁ and R _2, between atoms constituting R ₁ and Ar ₁ , or between atoms constituting R ₂ and Ar ₁ to form a nitrogen-containing heterocycle (depending on the nonmetallic atom group) May be. L ₁ , L ₂ and L ₃ each represent an optionally substituted methine group, m represents an integer of 0 to 2, and n represents an integer of 1 to 4. ]
(2 )
2. The semiconductor for a photoelectric conversion material according to 1 above, which is spectrally sensitized with the compound represented by the general formula (1).

(3 )
N of the said General formula (1) is 1, The semiconductor for photoelectric conversion materials as described in said ( 1 ) or ( 2 ) characterized by the above-mentioned .

(4 )
M of the said General formula (1) is 0 or 1, The semiconductor for photoelectric conversion materials as described in said ( 3 ) characterized by the above-mentioned .

(5 )
The photoelectric conversion material for semiconductor according to (1) to (4) wherein Ar ₂ in the general formula (1) is characterized in that it is a thienylene group.

(6 )
A compound for photoelectric conversion material, wherein a compound represented by the following general formula (2) is adsorbed on a semiconductor surface.

[Wherein R ₁ , R ₂ , L _{1 to} L ₃ and Cp are each a group defined in the general formula (1), and Z ₁ and Z ₂ are an oxygen atom, a sulfur atom, > N-Ra group, Ra is synonymous with R _{1 and} R ₂ , and R _{3 to} R ₆ each represent a hydrogen atom and a substituent. Further, R ₃ and R ₄ or R ₅ and R ₆ may be bonded to each other to form a condensed ring. p represents an integer of 0 or 1, and q represents an integer of 1. ]
(7 )
Cp of general formula (1) and (2) is represented by general formula Cp-3 or Cp-6, The photoelectric conversion material as described in any one of ( 1 ) to ( 6 ) above semiconductor.

[Wherein R ₂₁ represents an alkyl group, aryl group, heterocyclic group, acylamino group, amino group, cyano group, carboxyl group, alkoxycarbonyl group, carbamoyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, Represents a ureido group or an alkoxycarbonylamino group, and R ₂₂ represents an optionally substituted aliphatic group, an optionally substituted aromatic group, an optionally substituted heterocyclic group or an acyl group.

B ₁ is a nitrogen atom or = CR ₂₃ group, B ₂ is a nitrogen atom or = CR ₂₄ group, B ₃ is a nitrogen atom or = CR ₂₅ group, B ₄ is a nitrogen atom or = CR ₂₆ Represents. R _{23 to} R ₂₆ are each a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, acylamino group, alkane or arylsulfonylamino group, amino group, alkylthio group, arylthio group, alkoxy group, aryloxy group, It represents a ureido group, alkoxycarbonylamino group, carbamoyl group, sulfamoyl group, cyano group, carboxyl group, acyl group, aryloxycarbonyl group or alkoxycarbonyl group. ]
(8 )
A semiconductor for a photoelectric conversion material, wherein at least one compound represented by the following general formula (3) is adsorbed on a semiconductor surface.

[Wherein, R ₁ and R ₂ are groups defined in the general formula (1), R _{103 to} R ₁₀₈ each represent a hydrogen atom and a substituent, and R ₁ or R ₂ and R ₁₀₃ or R ₁₀₆ , R ₁₀₃ and R ₁₀₄ , or R ₁₀₅ and R ₁₀₆ may be bonded to each other to form a condensed ring, and R ₁₀₉ represents an alkyl group, an aryl group, or a heterocyclic group. Represents an acylamino group, an amino group, a cyano group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a ureido group or an alkoxycarbonylamino group, and R ₁₁₀ is substituted. An aliphatic group which may be substituted, an aromatic group which may be substituted, a heterocyclic group which may be substituted, or an acyl group. ]
(9 )
A semiconductor for a photoelectric conversion material, wherein at least one compound represented by the following general formula (4) or (5) is adsorbed on a semiconductor surface.

[Wherein R ₁ , R ₂ and R _{103 to} R ₁₁₀ are groups defined in the general formula (3), R ₁₁₁ is an optionally substituted aliphatic group, It may be an aromatic group, an optionally substituted heterocyclic group or an acyl group. ]
(10 )
The semiconductor surface for a photoelectric conversion material according to any one of ( 1 ) to ( 9 ) , wherein the semiconductor surface is a surface of a metal oxide or metal sulfide semiconductor.

(1 1)
The photoelectric conversion element characterized by providing the semiconductor for photoelectric conversion materials of any one of said ( 1 ) - ( 10 ) on the electroconductive support body.

(1 2)
It has a photoelectric conversion element provided with the layer containing the semiconductor for photoelectric conversion materials of any one of said ( 1 ) - ( 10 ) on the electroconductive support body, a charge-transfer layer, and a counter electrode. Solar cell featuring.

  By using the compound of the present invention, a photoelectric conversion element having high photoelectric conversion efficiency and excellent durability can be obtained, which is useful for various photoelectric conversion materials such as solar cells.

Next, the best mode for carrying out the present invention will be described, but the present invention is not limited thereto.
Although the semiconductor for photoelectric conversion materials of this invention, a photoelectric conversion element, and a solar cell are demonstrated using figures, this invention is not limited to this. In addition, the following description may include affirmative expressions for terms and the like, but it shows preferred examples of the present invention and limits the meaning and technical scope of the terms of the present invention. It is not a thing.

  FIG. 1 is a partial cross-sectional view showing an example of the structure of the photoelectric conversion element of the present invention.

  Reference numeral 1 denotes a conductive support. Reference numeral 2 denotes a layer containing a semiconductor for a photoelectric conversion material (hereinafter also referred to as a photosensitive layer). 3 is a charge transfer layer. Reference numeral 4 denotes a counter electrode. The conductive support 1 and the photosensitive layer 2 are also collectively referred to as a semiconductor electrode.

  The semiconductor for photoelectric conversion materials of the present invention is obtained by sensitizing a semiconductor by adsorbing at least one compound represented by the general formula (1) on the semiconductor.

In the general formula (1), the aliphatic groups represented by R ₁ and R ₂ each include an alkyl group, a cycloalkyl group, a bicycloalkyl group, an alkenyl group, and an alkynyl group. It may be substituted with a group.

The alkyl group represented by each of R ₁ and R ₂ is preferably a linear or branched alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Examples thereof include a tert-butyl group, an n-octyl group, an eicosyl group, a 2-chloroethyl group, a 2-cyanoethyl group, and a 2-ethylhexyl group.

The cycloalkyl group represented by each of R ₁ and R ₂ is preferably a cycloalkyl group having 3 to 30 carbon atoms, and examples thereof include a cyclohexyl group, a cyclopentyl group, and a 4-n-dodecylcyclohexyl group.

The bicycloalkyl group represented by each of R ₁ and R ₂ is preferably a C 5-30 bicycloalkyl group. Here, the bicycloalkyl group according to the present invention is a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, specifically, bicyclo [1,2,2] heptane- A 2-yl group, a bicyclo [2,2,2] octane-3-yl group, and the like can be given.

The alkenyl group represented by each of R ₁ and R ₂ is preferably an alkenyl group having 2 to 30 carbon atoms, and examples thereof include ethenyl group, allyl group, 2-pentenyl group, 2-ethylbutenyl group and the like, and alkynyl As a group, a C2-C30 alkynyl group is preferable, for example, an ethynyl group, 2-butynyl group, etc. are mentioned.

The aromatic group represented by each of R ₁ and R ₂ is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, p-tolyl group, naphthyl group, m-chlorophenyl group, o -Hexadecanoylaminophenyl group etc. are mentioned.

The heterocyclic group represented by each of R ₁ and R ₂ is a substituted or unsubstituted group such as pyridyl group, thiazolyl group, 2-benzothiazolyl group, oxazolyl group, imidazolyl group, 2-furyl group, 2- Examples include thienyl group, pyrrolyl group, pyrazinyl group, 2-pyrimidinyl group, pyridazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group, and tetrazolyl group.

