JP2005129329A - Semiconductor for photoelectric conversion material, photoelectric conversion element and solar cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a semiconductor for a photoelectric conversion material which has high photoelectric conversion efficiency and superior stability, and to provide a photoelectric element and a solar cell. <P>SOLUTION: The semiconductor for a photoelectric conversion material contains a dye expressed by a general formula (1). In the general formula (1), R<SB>1</SB>to R<SB>9</SB>and R represent hydrogen atoms or substituent groups. R<SB>1</SB>and R<SB>2</SB>, R<SB>2</SB>and R<SB>3</SB>, R<SB>3</SB>and R<SB>4</SB>, and R<SB>9</SB>and R may be bonded to one another to form a cyclic structure, and n is an integer from 0 to 4. R<SB>6</SB>-R<SB>8</SB>may be different from one another. If n≥1, R<SB>6</SB>to R<SB>8</SB>may be bonded to one another to form a cyclic structure. Y represents -O-, -S(O)<SB>m</SB>- or -NR<SB>21</SB>-, and m represents an integer from 0 to 2. Z represents -NR<SB>21</SB>- or -CR<SB>22</SB>R<SB>23</SB>-, and R<SB>21</SB>to R<SB>23</SB>represent hydrogen atoms or substituent groups. A molecule includes at least one -COOM- group, and M represents a hydrogen atom or a salt formation nature cation. <P>COPYRIGHT: (C)2005,JPO&NCIPI

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 for, for example, a solar cell. 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, and the basic structure specifically includes a metal oxide semiconductor, a dye adsorbed thereon, an electrolyte solution, and a counter electrode.

  In the conventional dye-sensitized solar cell as described above, a photoelectric conversion material in which a spectral sensitizing dye having absorption in the visible light region is adsorbed on the semiconductor surface is used. For example, a solar cell having a spectral sensitizing dye layer such as a transition metal complex on the surface of a metal oxide semiconductor is described (for example, see Patent Document 1), and a titanium oxide semiconductor doped with metal ions Examples include a solar cell having a spectral sensitizing dye layer such as a transition metal complex on the surface of the layer (for example, see Patent Document 2).

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.

  For example, it has been reported by Tsubomura et al. That a porous zinc oxide electrode adsorbing an organic dye has very high performance (for example, see Non-Patent Document 1).

  After that, the dye has also been improved, and Graetzel et al. Have adsorbed the ruthenium complex dye on the porous titanium oxide electrode, so that it now has the same performance as a silicon solar cell (for example, Non-patent document 2).

However, for practical use to replace silicon solar cells, higher energy conversion efficiency, higher short-circuit current, open-circuit voltage, and form factor are required than ever before. Technological developments using reported materials such as ZnO, TiO ₂ , zirconium oxide (ZrO ₂ ), niobium oxide (Nb ₂ O ₅ ) and the like have been carried out.

In addition, since dye-sensitized wet solar cells are much cheaper to manufacture than silicon solar cells, in the future, there is a possibility of replacing silicon solar cells used in the above-mentioned various products. In some cases, the characteristics of the solar cell according to each product are important. Among various characteristics of solar cells, the following are shown. 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 have been found to have relatively excellent characteristics, but the dyes are expensive and ruthenium, the central metal of the complex, is a rare element. Therefore, organic dyes that can be supplied at a lower cost and more stably are 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 (see, for example, Patent Documents 3, 4, and 5). Well-known dyes include merocyanine dyes, xanthene dyes, coumarin dyes, Examples include acridine dyes and phenylmethane dyes. In addition, new dye mother nuclei other than those have been developed (see, for example, Patent Document 6), but since none of the dyes has yet satisfactory performance, the adsorptive power is strong and extends to the long wavelength region. Further development of highly efficient dyes is desired.
Japanese Patent Laid-Open No. 1-220380 Japanese National Patent Publication No. 5-504023 JP-A-11-167937 Japanese Patent Laid-Open No. 11-214730 Japanese Patent Laid-Open No. 11-214731 JP 2001-76775 A Nature, 261 (1976) p402. J. et al. Am. Chem. Soc. 115 (1993) 6382

  The first object of the present invention is to provide a semiconductor for a photoelectric conversion material, a photoelectric conversion element, and a solar cell that exhibit high photoelectric conversion efficiency and excellent stability.