Examples of the group substituted by the alkyl group, cycloalkyl group, bicycloalkyl group, aromatic group, and heterocyclic group represented by R ₁ and R ₂ include an alkyl group (for example, methyl group, ethyl group, propyl group). Group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (for example, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc.) , Bicycloalkyl groups (for example, bicyclo [1,2,2] heptan-2-yl group, bicyclo [2,2,2] octane-3-yl group, etc.), alkenyl groups (for example, vinyl group, allyl group, Butenyl group, octenyl group, etc.), cycloalkenyl group (for example, 2-cyclopenten-1-yl group, 2-cyclohexene group) Sen-1-yl group, etc.), bicycloalkenyl group (for example, bicyclo [2,2,1] hept-2-en-1-yl group, bicyclo [2,2,2] oct-2-ene-4- Yl group), alkynyl group (eg, propargyl group, ethynyl group, trimethylsilylethynyl group, etc.), aryl group (eg, phenyl group, naphthyl group, p-tolyl group, m-chlorophenyl group, o-hexadecanoylaminophenyl). Group), heterocyclic group (for example, pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group) Group, morpholino group, etc.), heterocyclic oxy group (for example, 1-phenyltetrazol-5-oxy Group, 2-tetrahydropyranyloxy group, pyridyloxy group, thiazolyloxy group, oxazolyloxy group, imidazolyloxy group, etc.), halogen atom (eg, chlorine atom, bromine atom, iodine atom, fluorine atom), alkoxy group (For example, methoxy group, ethoxy group, propyloxy group, tert-butoxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group, etc.) ), Aryloxy groups (for example, phenoxy group, naphthyloxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group, etc.), alkylthio groups (for example, , Methylthio group, ethylthio Group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), heterocyclic ring Thio group (eg, pyridylthio group, thiazolylthio group, oxazolylthio group, imidazolylthio group, furylthio group, pyrrolylthio group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, dodecyl) Oxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfonyl group, methyl group) Nosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, Morpholinosulfonyl group, pyrrolidinosulfonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2 -Pyridylaminoureido group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group) Octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyl group) Oxy group, p-methoxyphenylcarbonyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), acylamino group (for example, acetylamino group, benzoylamino group) , Formylamino group, pivaloylamino group, lauroylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group, etc.), carbamoyl group (for example, amino Carbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, Naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, morpholinocarbonyl group, piperazinocarbonyl group, etc.), alkanesulfinyl group or arylsulfinyl group (for example, methanesulfinyl group, ethanesulfinyl group, butanesulfinyl group, cyclohexanesulfinyl group, 2-ethylhexanesulfinyl group, dodecanesulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridine Rusulfinyl group, etc.), alkanesulfonyl group or arylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group, butanesulfonyl group, cyclohexanesulfonyl group, 2-ethylhexanesulfonyl group, dodecanesulfonyl group, phenylsulfonyl group, naphthylsulfonyl group) 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, methylamino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, N-methylanilino group, diphenylamino group, naphthylamino group, 2-pyridylamino group, etc.), silyloxy group (for example, trimethylsilyloxy group, tert-butyldimethylsilyloxy group, etc.), aminocarbonyl Oxy group (for example, N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group) Etc.), alkoxycarbonyloxy groups (for example, methoxycarbonyloxy group, ethoxycarbonyloxy group, tert-butoxycarbonyloxy group, n-octylcarbonyloxy group, etc.), aryloxycarbonyloxy groups (for example, phenoxycarbonyloxy group, p -Methoxyphenoxycarbonyloxy group, pn-hexadecyloxyphenoxycarbonyloxy group, etc.), alkoxycarbonylamino group (for example, methoxycarbonylamino group, ethoxycarbonylamino group, tert-but Sicarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group, etc.), aryloxycarbonylamino group (for example, phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyl) Oxyphenoxycarbonylamino group, etc.), sulfamoylamino group (eg, sulfamoylamino group, N, N-dimethylaminosulfonylamino group, Nn-octylaminosulfonylamino group, etc.), mercapto group, arylazo group ( For example, phenylazo group, naphthylazo group, p-chlorophenylazo group, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group, etc., heterocyclic azo group (for example, pyridylazo group, thiazolylazo group, oxazolylazo group, imidazo Ruazo group, furylazo group, pyrrolylazo group), imino group (for example, N-succinimido-1-yl group, N-phthalimido-1-yl group, etc.), phosphino group (for example, dimethylphosphino group, diphenylphosphino group, Methylphenoxyphosphino group), phosphinyl group (for example, phosphinyl group, dioctyloxyphosphinyl group, diethoxyphosphinyl group, etc.), phosphinyloxy group (for example, diphenoxyphosphinyloxy group, dioctyloxy) Phosphinyloxy group, etc.), phosphinylamino group (eg, dimethoxyphosphinylamino group, dimethylaminophosphinylamino group, etc.), silyl group (eg, trimethylsilyl group, tert-butyldimethylsilyl group, phenyldimethyl) Silyl group, etc.), cyano group, nitro group, hydro A xyl group, a sulfo group, a carboxyl group, etc. are mentioned.

  These substituents may be further substituted with the substituents shown above.

R ₁ and R ₂ are preferably a hydrogen atom or an aliphatic group, more preferably a hydrogen atom or an alkyl group, and particularly preferably an alkyl group having 1 to 18 carbon atoms.
A nitrogen-containing heterocycle may be formed by bonding between R ₁ and R _2, between atoms constituting R ₁ and Ar ₁ (described later), and between atoms constituting R ₂ and Ar _1. The nitrogen-containing heterocycle may be substituted with the substituent shown above or may be further condensed with another ring structure.

The divalent 5-membered or 6-membered aromatic carbocyclic ring independently represented by Ar ₁ and Ar ₂ may be a monocyclic ring or a condensed ring, such as a benzene ring, a naphthalene ring, an indene ring, a tetralin ring, Anthracene ring, phenanthrene ring and the like are mentioned, and the 5-membered or 6-membered heterocyclic ring may be a monocyclic ring or a condensed ring, and is an aromatic heterocyclic ring (for example, furan ring, pyrrole ring, pyrazole ring, imidazole ring, oxazole ring, Thiazole ring, 1,2,3-oxadiazole ring, 1,2,3-triazole ring, 1,2,4-triazole ring, 1,3,4-thiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, Pyrazine ring, s-triazine ring, benzofuran ring, indole ring, benzothiophene ring, benzimidazole ring, benzothiazole ring, purine ring, quinoline ring and iso Quinoline ring, etc.).

Preferred ring groups represented by Ar ₁ and Ar ₂ are heterocyclic groups, and more preferred ring groups are a thiophene ring group and a furan ring group.

These rings may have an arbitrary substituent at an arbitrary position, and examples of the substituent include the groups defined in the above R ₁ and R _2. Preferred are each a hydrogen atom, A halogen atom, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, and an alkoxy group, more preferably a hydrogen atom, a substituted or unsubstituted alkyl group, and an alkoxy group.

Examples of the substituent of the optionally substituted methine group represented by L _{1 to} L ₃ include linear, branched and cyclic alkyl groups (eg, methyl group, ethyl group, isopropyl group, cyclopropyl group, cyclohexyl group, etc. ), An optionally substituted aryl group (for example, phenyl group, p-tolyl group, p-cyanophenyl group, etc.), aralkyl group (for example, benzyl group, phenethyl group, etc.), alkoxy group (for example, methoxy group, Ethoxy group etc.), aryloxy group (eg phenoxy group, o-methoxyphenoxy group etc.), heterocyclic group (eg tetrahydrofuryl group, furyl group, thienyl group etc.), and the like between L ₁ and L ₃ Can also form a 5- or 6-membered ring.

  As Cp which is an atomic group which can provide the compound represented by the general formula (1) with absorption ability in the visible region or the near infrared region, the following general formula (Cp-1) to the following general formula (Cp-32) An atomic group represented by (partial structure) is preferably used. However, Cp according to the present invention is not limited by these.

  Here, the atomic groups represented by (Cp-1) to (Cp-32) are bonded to the conjugated methine group of the general formula (1) at the position of the * mark.

  Hereinafter, the compounds represented by the general formulas (Cp-1) to (Cp-32) will be described in detail.

<< General Formula (Cp-1) >>
In the general formula (Cp-1), R ₁₁ has the same meaning as the groups represented by R ₁ and R ₂ in the general formula (1), and R ₁₂ represents a carboxyalkyl group, an acyl group, an alkane or an arylsulfonyl. Represents a group, a carbamoyl group or a cyano group.

Here, the group represented by R ₁₁ is preferably a tert-butyl group, a 1-ethylcyclopropyl group, a 1-methylcyclopropyl group, a 1-benzylcyclopropyl group, a phenyl group, an indolinin-1-yl group, Groups such as indol-3-yl group and hydroxyl group, and the group represented by R ₁₂ is preferably a carboxyl group-substituted benzenesulfonyl group, a carboxyl group-substituted phenylcarbamoyl group, or a cyano group.

<< General Formula (Cp-2) >>
In formula (Cp-2) Te at, R ₁₂ has the same meaning as R ₁₂ in the general formula ((Cp-1), R 13 represents an aryl group or a heterocyclic group, preferably a heterocyclic group, Specific examples include thiazol-2-yl group, benzothiazol-2-yl group, oxazol-2-yl group, benzoxazol-2-yl group, 1,2,4-oxadiazole-3 (or 5). -Yl group, 1,3,4-oxadiazol-2 (or 5) -yl group, 1,2,4-thiadiazol-3 (or 5) -yl group, 1,3,4-thiadiazole-2 ( Or 5) -yl group, pyrazol-3-yl group, indazol-3-yl group, 1,2,4-triazol-3-yl group, 2-pyridyl group, 2-pyrimidinyl group, 2-pyrazinyl group, quinazoline 2-yl group, quinazoline-4-y Group, and the like.

<< General Formula (Cp-3) to General Formula (Cp-5) >>
In general formula (Cp-3) to general formula (Cp-5), l represents an integer of 0 to 2, and A ₁ and A ₂ are each an oxygen atom, a sulfur atom, or a> N-Ra group (Ra Represents the same as the groups represented by R ₁ and R ₂ in the general formula (1), and V ₁ represents an oxygen atom, a sulfur atom, a> N—Ra group or a ═C (Q ₁ , Q ₂ ) group ( Q ₁ and Q ₂ each represents an acyl group, a cyano group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, an alkane or an arylsulfonyl group, and specific examples include an acetyl group, a benzoyl group, an ethoxycarbonyl group, a butoxycarbonyl group, And a methanesulfonyl group, a butanesulfonyl group, a benzenesulfonyl group, a toluenesulfonyl group, etc. provided that any _one of Q ₁ and Q ₂ is an acyl group, a cyano group, an alkoxycarbonyl group, a carbamoyl. Or a group selected from the group consisting of an alkane and an arylsulfonyl group.

R ₂₁ represents an alkyl group, aryl group, heterocyclic group, acylamino group, amino group, cyano group, carboxyl group, alkoxycarbonyl group, carbamoyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, ureido group or alkoxy group. Represents a carbonylamino group, and R ₂₂ represents an optionally substituted aliphatic group, an optionally substituted aromatic group, an optionally substituted heterocyclic group or an acyl group.

Here, the group represented by R ₂₁ preferably includes an alkyl group, an acylamino group, an amino group, a carboxyl group, a ureido group, an alkoxycarbonylamino group, and more preferably a substituted alkyl group. , An acylamino group and an anilino group, and specific examples include a carboxyl group, a trifluoromethyl group, an m-carboxybenzoylamino group, a p-carboxyanilino group, and the like.

Preferred examples of the group represented by R ₂₂ include a carboxyl group-substituted alkyl group and a carboxyl group-substituted aryl group. Specific examples include a carboxymethyl group, a p-carboxyphenyl group, an m-carboxyphenyl group, 3, 5 -A dicarboxyphenyl group etc. are mentioned.

<< General Formula (Cp-6) to General Formula (Cp-12) >>
In general formula (Cp-6) to general formula (Cp-12), B ₁ is a nitrogen atom or ═C—R ₂₃ group, B ₂ is a nitrogen atom or ═C—R ₂₄ group, and B ₃ is a nitrogen atom or ═C—R ₂₅ group, B ₄ represents a nitrogen atom or ═C—R ₂₆ , and B ₅ represents a nitrogen atom or ═C—R ₂₇ group. R _{23 to} R ₂₈ are each a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, acylamino group, alkane or arylsulfonylamino group, amino group, alkylthio group, arylthio group, alkoxy group, aryloxy group, It represents a ureido group, alkoxycarbonylamino group, carbamoyl group, sulfamoyl group, cyano group, carboxyl group, acyl group, aryloxycarbonyl group or alkoxycarbonyl group. Here, each of the groups represented by R _{23 to} R ₂₈ is preferably a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a carboxyl group, an alkoxy group, a carbamoyl group, a cyano group, an alkoxycarbonyl group, or an acyl group. Can be mentioned.

<< General Formula (Cp-13), General Formula (Cp-14) >>
In the general formula (Cp-13) and (Cp-14), R _{31 to} R ₃₅ are each a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acylamino group, an alkane or an arylsulfonylamino group, An amino group, an alkylthio group, an arylthio group, an alkoxy group, an aryloxy group, a ureido group, an alkoxycarbonylamino group, an acyl group, an alkoxycarbonyl group or a carbamoyl group, a carboxyl group, preferably a hydrogen atom, an alkyl group, an aryl group A heterocyclic group, an acylamino group, an alkane or arylsulfonylamino group, and a carboxyl group.

<< General formula (Cp-15) >>
In the general formula (Cp-15), D represents an oxygen atom or> N-Ra group (Ra is the same as defined in the general formula (Cp-5)). R ₃₇ and R ₃₈ are each a hydrogen atom, alkyl group, aryl group, heterocyclic group, acylamino group, alkane or arylsulfonylamino group, amino group, alkylthio group, arylthio group, alkoxy group, aryloxy group, ureido group, An alkoxycarbonylamino group, an acyl group, an alkoxycarbonyl group, a carbamoyl group or a cyano group is represented. Here, R ₃₇ and R ₃₈ are preferably a hydrogen atom, an aryl group, a heterocyclic group, an acylamino group, an alkane or arylsulfonylamino group, a carbamoyl group, a cyano group, or the like.

<< General Formula (Cp-16) to General Formula (Cp-19) >>
In the general formula (Cp-16) to general formula (Cp-19), R ₄₁ , R ₄₈ , R ₄₉ and R ₅₀ are each a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a carbamoyl group, an alkoxy group. Carbonyl, aryloxycarbonyl, cyano, acylamino, ureido, alkoxycarbonylamino, sulfamoyl, alkane or arylsulfonyl, nitro, halogen, carboxyl, amino, alkylthio, arylthio, alkoxy Represents a group or an aryloxy group.

R ₄₆ includes the substituents defined in R ₁ and R ₂ in the general formula (1), and R ₄₇ has the same meaning as the groups represented by R ₁ and R ₂ in the general formula (1). is there.

Here, the group represented by R ₄₁ is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a carbamoyl group, an alkoxycarbonyl group, a cyano group, a carboxyl group, or the like, specifically, methyl, tert-butyl, Examples include dodecyl, benzyl, phenyl, m-carboxyphenyl, p-chlorophenyl, thienyl, 2-thiazolyl, furyl, pyrrolyl, carbamoyl, morpholinocarbonyl, methoxycarbonyl, butoxycarbonyl, and the like, and R ₄₈ , R ₄₉ , The group represented by each R ₅₀ is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, a cyano group, a halogen atom, a carboxyl group, an alkoxycarbonyl group, an amino group, etc. For chlorine, bromine, iodine, methyl, ethyl, hexyl, allyl p-carboxybenzyl, phenyl, 3-bromophenyl, 4-carboxyphenyl, pyrrolidyl, piperidyl, thienyl, pyridyl, imidazolyl, methoxycarbonyl, N, N-tetramethyleneamino, N-butylamino N, N-diphenylamino, etc. Examples of the group represented by R ₄₆ include a halogen atom, alkyl group, aryl group, heterocyclic group, acylamino group, alkane or arylsulfonyl group, amino group, alkylthio group, arylthio group, alkoxy group, aryl An oxy group, a carboxyl group, a carbamoyl group, a sulfamoyl group, a ureido group, or an alkoxycarbonylamino group is preferable. Specifically, a chlorine atom, a bromine atom, an iodine atom, methyl, ethyl, hexyl, allyl, phenyl, 3-bromophenyl , 4-cal Boxyphenyl, thienyl, pyridyl, imidazolyl, acetylamino, benzoylamino, methanesulfonyl, butanesulfonyl, toluenesulfonyl, 4-chlorobenzenesulfonyl, methylthio, phenylthio, methoxyphenylthio, methoxy, butoxy, 2-methoxyethoxy, 3,6-di Examples include oxaheptyloxy, phenoxy, p-carboxyphenoxy, p-methoxyphenoxy, carbamoyl, N-methylcarbamoyl, sulfamoyl, morpholinosulfonyl, 3-methylureido, methoxycarbonylamino, and the like represented by R47. The group is preferably a hydrogen atom, a substituted or unsubstituted aliphatic group, or an aryl group, and specifically, methyl, ethyl, allyl, 3-carboxyallyl, benzyl, phenyl, 3,4-di Rorofeniru include the group such 4-carboxyphenyl. a represents an integer of 0 to 3, and when a is plural, a plurality of R ₄₆ may be the same or different.