The above object of the present invention has been achieved by the following constitution.
(Claim 1)
The semiconductor for photoelectric conversion materials characterized by including the pigment | dye represented by following General formula (1).

(Wherein R _{1 to} R ₉ and R represent a hydrogen atom or a substituent, R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R _4, and R ₉ and R are bonded to each other to form a cyclic structure. N is an integer from 0 to 4, R _{6 to} R ₈ may be different from each other, and when n is 1 or more, they may be bonded to each other to form a cyclic structure. -O -, - S (O) m - or -NR ₂₁ - represents, m represents an integer of 0 to 2, Z is -NR ₂₁ - or -CR ₂₂ R ₂₃ - represents, R ₂₁ to R ₂₃ Represents a hydrogen atom or a substituent, contains at least one -COOM group in the molecule, and M represents a hydrogen atom or a salt-forming cation.)
(Claim 2)
The semiconductor for photoelectric conversion materials characterized by including the pigment | dye represented by General formula (2).

(Wherein R _{1 to} R ₈ and R represent a hydrogen atom or a substituent, R ₁ and R ₂ , R ₂ and R _3, and R ₃ and R ₄ may be bonded to each other to form a cyclic structure; n is an integer of 0 to 4, R _{6 to} R ₈ may be different from each other, and when n is 1 or more, they may be bonded to each other to form a cyclic structure, and Y is —O—, — S (O) _m — or —NR ₂₁ —, m represents an integer of 0 to 2, Z represents —NR ₂₁ — or —CR ₂₂ R ₂₃ —, and R _{21 to} R ₂₃ represent a hydrogen atom or a substituent. And M represents a hydrogen atom or a salt-forming cation.)
(Claim 3)
The semiconductor for photoelectric conversion materials characterized by including the pigment | dye represented by General formula (3).

(Wherein R _{1 to} R ₈ represent a hydrogen atom or a substituent, R ₁ and R ₂ , R ₂ and R ₃ and R ₃ and R ₄ may be bonded to each other to form a cyclic structure, and n is R is an integer of 0 to 4, R _{6 to} R ₈ may be different from each other, and when n is 1 or more, they may be bonded to each other to form a cyclic structure, and A is a 5- or 6-membered heterocyclic ring the stands, Y is -O -, - S (O) m - or -NR ₂₁ - represents, m represents an integer of 0 to 2, Z is -NR ₂₁ - or -CR ₂₂ R ₂₃ - represents, R _{21 to} R ₂₃ represent a hydrogen atom or a substituent, and at least one —COOM group is contained in the molecule, and M represents a hydrogen atom or a salt-forming cation.)
(Claim 4)
The semiconductor for photoelectric conversion materials characterized by including the pigment | dye represented by General formula (4).

(Wherein R _{1 to} R ₈ represent a hydrogen atom or a substituent, R ₁ and R ₂ , R ₂ and R ₃ and R ₃ and R ₄ may be bonded to each other to form a cyclic structure, and n is R _{6 to} R ₈ may be different from each other, and when n is 1 or more, they may be bonded to each other to form a cyclic structure, and R ₁₀ and R ₁₁ may be substituted. Y represents —O—, —S (O) _m — or —NR ₂₁ —, m represents an integer of 0 to 2, Z represents —NR ₂₁ — or —CR ₂₂ R ₂₃ —, R ₂₁ to R ₂₃ represents a hydrogen atom or a substituent, at least one contains a -COOM group in a molecule, M represents a hydrogen atom or a salt-forming cation.)
(Claim 5)
The semiconductor for photoelectric conversion materials characterized by including the pigment | dye represented by General formula (5).

(Wherein R _{1 to} R ₈ represent a hydrogen atom or a substituent, R ₁ and R ₂ , R ₂ and R ₃ and R ₃ and R ₄ may be bonded to each other to form a cyclic structure, and n is R _{6 to} R ₈ may be different from each other, and when n is 1 or more, they may be bonded to each other to form a cyclic structure, and B ₁ or B ₂ are each independently represents -CR ₁₃ = or -N = Te, R ₁₂ and R ₁₃ represents a substituent, Y is -O -, - S (O) m - or -NR ₂₁ - represents, m is 0 to 2 Represents an integer, Z represents —NR ₂₁ — or —CR ₂₂ R ₂₃ —, R _{21 to} R ₂₃ each represents a hydrogen atom or a substituent, contains at least one —COOM group in the molecule, and M represents hydrogen. Represents an atom or a salt-forming cation.)
(Claim 6)
The semiconductor for a photoelectric conversion material according to claim 5, wherein the general formula (5) is a dye represented by the following general formula (6).

(Wherein R _{1 to} R ₈ represent a hydrogen atom or a substituent, R ₁ and R ₂ , R ₂ and R ₃ and R ₃ and R ₄ may be bonded to each other to form a cyclic structure, and n is R _{6 to} R ₈ may be different from each other, and when n is 1 or more, they may be bonded to each other to form a cyclic structure, and R ₁₂ and R ₁₃ represent a substituent. Y represents —O—, —S (O) _m — or —NR ₂₁ —, m represents an integer of 0 to 2, Z represents —NR ₂₁ — or —CR ₂₂ R ₂₃ —, R ₂₁ to R ₂₃ represents a hydrogen atom or a substituent, at least one contains a -COOM group in a molecule, M represents a hydrogen atom or a salt-forming cation.)
(Claim 7)
In said general formula (1)-(6), R < ₂ > or R < ₃ > is following General formula (7), The semiconductor for photoelectric conversion materials of any one of Claims 1-6 characterized by the above-mentioned.

(In the formula, R ₀₁ and R ₀₂ represent a hydrogen atom, an alkyl, an aryl group or a heterocyclic group, and R ₀₁ or R ₀₂ and R ₁ or R ₃ , R ₀₁ or R in the general formulas (1) to (6)) ₀₂ and R ₂ or R ₄ in the general formulas (1) to (6) may be bonded to each other to form a cyclic structure.)
(Claim 8)
8. The semiconductor for a photoelectric conversion material according to claim 1, wherein Y is an oxygen atom and Z is —CR ₂₂ R ₂₃ — in the general formulas (1) to (6). .
(However, R ₂₂ and R ₂₃ represent a hydrogen atom or a substituent.)
(Claim 9)
The semiconductor for photoelectric conversion materials according to any one of claims 1 to 8, wherein the semiconductor for photoelectric conversion materials is a metal oxide or a metal sulfide semiconductor.
(Claim 10)
The photoelectric conversion element characterized by the layer containing the semiconductor for photoelectric conversion materials of any one of Claims 1-9 being provided on the electroconductive support body.
(Claim 11)
A solar cell comprising the photoelectric conversion element according to claim 10, a charge transfer layer, and a counter electrode.

  According to the present invention, it was possible to provide a semiconductor for a photoelectric conversion material, a photoelectric conversion element, and a solar cell that exhibit high photoelectric conversion efficiency and excellent stability.

  Hereinafter, the present invention will be described in detail.

  As a result of intensive studies to solve the above problems, the present inventors have found specific structures as represented by the general formulas (1) to (7) described in claims 1 to 11, respectively. The semiconductor for photoelectric conversion materials which sensitized using the compound which has it succeeded in obtaining the semiconductor for photoelectric conversion materials which shows the effect as described in this invention, ie, the high photoelectric conversion efficiency, and the outstanding stability.

<< Semiconductor for photoelectric conversion material >>
As a semiconductor used for the semiconductor for a photoelectric conversion material of the present invention, a simple substance such as silicon or germanium, a group 3 to group 5 of a periodic table (also referred to as an element periodic table), or a group 13 to group 15 system. A compound having an element, a metal chalcogenide (eg, an oxide, sulfide, selenide, etc.), a metal nitride, or the like can be used.

  Preferred metal chalcogenides include titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium or tantalum oxides, cadmium, zinc, lead, silver, antimony or Bismuth sulfide, cadmium or lead selenide, cadmium telluride and the like. Other compound semiconductors include phosphides such as zinc, gallium, indium and cadmium, gallium-arsenic or copper-indium selenide, copper-indium sulfide, titanium nitride, and the like.

Specific examples of the semiconductor according to the semiconductor for photoelectric conversion material of the present invention include TiO ₂ , SnO ₂ , Fe ₂ O ₃ , WO ₃ , ZnO, Nb ₂ O ₅ , CdS, ZnS, PbS, Bi ₂ S ₃ , CdSe. , CdTe, GaP, InP, GaAs, CuInS ₂ , CuInSe ₂ , Ti ₃ N _4, etc., but TiO ₂ , ZnO, SnO ₂ , Fe ₂ O ₃ , WO ₃ , Nb ₂ O are preferably used. ₅ , CdS, and PbS, and TiO ₂ or Nb ₂ O ₅ is more preferably used, and TiO ₂ is preferably used among them.