<< General Formula (Cp-20) to General Formula (Cp-23) >>
In the general formula (Cp-20) to general formula (Cp-23), E represents a nitrogen atom or a methine carbon, and R ₅₁ represents an alkyl group, an aryl group, a heterocyclic group, an amino group, an alkoxy group, or Represents an aryloxy group, R ₄₆ has the same definition as in formula (Cp-16), and R ₅₂ represents a hydrogen atom, a carbamoyl group, an alkoxycarbonyl group, a carboxyl group, a cyano group, a sulfamoyl group, an acylamino group, or a ureido. A group, an alkoxycarbonylamino group, or an alkane or arylsulfonylamino group, R ₅₃ and R ₅₄ each represent a hydrogen atom or an alkyl group, b represents an integer of 0 to 3, and c represents 0 to 2 And d represents any integer of 0 to 4. When b, c or d is plural, a plurality of R ₄₆ may be the same or different.

Here, the group represented by R ₅₁ is preferably an alkyl group or an aryl group, and the group represented by R ₅₂ is preferably an alkoxycarbonyl group, a carboxyl group, a carbamoyl group, a sulfamoyl group, or an acylamino group. The group represented by each of R ₅₃ and R ₅₄ is preferably a hydrogen atom, a methyl group, or an ethyl group. Preferably, b represents 1 or 2, c represents 1 or 2, and d represents an integer of 0 to 2.

<< General Formula (Cp-24), General Formula (Cp-25) >>
In general formula (Cp-24) and general formula (Cp-25), R _{46 and} d are the same as defined in general formula (Cp-22). R ₅₅ and R ₅₆ each have the same meaning as the group represented by R ₅₂ in Formula (Cp-22).

W ₁ and W ₂ each represent a cyano group, a sulfamoyl group, an alkane or arylsulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group.

Here, the groups represented by R ₅₅ and R ₅₆ are each preferably a halogen atom, an alkyl group or an aryl group, and the groups represented by W ₁ and W ₂ are each preferably a cyano group. e represents an integer of 1 or 2.

<< General Formula (Cp-26) to General Formula (Cp-28) >>
In the general formula (Cp-26) to general formula (Cp-28), R ₅₇ and R ₅₈ have the same meanings as R ₅₅ and R ₅₆ in the general formula (Cp-24), and R ₅₉ represents the general formula (Cp −16) is the same as the group represented by R ₄₁ , and R _{46 and} d are the same as defined in the general formula (Cp-22).

G is an oxygen atom or> N-Ra group (Ra is the same as defined in the general formula (Cp-5)), Z ₃ represents a nonmetallic atom group necessary for forming a condensed ring, specifically, Is a cyclohexene ring, cyclopentene ring, benzene ring, naphthalene ring, indane ring, etc. 5-membered, 6-membered non-aromatic or aromatic carbocyclic ring, pyrroline ring, pyran ring, thiopyran ring, furan ring, pyrrole ring, thiophene Examples thereof include 5-membered and 6-membered non-aromatic or aromatic heterocycles such as a ring, a pyridine ring, an indole ring, a benzothiophene ring, and a benzofuran ring. E represents an integer of 1 or 2.

<< General Formula (Cp-29), General Formula (Cp-30) >>
In general formula (Cp-29) and general formula (Cp-30), Z ₃ has the same definition as in general formula (Cp-27), and R ₄₇ represents the general formula (Cp-18, 19). And R ₆₀ represents a hydrogen atom, an alkyl group, a carbamoyl group, an acylamino group, or an alkoxycarbonyl group. Specific examples include groups such as methyl, ethyl, acetylamino, methoxycarbonyl, and the like. Is an oxygen atom, sulfur atom, selenium atom, tellurium atom,> N-Ra group (Ra is the same as defined in the general formula (Cp-5)),> CRb (Rc) (Rb and Rc are each independently Represents the same as the groups represented by R ₅₃ and R ₅₄ in formula (Cp-23).

Here, the group represented by R ₆₀ is preferably a hydrogen atom.

<< General formula (Cp-31) >>
In the general formula (Cp-31), R _{62 to} R ₆₄ each represents a hydrogen atom, a cyano group, a sulfamoyl group, an alkane or an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group, and R ₆₁ represents Represents an amino group, an alkylthio group, an arylthio group, an alkoxy group or an aryloxy group.

Here, the groups represented by R _{62 to} R ₆₄ are each preferably a hydrogen atom, a cyano group or the like, and the group represented by R ₆₁ is preferably an N-arylamino group.

<< General Formula (Cp-32) >>
In the general formula (Cp-32), R ₆₅ and R ₆₆ are each a hydrogen atom, a perfluoroalkyl group, a cyano group, a nitro group, a sulfamoyl group, an alkanesulfonyl group, an arylsulfonyl group, an acyl group, or an alkoxycarbonyl group. Represents a carbamoyl group, an alkylthio group, or an arylthio group, and R ₆₇ represents an alkyl group, an aryl group, a heterocyclic group, a sulfamoyl group, an alkanesulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group.

Here, the groups represented by R ₆₅ and R ₆₆ preferably include a hydrogen atom, a perfluoroalkyl group, a cyano group, a nitro group, an alkane or arylsulfonyl group, an alkylthio group, an arylthio group, and the like. , R ₆₇ is preferably an aryl group, a heterocyclic group or the like.

  Among Cp according to the present invention, among the groups represented by the above general formulas (Cp-1) to (Cp-32), general formulas (Cp-3), (Cp-4), (Cp-5), (Cp-6), (Cp-7), (Cp-8), (Cp-9), (Cp-10), (Cp-11), (Cp-12), (Cp-16), (Cp -17), (Cp-18), (Cp-19), (Cp-20), (Cp-21), (Cp-22), (Cp-23), (Cp-24), (Cp-25) ), (Cp-26), (Cp-28), and (Cp-30) are preferred. More preferably, it is general formula (Cp-3) or (Cp-6).

  Specific examples of the structure represented by Cp according to the present invention in the present invention are shown below, but are not limited to these exemplified compounds as long as they do not exceed the gist of the invention described in the claims. In addition, * has shown the coupling | bonding position.

  Particularly preferred structures in the general formula (1) are represented by the general formulas (2) to (5).

  The general formula (2) will be described.

In the general formula (2), R ₁ , R ₂ , L _{1 to} L ₃ and Cp are each a group defined in the general formula (1), and Z ₁ and Z ₂ are each an oxygen atom, A sulfur atom and a> N-Ra group are represented, Ra is synonymous with R _{1 and} R ₂ , and R _{3 to} R ₆ each represents a hydrogen atom and a substituent. Further, they may be bonded to each other between R ₃ and R ₄ or R ₅ and R ₆ to form a condensed ring. p represents an integer of 0 or 1, and q represents an integer of 1.

Examples of the substituent represented by R _{3 to} R ₆ in the general formula (2) include groups defined in R ₁ and R ₂ in the general formula (1), and R ₃ and R ₄ Or a fused ring formed by bonding between R ₅ and R ₆ as a 5-membered to 7-membered carbon ring (for example, benzofuran ring, tetrahydrobenzofuran ring, benzothiophene ring, naphththiophene ring, indole ring) Etc.) 5-membered and 6-membered heterocycles (for example, thienothiophene ring, pyridinofuran ring, pyrrolothiophene ring, pyrrolopyrrole ring, etc.).

  The compounds of the general formulas (1) and (2) in the present invention include ions and salts derived from the compounds in addition to the compounds themselves represented by the general formulas (1) and (2).

  For example, when the compound of the general formula (1) has a sulfonic acid group in the molecular structure, in addition to the compound, an anion generated by dissociation of the sulfonic acid group and an anion and a counter cation Including the salt formed.

  Such a salt may be a salt formed with a metal ion such as sodium salt, potassium salt, magnesium salt or calcium salt, or an organic base such as pyridine, piperidine, triethylamine, aniline or diazabicycloundecene. It may be the salt formed. Similarly, in the case of a compound having a basic group in the molecule, an acid such as a cation and a hydrochloride, sulfate, acetate, methylsulfonate, p-toluenesulfonate, etc. produced by protonating the compound And the formed salt.

  Next, the general formula (3) will be described.

In the formula, R ₁ and R ₂ are groups defined in the general formula (1), and R _{103 to} R ₁₀₈ each represent a hydrogen atom and a substituent, each represented by R _{103 to} R _108. Examples of the substituent include the groups defined in R ₁ and R ₂ in the general formula (1). Further, R ₁ and R ₂ may be bonded to form a condensed ring, and for example, a morpholine ring, piperidine ring, pyrrolidine ring, or the like may be formed. In addition, a fused ring may be formed by bonding between R ₁ or R ₂ and R ₁₀₃ or R ₁₀₆ , or between R ₁₀₃ and R ₁₀₄ , or between R ₁₀₅ and R ₁₀₆ , such as a piperazine ring, A pyrrolidine ring or the like, or a ring formed by R ₁ and R ₁₀₆ and R ₂ and R ₁₀₃ may form a julolidine ring or the like.