The semiconductor used for the photoelectric conversion material semiconductor of the present invention may be a combination of the above-described plurality of semiconductors. For example, several types of metal oxides or metal sulfides described above can be used in combination, or 20% by mass of titanium nitride (Ti ₃ N ₄ ) may be mixed and used in the titanium oxide semiconductor. In addition, J.H. Chem. Soc. , Chem. Commun. 15 (1999). At this time, when a component is added as a semiconductor in addition to the metal oxide or metal sulfide, the mass ratio of the additional component to the metal oxide or metal sulfide semiconductor is preferably 30% or less.

  High photoelectric conversion which is one of the objects described in the present invention by sensitizing the semiconductor for photoelectric conversion material with any one of the compounds represented by the general formulas (1) to (7). The semiconductor for photoelectric conversion materials of the present invention showing efficiency and excellent stability can be obtained.

  Hereinafter, the compounds represented by the general formulas (1) to (7) will be described.

<< Compound Represented by Formula (1) >>
The compound represented by the general formula (1) according to the present invention will be described.

In the general formula (1), R _{1 to} R ₉ and R represent a hydrogen atom or a substituent, R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R _4, and R ₉ and R are bonded to each other to form a cyclic structure. The ring structure formed may be either an aliphatic ring or an aromatic ring, and may be a hydrocarbon ring or a heterocyclic ring. n is an integer of 0 to 4, and R _{6 to} R ₈ may be different from each other. When n is 1 or more, they may be bonded to each other to form a cyclic structure, and are substituted by a substituent described later. Or may be condensed with another ring structure. When n is 1 or more, R ₆ and R _{7 as} repeating units may be different from each other, and a ring may be formed between adjacent repeating units R ₆ or R ₇ . R ₉ and R may combine to form a ring structure. Y represents —O—, —S (O) _m — or —NR ₂₁ —, m represents an integer of 0 to 2, Z represents —NR ₂₁ — or —CR ₂₂ R ₂₃ —, R ₂₁ to R ₂₃ represents a hydrogen atom or a substituent, contains at least one —COOM group in the molecule, and M represents a hydrogen atom or a salt-forming cation.

In the general formula (1), the substituents represented by R _{1 to} R ₉ , R _{21 to} R ₂₃ and R are not particularly limited as long as they can be substituted. For example, an alkyl group (for example, a methyl group, An ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, etc. may have a substituent, for example, a trifluoromethyl group Etc.), a cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), a bicycloalkyl group (eg, bicyclo [1,2,2] heptan-2-yl group, bicyclo [2,2,2] octane-3- Yl group), alkenyl group (for example, vinyl group, allyl group, prenyl group, octenyl group, etc.), cycloalkenyl group (for example, 2-cyclope). Nten-1-yl group, 2-cyclohexen-1-yl group, etc.), bicycloalkenyl group (for example, bicyclo [2,2,1] hept-2-en-1-yl group, bicyclo [2,2,2] Oct-2-en-4-yl group, etc.), 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, etc.), 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, etc.), heterocyclic oxy group (for example, 1-phenyltetra -5-oxy group, 2-tetrahydropyranyloxy group, pyridyloxy group, thiazolyloxy group, oxazolyloxy group, imidazolyloxy group, etc.), halogen atom (for example, chlorine atom, bromine atom, iodine atom, fluorine) Atoms), alkoxy groups (eg, methoxy, ethoxy, propyloxy, tert-butoxy, pentyloxy, hexyloxy, octyloxy, dodecyloxy, etc.), cycloalkoxy (eg, cyclopentyloxy) Group, cyclohexyloxy group, etc.), aryloxy group (for example, phenoxy group, naphthyloxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group, etc.) ), Alkylthio groups (eg Thio 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.) ), A heterocyclic thio group (for example, pyridylthio group, thiazolylthio group, oxazolylthio group, imidazolylthio group, furylthio group, pyrrolylthio group, etc.), alkoxycarbonyl group (for example, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group) Octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, Aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2 -Pyridylaminosulfonyl 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) 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy 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.), amide group (for example, methylcarbonylamino group, ethyl Carbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group ), Carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecyl) Aminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), Alkylsulfinyl group or arylsulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc. ), Alkylsulfonyl group or arylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group) Group), amino group (for example, amino group, methylamino group, ethylamino group, dimethylamino group, butylamino group, cyclo Nylamino 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-butyldimethylsilyl) Oxy group, etc.), aminocarbonyloxy group (for example, N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, N -N-octylcarbamoyloxy group, etc.), alkoxycarbonyloxy group (for example, methoxycarbonyloxy group, ethoxycarbonyloxy group, tert-butoxycarbonyloxy group, n-octylcarbonyloxy group, etc.), aryloxy Sicarbonyloxy group (for example, phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxyphenoxycarbonyloxy group, etc.), alkoxycarbonylamino group (for example, methoxycarbonylamino group, ethoxycarbonylamino group) , Tert-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group, etc.), aryloxycarbonylamino group (for example, phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, m- n-octyloxyphenoxycarbonylamino group, etc.), sulfamoylamino group (for example, sulfamoylamino group, N, N-dimethylaminosulfonylamino group, Nn-octylamino) Nosulfonylamino group, etc.), mercapto group, arylazo group (eg, phenylazo group, naphthylazo group, p-chlorophenylazo group, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group), heterocyclic azo group (For example, pyridylazo group, thiazolylazo group, oxazolylazo group, imidazolylazo group, furylazo group, pyrrolylazo group), imino group (for example, N-succinimido-1-yl group, N-phthalimido-1-yl group, etc.), phosphino group (Eg, dimethylphosphino group, diphenylphosphino group, methylphenoxyphosphino group, etc.), phosphinyl group (eg, phosphinyl group, dioctyloxyphosphinyl group, diethoxyphosphinyl group, etc.), phosphinyloxy group (For example, diphenoxyphosphinyloxy group, Octyloxyphosphinyloxy group, etc.), phosphinylamino group (eg, dimethoxyphosphinylamino group, dimethylaminophosphinylamino group, etc.), silyl group (eg, trimethylsilyl group, tert-butyldimethylsilyl group, Phenyldimethylsilyl group, etc.), cyano group, nitro group, hydroxyl group, sulfo group, carboxyl group and the like. In addition, they may be substituted with another substituent.

  In the general formula (1), the molecule has at least one —COOM group, and when M is other than a hydrogen atom, the salt-forming cation represented by M includes sodium salt, potassium salt, and magnesium salt. Further, it may be a salt formed with a metal ion such as calcium salt, or a salt formed with a protonated cation of an organic base such as pyridine, piperidine, triethylamine, aniline, diazabicycloundecene. Good.

R ₁ and R ₄ are preferably a hydrogen atom or an alkyl group. As described above, R ₁ and R ₂ , R ₂ and R _3, or R ₃ and R ₄ are bonded to each other to form a 5- or 6-membered cyclic structure. It is also preferable to form

R ₂ and R ₃ are preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, or the like, and it is preferable that either R ₂ or R ₃ is represented by the following general formula (7). It is also preferable that R ₁ and R ₂ , R ₂ and R _3, or R ₃ and R ₄ are bonded to each other to form a 5- or 6-membered cyclic structure, and R ₂ or R ₃ is represented by the general formula ( In the case of 7), R ₀₁ or R ₀₂ and R ₁ or R ₃ , R ₀₁ or R ₀₂ and R ₂ or R ₄ are bonded to each other to form a 5- or 6-membered cyclic structure (for example, pyrrolidine ring, morpholine ring, piperidine) A ring, a julolidine ring, etc.).

R ₅ is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a cyano group, an alkoxy group, an amino group, an acylamino group, etc., more preferably a hydrogen atom, a substituted or unsubstituted alkyl group, or an alkoxy group. is there.

R ₆ , R ₇ and R ₈ are preferably a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, an alkoxy group, an amino group, etc., more preferably a hydrogen atom, a substituted or unsubstituted alkyl. A group, and when R ₆ and R ₇ , or n is 1 or more, they are bonded to each other at any R ₆ , R ₇ or R ₈ and have a 5- or 6-membered cyclic structure (eg thiophene ring, furan ring, cyclohexene ring) , Pyran ring, etc.) is also preferred.

R ₉ and R are preferably hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, cyano group, alkoxy group, amino group, acyl group, acylamino group, alkoxycarbonyl group, carboxyl group (meaning including —COOM), etc. More preferably, it is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a cyano group, an acyl group, an alkoxycarbonyl group, or a carboxyl group, but is bonded to R9 to form a 5- or 6-membered cyclic structure ( For example, imidazolidine-2,4-dione, oxazolidine-2,4-dione, 2-thioxothiazolidine-4-one, pyrazol-3-one, pyrazolotriazole, pyrazoloimidazole, pyrrole ring, etc.) Is also preferable.