R ₁₀₉ is an alkyl group, aryl group, heterocyclic group, acylamino group, amino group, cyano group, carboxyl group, alkoxycarbonyl group, carbamoyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, ureido group or alkoxy group. Represents a carbonylamino group, preferably an alkyl group, an aryl group, or a carboxyl group, and most preferably a carboxyl group.

R ₁₁₀ is an optionally substituted aliphatic group, an optionally substituted aromatic group, an optionally substituted heterocyclic group or an acyl group. Examples of the substituent include those shown in the general formula (1), and most preferably an aromatic group which may be substituted.

  Next, general formulas (4) and (5) will be described.

R ₁ , R ₂ and R _{103 to} R ₁₁₀ are groups defined in the general formula (3), and preferred groups are also the same.

R ₁₁₁ is an optionally substituted aliphatic group, an optionally substituted aromatic group, an optionally substituted heterocyclic group or an acyl group. Examples of the substituent include those shown in the general formula (1), and preferred are an aliphatic group and an aromatic group which may be substituted.

  The terminal bis-pentakis (hetero) aryl group partial structure (CD) represented by the general formulas (1) and (2) in the present invention is shown below.

Specific examples of these are shown below, but are not limited to these exemplified compounds as long as they do not exceed the gist of the invention described in the claims. These are bonded to the methine group represented by L ₁ , L ₂ , or L ₃ at the position indicated by *.

Specific examples of the compounds represented by the general formulas (1) to (5) in the present invention are shown below, but the content of the present invention is exemplified as long as the gist of the invention described in the claims is not exceeded. It is not limited to compounds. Cp, L ₁ , L ₂ , L ₃ , and CD each represent the above partial structure, and CD and Cp are located at the position indicated by * via a methine group represented by L ₁ , L ₂ , or L _3. Are combined.

  The above-mentioned compounds of the present invention are described in, for example, “Myanine Soybean and Relayed Compounds” (1964, published by Inter Science Publishers) by F.M. Org. Chem. 61, 242-22246 (1996). Heterocycles, 31, 11, 1951-1958 (1990). , J .; Chem. Soc. , 2512-2517 (1957). Can be synthesized with reference to conventionally known methods described in US Pat. Nos. 2,454,629, 2,493,748, and JP-A-6-301136.

  As an example, a method for synthesizing a specific compound of the present invention will be described below. However, other compounds can be synthesized in the same manner and are not limited thereto.

Synthesis example 1
Exemplified Compound No. Synthesis of 34 1) Synthesis route

0.59 g of intermediate 1 in 15 ml of toluene; Org. Chem. 61, 242-22246 (1996). 0.8 g of the oligothiophene derivative (intermediate 2) synthesized by the method described in 1) was added, 0.26 g of morpholine was added, and the mixture was heated to reflux for 2 hours. Toluene was concentrated and distilled off under reduced pressure, and a small amount of methanol was added to the resulting residue to cause crystallization. 0.91 g of the crude product was recrystallized from 6 ml of acetonitrile to obtain 0.5 g of the desired product. The product was identified by MASS, ¹ H-NMR, and IR spectrum, and confirmed to be the target product.

Synthesis example 2
Exemplified Compound No. Synthesis of 36

30 ml of toluene and 1.20 g of intermediate 3 Org. Chem. , 60, 2082-2091 (1995). 1.42 g of the oligothiophene derivative (intermediate 4) synthesized by the method described in 1) was added, 0.42 g of morpholine was added, and the mixture was heated to reflux for 2 hours. Toluene was concentrated and distilled off under reduced pressure, and a small amount of methanol was added to the resulting residue to cause crystallization. The crude product (1.7 g) was recrystallized from 20 ml of acetonitrile to obtain 1.13 g of the desired product. The product was identified by MASS, ¹ H-NMR, and IR spectrum, and confirmed to be the target product.

Synthesis example 3
Exemplified Compound No. Synthesis of 164

(1) Synthesis of Intermediate 6 Heterocycles, 31, 11, 1951-1958 (1990). J. et al. Chem. Soc. , 2512-2517 (1957). Intermediate 5 synthesized with reference to the above was dissolved in a mixed solution of 80 ml of methanol, 40 ml of tetrahydrofuran and 40 ml of N, N-dimethylformamide (hereinafter abbreviated as DMF), and 1.10 g of Pd / C catalyst was dissolved. In addition, reduction was performed with hydrogen. After confirming the completion of the reaction, the catalyst was removed by filtration and concentrated.

After 30 ml of ethanol and 5 ml of water were added to this viscous oil and dissolved, 2.36 g of potassium carbonate was added with stirring, 6.90 g of butyl iodide was further added, and the mixture was heated to reflux for 5 hours. Column purification with an ethyl acetate / n-hexane mixed system yielded 3.1 g of Intermediate 6. The product was identified by MASS, ¹ H-NMR, and IR spectrum, and confirmed to be the target product.

(2) Synthesis of Intermediate 7 Intermediate 8 is dissolved in 2.85 g and DMF 13 ml, cooled to 5 ° C., and 1.82 g of phosphorus oxychloride is gradually added at an internal temperature of 15 ° C. or lower. After completion of the addition, the temperature was raised to room temperature, and further reacted at 85 to 90 ° C. for 2 hours. This reaction solution is dropped into warm water at 60 ° C., an aqueous solution in which 1.3 g of sodium acetate is dissolved in 10 ml of water is added, and reacted at 60 ° C. for 1 hour. When the reaction was cooled, crystals were precipitated, which was filtered to obtain 2.2 g of Intermediate 7. The product was identified by MASS, ¹ H-NMR, and IR spectrum, and confirmed to be the target product.

(3) Exemplified Compound No. Synthesis of 164 To 30 ml of toluene, 0.61 g of Intermediate 8 and 1.04 g of Intermediate 7 were weighed, 0.29 g of morpholine was added, and the mixture was heated to reflux for 2 hours. Toluene was concentrated and evaporated under reduced pressure, and the resulting residue was purified by column using an ethyl acetate / n-hexane mixed system to obtain 1.15 g of the desired product. The product was identified by MASS, ¹ H-NMR, and IR spectrum, and confirmed to be the target product.

Synthesis example 4
Exemplified Compound No. Synthesis of 184

To 30 ml of toluene, 0.89 g of Intermediate 3 and 1.04 g of Intermediate 7 were weighed, morpholine: 0.29 g was added, and the mixture was heated to reflux for 2 hours. The mixture was cooled as it was, and the precipitated crystals were collected by filtration and recrystallized with a methanol / acetonitrile mixed solvent to obtain 1.02 g of the desired product. The product was identified by MASS, ¹ H-NMR, and IR spectrum, and confirmed to be the target product.

<< Sensitivity treatment of semiconductor for photoelectric conversion material >>
The semiconductor for photoelectric conversion materials of the present invention is sensitized by including any one compound represented by the general formulas (1) to (5), and can exhibit the effects described in the present invention. Become. Here, including the compound includes various modes such as adsorption to the semiconductor surface, and when the semiconductor has a porous structure such as a porous structure, the compound enters the porous structure of the semiconductor.

The total content of each compound represented by the general formulas (1) to (5) per 1 m ² of the semiconductor layer (which may be a semiconductor) is preferably in the range of 0.01 mmol to 100 mmol, and more preferably. Is from 0.1 to 50 mmol, particularly preferably from 0.5 to 20 mmol.

  When performing sensitization using any one of the compounds represented by the general formulas (1) to (5) according to the present invention, the compounds may be used alone or in combination. Any one of the compounds represented by the general formulas (1) to (5) according to the present invention and other compounds (for example, U.S. Pat. Nos. 4,684,537, 4,927, No. 721, No. 5,084,365, No. 5,350,644, No. 5,463,057, No. 5,525,440, etc. The compounds described in each specification, JP-A-7-249790, JP-A-2000-150007, and the like can also be used as a mixture.

  In particular, when the application of the semiconductor for photoelectric conversion material of the present invention is a solar cell described later, two types of absorption wavelengths are different so that the wavelength range of photoelectric conversion can be made as wide as possible to effectively use sunlight. It is preferable to use a mixture of the above dyes.

  In order to include any one compound represented by the general formulas (1) to (5) in the semiconductor, the compound was dissolved in an appropriate solvent (such as ethanol) and dried well in the solution. A method of immersing a semiconductor for a long time is common.

  When producing a semiconductor for a photoelectric conversion material using a combination of any one of the compounds represented by the general formulas (1) to (5) or another sensitizing dye compound, A mixed solution of these compounds may be prepared and used. Alternatively, a solution may be prepared for each compound and immersed in each solution in order. When preparing a separate solution for each compound and immersing in each solution in order, the effects described in the present invention can be obtained regardless of the order in which the semiconductor, the sensitizing dye, and the like are included in the semiconductor. be able to. Moreover, you may produce by mixing the semiconductor fine particle which adsorb | sucked the said compound independently.