Y is preferably —O— or —NR ₂₁ —, and most preferably —O—.

When Y is —S (O) _m —, m is preferably 0 or 2, and more preferably 0.

Z is preferably —CR ₂₂ R ₂₃ —.

R _{21 to} R ₂₃ preferably represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and more preferably a hydrogen atom or an alkyl group.

  M is preferably a hydrogen atom or a sodium salt, potassium salt, triethylammonium salt and the like, and more preferably a hydrogen atom or a sodium salt.

<< Compound Represented by Formula (2) >>
Next, general formula (2) will be described.

In the general formula (2), R _{1 to} R ₈ and R represent a hydrogen atom or a substituent, R ₁ and R ₂ , R ₂ and R _3, and R ₃ and R ₄ are bonded to each other to form a cyclic structure. N is an integer of 0 to 4, R _{6 to} R ₈ may be different from each other, and when n is 1 or more, they may be bonded to each other to form a cyclic structure, and Y is —O _{-, - S (O) m} - or -NR ₂₁ - represents, m represents an integer of 0 to 2, Z is -NR ₂₁ - or -CR ₂₂ R ₂₃ - represents, R ₂₁ to R ₂₃ are hydrogen An atom or a substituent is represented, and M represents a hydrogen atom or a salt-forming cation.

R _{1 to} R ₈ , R _{21 to} R ₂₃ , R, Y, Z, m, n, and M mentioned here have the same meaning as in the general formula (1), and preferred explanations are also the same.

<< Compound Represented by Formula (3) >>
Next, general formula (3) will be described.

In the general formula (3), R _{1 to} R ₈ may represent a hydrogen atom or a substituent, and R ₁ and R ₂ , R ₂ and R _3, and R ₃ and R ₄ may be bonded to each other to form a cyclic structure. , N is an integer of 0 to 4, R _{6 to} R ₈ may be different from each other, and when n is 1 or more, they may be bonded to each other to form a cyclic structure, and A is a 5 or 6 member Y represents —O—, —S (O) _m — or —NR ₂₁ —, m represents an integer of 0 to 2, and Z represents —NR ₂₁ — or —CR ₂₂ R ₂₃ —. R _{21 to} R _{23 each} represents a hydrogen atom or a substituent, contains at least one —COOM group in the molecule, and M represents a hydrogen atom or a salt-forming cation.

The term _{R 1 ~R 8, R 21 ~R} 23, Y, Z, m, n and M are as in formula (1) synonymous.

  Examples of the 5- or 6-membered heterocyclic ring represented by A include thiazole, benzothiazole, oxazole, benzoxazole, selenazole, benzoselenazole, indole, phenylxanthene, thiophene, furan, and imidazole described in the above heterocyclic ring. In addition, cyclopentane-1,3-dione, cyclopentene-1,3-dione, cyclohexane-1,3-dione, imidazolidine ring (for example, imidazolidine-2,4-dione), and oxazolidine ring (for example, oxazolidine) -2,4-dione), thiazolidine ring (eg 2-thioxothiazolidine-4-one), pyrazolidine ring (eg pyrazolidine-3,5-dione), thiazole (eg thiazol-5-one) ring, pyrazole ring ( For example, pyrazol-3-one), pyrazo Triazole ring, pyrazolotriazole imidazole ring, pyrazolotetrazole ring, pyrrole ring and the like.

Preferable examples of R _{1 to} R ₈ , R _{21 to} R ₂₃ , Y, Z, m, n, and M include the same as those described in the general formula (1).

  A is preferably cyclopentene-1,3-dione, imidazolidine-2,4-dione, oxazolidine-2,4-dione, 2-thioxothiazolidine-4-one, pyrazol-3-one, pyrazolotriazole, pyra Examples include zoloimidazole and pyrrole ring, and more preferable examples include 2-thioxothiazolidine-4-one, pyrazol-3-one, pyrazolotriazole, pyrazoloimidazole, and pyrrole ring.

<< Compound Represented by Formula (4) >>
Next, general formula (4) will be described.