  The adsorption treatment may be performed when the semiconductor is in the form of particles, or may be performed after forming a film on the support. The solution in which the compound used for the adsorption treatment is dissolved may be used at room temperature, or may be used by heating in a temperature range in which the compound does not decompose and the solution does not boil. Moreover, you may implement adsorption | suction of the said compound after application | coating of a semiconductor fine particle (after formation of a photosensitive layer) like manufacture of the photoelectric conversion element mentioned later. Moreover, you may implement adsorption | suction of the said compound by apply | coating a semiconductor fine particle and the said compound of this invention simultaneously. Unadsorbed compounds can be removed by washing.

  Moreover, about the sensitization process of the semiconductor for photoelectric conversion materials of this invention, a sensitization process is performed when a semiconductor contains any one type compound represented by the said General formula (1)-(5). However, the details of the sensitization process will be specifically described in the photoelectric conversion element described later.

  Further, in the case of a semiconductor for a photoelectric conversion material having a semiconductor thin film with a high porosity, the above compound or sensitization is performed before water is adsorbed on the semiconductor thin film and in the voids inside the semiconductor thin film by moisture, water vapor, etc. It is preferable to complete the adsorption treatment (sensitization treatment of a semiconductor for a photoelectric conversion material) such as a dye compound.

  You may surface-treat the semiconductor for photoelectric conversion materials of this invention using an organic base. Examples of the organic base include diarylamine, triarylamine, pyridine, 4-t-butylpyridine, polyvinylpyridine, quinoline, piperidine, amidine, and the like. Among them, pyridine, 4-t-butylpyridine, and polyvinylpyridine are preferable. preferable.

  When the organic base is a liquid, it can be surface treated by preparing a solution dissolved in an organic solvent as it is, and immersing the semiconductor for a photoelectric conversion material of the present invention in a liquid amine or an amine solution. .

  In addition, as a dye that can be used in combination with any one of the compounds represented by the general formulas (1) to (5) according to the present invention, those that can spectrally sensitize the semiconductor according to the present invention. Any dye can be used. In order to make the wavelength range of photoelectric conversion as wide as possible and increase the conversion efficiency, it is also preferable to mix two or more kinds of dyes. Moreover, the pigment | dye to mix and its ratio can be selected so that it may match with the wavelength range and intensity distribution of the target light source. Moreover, another pigment | dye can be adsorb | sucked on another board | substrate, and they can also be piled up.

  Among the dyes according to the present invention, metal complex dyes, phthalocyanine dyes, porphyrin dyes, and polymethine dyes are preferably used from the comprehensive viewpoints such as photoelectron transfer reaction activity, light durability, and photochemical stability.

  Among the metal complex dyes, JP-A Nos. 2001-223037, 2001-226607, US Pat. Nos. 4,927,721, 4,684,537, 5,084,365, Ruthenium complexes described in 5,350,644, 5,463,057, 5,525,440, JP-A-7-249750, JP-T-10-504521, WO98 / 50393, etc. A dye is preferably used.

  Examples of the porphyrin dye and the phthalocyanine dye include dyes described in JP-A No. 2001-223037 as preferable dyes.

  Examples of the polymethine dye include conventionally known methine dyes, JP-A Nos. 11-35836, 11-158395, 11-163378, 11-214730, and 11-214731. 10-093118, 11-273754, JP-A-2000-106224, 2000-357809, 2001-052766, EP 892,411, 911,841, etc. Those described are mentioned.

<< Method for Manufacturing Semiconductor for Photoelectric Conversion Material >>
A method for manufacturing a semiconductor for a photoelectric conversion material of the present invention will be described.

  As one embodiment of the semiconductor for a photoelectric conversion material of the present invention, a method such as forming the above semiconductor for a photoelectric conversion material on a conductive support by firing is exemplified.

As another example, in the case of titanium oxide, Ti (OC ₃ H ₇ ) 4 vapor heated at a low temperature (for example, 80 ° C.) after titanium oxide particles are formed on a substrate (made of glass or polymer) by electrophoresis. There are a method of adsorbing light and irradiating light, a method of forming by irradiating microwaves, and the like. In addition, when zinc oxide is used, there is a method in which a zinc oxide thin film is formed by electrolytic deposition from a zinc chloride aqueous solution and used as a semiconductor.

  When the semiconductor for a photoelectric conversion material of the present invention is produced by firing, the semiconductor is sensitized (adsorption, penetration into a porous layer, etc.) with the above-described compound or sensitizing dye after firing. It is preferable to do. It is particularly preferable to perform the compound adsorption treatment quickly after the firing and before the water is adsorbed to the semiconductor.

  When the semiconductor for photoelectric conversion materials of the present invention is in the form of particles, the semiconductor electrode is preferably prepared by applying or spraying the semiconductor for photoelectric conversion materials onto a conductive support. Moreover, when the semiconductor for photoelectric conversion materials of this invention is a film | membrane form, Comprising: It is not hold | maintained on an electroconductive support body, the semiconductor electrode for photoelectric conversion materials is bonded on an electroconductive support body, and a semiconductor electrode is attached. It is preferable to produce it.

  Hereinafter, a process for producing a semiconductor for a photoelectric conversion material of the present invention will be specifically described.

<< Preparation of coating liquid containing semiconductor fine powder >>
First, a coating solution containing fine semiconductor powder is prepared. The semiconductor fine powder preferably has a finer primary particle diameter, and the primary particle diameter is preferably 1 nm to 5000 nm, and more preferably 2 nm to 50 nm. The coating liquid containing the semiconductor fine powder can be prepared by dispersing the semiconductor fine powder in a solvent. The semiconductor fine powder dispersed in the solvent is dispersed in the form of primary particles. The solvent is not particularly limited as long as it can disperse the semiconductor fine powder.

  Examples of the solvent include water, an organic solvent, and a mixed solution of water and an organic solvent. As the organic solvent, alcohols such as methanol and ethanol, ketones such as methyl ethyl ketone, acetone and acetyl acetone, hydrocarbons such as hexane and cyclohexane, and the like are used. A surfactant and a viscosity modifier (polyhydric alcohol such as polyethylene glycol) can be added to the coating solution as necessary. The range of the semiconductor fine powder concentration in the solvent is preferably 0.1% by mass to 70% by mass, and more preferably 0.1% by mass to 30% by mass.

<< Application of Semiconductor Fine Powder-Containing Coating Liquid and Firing Process of Formed Semiconductor Layer >>
The semiconductor fine powder-containing coating solution obtained as described above is applied or sprayed onto a conductive support, dried, etc., and then baked in air or in an inert gas, on the conductive support. A semiconductor layer (semiconductor film) is formed.

  The film obtained by applying and drying the coating liquid on the conductive support is composed of an aggregate of semiconductor fine particles, and the particle size of the fine particles corresponds to the primary particle size of the semiconductor fine powder used. is there.

  The semiconductor fine particle aggregate film formed on the substrate such as the conductive support in this way has a low bonding strength with the conductive support and a bonding strength between the fine particles and a low mechanical strength. From the above, the semiconductor fine particle aggregate film is preferably fired to increase the mechanical strength and to obtain a fired product film firmly fixed to the substrate.

  In the present invention, the fired product film may have any structure, but is preferably a porous structure film (also referred to as a porous layer having voids).

  Here, the porosity of the semiconductor thin film according to the present invention is preferably 10% by volume or less, more preferably 8% by volume or less, and particularly preferably 0.01% by volume to 5% by volume. The porosity of the semiconductor thin film means a porosity that is penetrable in the thickness direction of the dielectric, and can be measured using a commercially available apparatus such as a mercury porosimeter (Shimadzu Polarizer 9220 type).

  The film thickness of the semiconductor layer that is a fired product film having a porous structure is preferably at least 10 nm or more, more preferably 100 nm to 10,000 nm.

  From the viewpoint of appropriately adjusting the actual surface area of the fired product film during the firing treatment and obtaining a fired product film having the above porosity, the firing temperature is preferably lower than 1000 ° C, more preferably 200 ° C to 800 ° C. It is the range of 300 degreeC, Most preferably, it is the range of 300 to 800 degreeC.

  Further, the ratio of the actual surface area to the apparent surface area can be controlled by the particle diameter and specific surface area of the semiconductor fine particles, the firing temperature, and the like. In addition, after heat treatment, for example, chemical plating or aqueous trichloride using a titanium tetrachloride aqueous solution is used to increase the surface area of the semiconductor particles, increase the purity in the vicinity of the semiconductor particles, and increase the efficiency of electron injection from the dye into the semiconductor particles. Electrochemical plating using a titanium aqueous solution may be performed.

<Semiconductor sensitization processing>
As described above, the semiconductor sensitization treatment is performed by dissolving the dye in an appropriate solvent and immersing the substrate obtained by firing the semiconductor in the solution. In that case, a substrate on which a semiconductor layer (also referred to as a semiconductor film) is formed by baking is subjected to pressure reduction treatment or heat treatment beforehand to remove bubbles in the film, and the general formulas (1) to (5) It is preferable that any one of the above compounds can enter deep inside the semiconductor layer (semiconductor film), and it is particularly preferable when the semiconductor layer (semiconductor film) is a porous structure film.

"solvent"
The solvent used for dissolving any one compound of the general formulas (1) to (5) can dissolve the compound, and can dissolve the semiconductor or react with the semiconductor. There is no particular limitation if it is not present, but in order to prevent moisture and gas dissolved in the solvent from entering the semiconductor film and hindering the sensitization treatment such as adsorption of the compound, degassing and distillation in advance. It is preferable to purify it.

  Solvents preferably used in dissolving the above compounds are alcohol solvents such as methanol, ethanol and n-propanol, ketone solvents such as acetone and methyl ethyl ketone, ether solvents such as diethyl ether, diisopropyl ether, tetrahydrofuran and 1,4-dioxane. Solvents and halogenated hydrocarbon solvents such as methylene chloride and 1,1,2-trichloroethane, particularly preferably methanol, ethanol, acetone, methyl ethyl ketone, tetrahydrofuran and methylene chloride.

《Tensing temperature and time》
The time for immersing the substrate on which the semiconductor has been baked in the solution containing any one compound of the general formulas (1) to (5) is such that the compound enters the semiconductor layer (semiconductor film) deeply and adsorbs it. From the viewpoint of sufficiently proceeding, sufficiently sensitizing the semiconductor, and suppressing degradation of the compound, which is generated by decomposition of the compound in a solution and hinders adsorption of the compound, at 25 ° C., It is preferably 3 hours to 48 hours, more preferably 4 hours to 24 hours. This effect is particularly remarkable when the semiconductor film is a porous structure film. However, the immersion time is a value under the condition of 25 ° C., and is not limited to the above when the temperature condition is changed.

  In soaking, the solution containing any one compound of the general formulas (1) to (5) may be heated to a temperature that does not boil as long as the compound is not decomposed. A preferable temperature range is 10 ° C to 100 ° C, and more preferably 25 ° C to 80 ° C. However, as described above, this is not the case when the solvent boils in the temperature range.

<< Photoelectric conversion element >>
The photoelectric conversion element of this invention is demonstrated using FIG.

  FIG. 1 is a partial cross-sectional view showing an example of the structure of the photoelectric conversion element of the present invention.

  Reference numeral 1 denotes a conductive support, 2 denotes a photosensitive layer, 3 denotes a charge transfer layer, and 4 denotes a counter electrode. The conductive support 1 and the photosensitive layer 2 are also collectively referred to as a semiconductor electrode.

  Here, the photosensitive layer 2 is a layer having the semiconductor for a photoelectric conversion material of the present invention, and the charge transfer layer 3 usually contains a redox electrolyte and is in contact with the conductive support 1, the photosensitive layer 2, and the counter electrode 4. Used in form.

<< Method for Manufacturing Photoelectric Conversion Element >>
The manufacturing method of a photoelectric conversion element is demonstrated using FIG.

  In the photoelectric conversion element of the present invention, a semiconductor thin film is formed on the conductive support 1 as shown in FIG. 1 as described above, and then the general formulas (1) to (5) according to the present invention are used. It is manufactured through a process of adsorbing any one of the compounds represented.

  In addition, the surface area of the semiconductor thin film is increased or impurities on the surface of the semiconductor thin film are removed to increase the purity of the semiconductor, and the semiconductor is formed from any one compound represented by the general formulas (1) to (5). For example, chemical plating using a titanium tetrachloride aqueous solution or electrochemical plating using a titanium trichloride aqueous solution may be performed for the purpose of increasing the efficiency of electron injection into the substrate. In order to obtain the same effect, carboxylic acids (acetic acid, propionic acid, hexanoic acid, benzoic acid, etc.) may be adsorbed on the semiconductor surface after dye adsorption.

  The semiconductor film formed on the conductive support 1 adsorbs any one of the compounds represented by the above general formulas (1) to (5) to sensitize the semiconductor film, thereby photosensitive layer 2. Form. As described above, the sensitizing treatment method is performed by dissolving the compound in an appropriate solvent and immersing the semiconductor film formed on the conductive support 1 in the solution. In that case, the semiconductor film is preliminarily decompressed or heat-treated to remove bubbles in the film, and any one compound represented by the general formulas (1) to (5) is converted into a semiconductor film. It is preferable to be able to enter deep inside.

  When any one of the compounds represented by the general formulas (1) to (5) is adsorbed to the semiconductor according to the present invention, it may be used alone or in combination. Further, a conventionally known sensitizing dye compound may be mixed and adsorbed.

  In particular, when the application of the semiconductor is a solar cell, it is preferable to use a mixture of two or more dyes so that the wavelength range of photoelectric conversion is widened and sunlight can be used as effectively as possible.

  A semiconductor for a photoelectric conversion material sensitized by using a plurality of compounds of any one of the general formulas (1) to (5) described above in combination is a solution prepared by mixing the compounds to be used together It may be prepared by immersing in a solution, or a solution may be prepared for each compound, and it may be prepared by immersing in each solution in turn.

  When preparing a separate solution for each compound and immersing in each solution in order, the effect of the present invention regardless of the order in which the compound or a conventionally known sensitizing dye is adsorbed to the semiconductor Can be obtained.

  The adsorption treatment may be performed at room temperature using a solution in which the compound is dissolved as described above, or may be performed by heating the solution to a temperature that does not affect the compound. Furthermore, it is preferable to remove the dye that has not been adsorbed during the adsorption treatment by washing treatment with a solvent or the like.

  After the dye is adsorbed to the semiconductor film formed on the conductive support 1 to form the photosensitive layer 2, the counter electrode 4 is disposed so as to face the photosensitive layer 2. Further, a redox electrolyte as a charge transfer layer is injected between the semiconductor electrode and the counter electrode 4 to obtain a photoelectric conversion element.

《Solar cell》
The solar cell of the present invention will be described.

  As shown in FIG. 1, the solar cell of the present invention is optimally designed for sunlight and circuit design as one aspect of the photoelectric conversion element of the present invention, and is optimal when sunlight is used as a light source. It has a structure in which photoelectric conversion is performed. That is, the semiconductor for photoelectric conversion material has a structure that can be irradiated with sunlight. When constituting the solar cell of the present invention, it is preferable that the semiconductor electrode, the charge transfer layer and the counter electrode are housed in a case and sealed, or the whole is sealed with resin.

  When the solar cell of the present invention is irradiated with sunlight or an electromagnetic wave equivalent to sunlight, the compound of the present invention adsorbed on the semiconductor for photoelectric conversion material absorbs the irradiated light or electromagnetic wave and excites it. Electrons generated by excitation move to the semiconductor, and then move to the counter electrode 4 via the conductive support 1 to reduce the redox electrolyte of the charge transfer layer 3. On the other hand, the compound of the present invention in which electrons are transferred to a semiconductor is an oxidant, but is reduced by the supply of electrons from the counter electrode 4 via the redox electrolyte of the charge transfer layer 3 and is reduced to the original. At the same time, the redox electrolyte of the charge transfer layer 3 is oxidized and returned to a state where it can be reduced again by the electrons supplied from the counter electrode 4. In this way, electrons flow, and a solar cell using the photoelectric conversion element of the present invention can be configured.

<Conductive support>
The conductive support used in the photoelectric conversion element of the present invention and the solar battery of the present invention is provided with a conductive material such as a conductive material such as a metal plate or a non-conductive material such as a glass plate or a plastic film. A structure having a different structure can be used. Examples of materials used for the conductive support include metal (for example, platinum, gold, silver, copper, aluminum, rhodium, indium) or conductive metal oxide (for example, indium-tin composite oxide, tin oxide doped with fluorine) And carbon). The thickness of the conductive support is not particularly limited, but is preferably 0.3 mm to 5 mm.

  The conductive support is preferably substantially transparent, and substantially transparent means that the light transmittance is 10% or more, more preferably 50% or more, and 80 % Or more is most preferable. In order to obtain a transparent conductive support, it is preferable to provide a conductive layer made of a conductive metal oxide on the surface of a glass plate or a plastic film. When the transparent conductive support 1 is used, light is preferably incident from the support side.

The conductive support preferably has a surface resistance of 50 Ω / cm ² or less, and more preferably 10 Ω / cm ² or less.

《Charge transfer layer》
The charge transfer layer used in the present invention will be described.

A redox electrolyte is preferably used for the charge transfer layer. Here, examples of the redox electrolyte include I ⁻ / I ₃ ⁻ system, Br ⁻ / Br ₃ ⁻ system, and quinone / hydroquinone system. Such a redox electrolyte can be obtained by a conventionally known method. For example, an I ⁻ / I ₃ ⁻ based electrolyte can be obtained by mixing iodine ammonium salt and iodine. The charge transfer layer is composed of dispersions of these redox electrolytes. These dispersions are liquid electrolytes when they are in solution, and are dispersed in solid polymer electrolytes and gel substances when dispersed in polymers that are solid at room temperature. When called, it is called a gel electrolyte. When a liquid electrolyte is used as the charge transfer layer, an electrochemically inert solvent is used as the solvent, for example, acetonitrile, propylene carbonate, ethylene carbonate, or the like is used. Examples of the solid polymer electrolyte include those described in JP-A No. 2001-160427, and examples of the gel electrolyte include those described in “Surface Science” Vol. 21, No. 5, pages 288 to 293.

《Counter electrode》
The counter electrode used in the present invention will be described.

Counter electrode, as long as it has conductivity, but any conductive material is used, I ₃ ^- catalytic ability to perform fast enough the reduction reaction of oxidation and other redox ions such as ions It is preferable to use what you have. Examples of such a material include a platinum electrode, a surface of a conductive material subjected to platinum plating or platinum deposition, rhodium metal, ruthenium metal, ruthenium oxide, and carbon.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

Example 1
62.5 ml of titanium tetraisopropoxide (first grade, manufactured by Wako Pure Chemical Industries, Ltd.) was dropped into 375 ml of pure water at room temperature with vigorous stirring for 10 minutes (a white precipitate was formed), and then 70% aqueous nitric acid was added. After 2.65 ml was added and the reaction system was heated to 80 ° C., stirring was continued for 8 hours. Furthermore, after concentrating under reduced pressure until the volume of the reaction mixture becomes about 200 ml, 125 ml of pure water and 140 g of titanium oxide powder (Super Titania F-6 manufactured by Showa Titanium Co., Ltd.) are added to a titanium oxide suspension (about 800 ml). ) Was prepared. The titanium oxide suspension is applied onto a transparent conductive glass plate coated with fluorine-doped tin oxide, dried naturally and then fired at 300 ° C. for 60 minutes to form a film-like titanium oxide on the support. did.

  In 200 ml of methanol solution, Compound No. A solution in which 5 g of 6 was dissolved was prepared, the film-like titanium oxide was immersed in the support, and 1 g of trifluoroacetic acid was further added, followed by ultrasonic irradiation for 2 hours. After the reaction, the film-like titanium oxide was washed with chloroform and vacuum-dried to obtain the photoelectric conversion element 1 of the present invention. Compound no. The photoelectric conversion elements 2 to 60 of the present invention were prepared by the same method except that 6 was changed as shown in Table 1 below, and each compound (dye) was adsorbed. Further, comparative photoelectric conversion elements R1 and R2 were obtained in the same manner except that the following comparative compound R-1 (Exemplary Compound S-4 described in JP-A-2001-76775) and R-2 were used.

Example 2
One of the photoelectric conversion elements prepared in Example 1 was provided as one electrode, and a transparent conductive glass plate coated with platinum on which fluorine was doped as a counter electrode was further used. It was. An electrolyte was placed between the two electrodes, and this side surface was sealed with resin, then lead wires were attached, and the solar cells SC-1 to SC-60 of the present invention and the comparative solar cells SC-R1 and SC-R2 were assembled. Three each were prepared. The electrolyte is prepared by mixing tetrapropylammonium iodide and iodine in a mixed solvent of acetonitrile / ethylene carbonate having a volume ratio of 1: 4, with respective concentrations of 0.46 mol / liter and 0.06 mol / liter. What was melt | dissolved so that it might become a liter was used.

Example 3
The short-circuit current value Jsc when the solar cell produced in Example 2 was irradiated with light having an intensity of 100 mW / m ² by a solar simulator (manufactured by JASCO (JASCO), low energy spectral sensitivity measuring device CEP-25) The open-circuit voltage value Voc was measured and shown in Tables 1 and 2 below together with the compound / photoelectric conversion element used in each solar cell. The indicated value was the average value of the measurement results for three solar cells having the same configuration and production method.

All of these results indicate that the solar cell using the compound of the present invention has higher photoelectric conversion efficiency than the comparative example, and it can be seen that the compound of the present invention is useful. Furthermore, in the solar cells SC-1 to SC-60, a decrease in photoelectric conversion efficiency is not observed even after 100 hours of light irradiation of 100 mW / m ² by a solar simulator, and the solar cells using the compound of the present invention are stable. It was found that the compounds of the present invention are useful.

It is a fragmentary sectional view which shows an example of the structure of the photoelectric conversion element of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Conductive support body 2 Photosensitive layer 3 Charge transfer layer 4 Counter electrode

Claims (6)

A compound for photoelectric conversion material, wherein a compound represented by the following general formula ( 2 ) is adsorbed on a semiconductor surface.

Wherein each R _1, R ₂ represent independently a hydrogen atom, an optionally substituted aliphatic group, an optionally substituted aromatic group, a heterocyclic group which may be substituted, also , R ₁ and R ₂ may be combined to form a nitrogen-containing heterocycle (due to the nonmetallic atom group). Cp is a 5-membered or 6-membered aromatic carbocyclic group or a heterocyclic group, to Table Wa an atomic group having a compound having at least one carboxyl group as a substituent. Each L ₁ ~ L ₃ represents a methine group which may be substituted, _{Z 1} and _{Z 2} are each an oxygen atom, a sulfur atom,> N-Ra group, Ra is _{R 1} and _{R 2} as defined And R _{3 to} R ₆ each represent a hydrogen atom or a substituent. Further, R ₃ and R ₄ or R ₅ and R ₆ may be bonded to each other to form a condensed ring. p represents an integer of 0 or 1, and q represents an integer of 1. ] Semiconductor for a photoelectric conversion material according to claim 1, wherein Cp in formula (2), characterized in Rukoto represented by Cp-6.

[In the formula, B ₁ is a nitrogen atom or = CR ₂₃ group, B ₂ is a nitrogen atom or = CR ₂₄ group, B ₃ is a nitrogen atom or = CR ₂₅ group, B ₄ is a nitrogen atom or = It represents a _{C-R 26.} R _{23 to} R ₂₆ are each a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, acylamino group, alkane or arylsulfonylamino group, amino group, alkylthio group, arylthio group, alkoxy group, aryloxy group, It represents a ureido group, alkoxycarbonylamino group, carbamoyl group, sulfamoyl group, cyano group, carboxyl group, acyl group, aryloxycarbonyl group or alkoxycarbonyl group. ] Under following general formula (4) or (5) at least one semiconductor for a photoelectric conversion material you characterized that you have been adsorbed on the semiconductor surface of the compound represented by.

Wherein each R _1, R ₂ represent independently a hydrogen atom, an optionally substituted aliphatic group, an optionally substituted aromatic group, a heterocyclic group which may be substituted, also , R ₁ and R ₂ may be combined to form a nitrogen-containing heterocycle (due to the nonmetallic atom group). R _{103 to} R ₁₀₈ each represent a hydrogen atom or a substituent , and are bonded to each other between R ₁ or R ₂ and R ₁₀₃ or R ₁₀₆ , between R ₁₀₃ and R ₁₀₄ , and between R ₁₀₅ and R _106. R ₁₀₉ may be an alkyl group, aryl group, heterocyclic group, acylamino group, amino group, cyano group, carboxyl group, alkoxycarbonyl group, carbamoyl group, alkoxy group, aryloxy group, Represents an alkylthio group, an arylthio group, a ureido group or an alkoxycarbonylamino group, and R ₁₁₀ and R ₁₁₁ are an optionally substituted aliphatic group, an optionally substituted aromatic group, and an optionally substituted heterocyclic ring. Group or an acyl group. ] The semiconductor surface for a photoelectric conversion material according to any one of claims 1 to 3 , wherein the semiconductor surface is a surface of a metal oxide or metal sulfide semiconductor. The photoelectric conversion element characterized by providing the semiconductor for photoelectric conversion materials of any one of Claims 1-4 on the electroconductive support body . It has a photoelectric conversion element provided with the layer containing the semiconductor for photoelectric conversion materials of any one of Claims 1-4 on the electroconductive support body, a charge-transfer layer, and a counter electrode, It is characterized by the above-mentioned. Solar cell .

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