In the general formula (4), R _{1 to} R ₈ may represent a hydrogen atom or a substituent, and R ₁ and R ₂ , R ₂ and R _3, and R ₃ and R ₄ may be bonded to each other to form a cyclic structure. , n is an integer from 0 to 4, may be different each R6 to R8, when n is 1 or more may be bonded to form a cyclic structure with each other, R ₁₀ and R ₁₁ substituents the stands, Y is -O -, - S (O) m - or -NR ₂₁ - represents, m represents an integer of 0 to 2, Z is -NR ₂₁ - or -CR ₂₂ R ₂₃ - represents, R _{21 to} R ₂₃ each represents a hydrogen atom or a substituent, contains at least one —COOM group in the molecule, and M represents a hydrogen atom or a salt-forming cation.

The term _{R 1 ~R 8, R 21 ~R} 23, Y, Z, m, n and M are as in formula (1) synonymous.

The substituent represented by R ₁₀ and R ₁₁ in the general formula (4) is also synonymous with the general formula (1).

In the general formula (4), preferable examples of R _{1 to} R ₈ , R _{21 to} R ₂₃ , Y, Z, m, n, and M include the same as those described in the general formula (1).

In the general formula (3), R ₁₀ and R ₁₁ are preferably substituted or unsubstituted alkyl groups, aryl groups, heterocyclic groups, amino groups, acylamino groups, alkoxy groups, alkenyl groups, alkoxycarbonyl groups, cyano groups, carboxyl groups. (Means including -COOM), and more preferably a substituted or unsubstituted alkyl group, aryl group, alkenyl group, or carboxyl group.

<< Compound Represented by Formula (5) >>
Next, general formula (5) will be described.

In the general formula (5), R _{1 to} R ₈ may represent a hydrogen atom or a substituent, and R ₁ and R ₂ , R ₂ and R _3, and R ₃ and R ₄ may be bonded to each other to form a cyclic structure. , N is an integer from 0 to 4, R 6 to R 8 may be different from each other, and when n is 1 or more, they may be bonded to each other to form a cyclic structure, and B ₁ or B ₂ are each independently represents -CR ₁₃ = or -N = and, R ₁₂ and R ₁₃ represents a substituent, Y is -O -, - S (O) m - or -NR ₂₁ - represents, m is 0 to 2 represents an integer, Z is -NR ₂₁ - or -CR ₂₂ R ₂₃ - represents, R ₂₁ to R ₂₃ represents a hydrogen atom or a substituent, at least one contains a -COOM group in a molecule, M is Represents a hydrogen atom or a salt-forming cation.

The term _{R 1 ~R 8, R 21 ~R} 23, Y, Z, m, n and M are as in formula (1) synonymous.

The substituent represented by R ₁₂ in the general formula (5) is also synonymous with the general formula (1).

In the general formula (5), when B ₁ and B ₂ are —CR ₁₃ ═, the substituent represented by R ₁₃ has the same meaning as in the general formula (1).

More specifically, the compound represented by the general formula (5) has a partial structure of four kinds of condensed rings represented by the following general formulas (5-1) to (5-4) due to the difference between B ₁ and B _2. It is possible to take it (in this case, it binds to the methine chain at *). In these structures, the substituents of R ₁₂ and R ₁₃ have the same meanings as described in the general formula (1) as described above, and in the general formula (5-3), each R ₁₃ is independently the same or different substituent. It may be a group.

Further, the same meaning as R ₁₀ and R ₁₁ in the general formula (4) is the preferred group.

In the general formula (5), preferable examples of R _{1 to} R ₈ , R _{21 to} R ₂₃ , Y, Z, m, n, and M include the same as those described in the general formula (1).

B ₁ and B ₂ are preferably when B ₁ is —CR ₁₃ ═, and R ₁₃ is preferably the same as R ₁₀ and R _{11 in} formula (4), and is a substituted or unsubstituted alkyl group or aryl group A heterocyclic group, an amino group, an acylamino group, an alkoxy group, an alkenyl group, an alkoxycarbonyl group, a carboxyl group (meaning including —COOM), and more preferably a substituted or unsubstituted alkyl group, aryl group, alkenyl group. , A carboxyl group. More preferably when B ₁ is at -CR ₁₃ = B ₂ is -N =.

<< Compound Represented by Formula (6) >>
Next, general formula (6) will be described.

In the general formula (6), R ₁ and R ₂ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, R _{2 to} R ₆ represent a hydrogen atom or a substituent, and R ₁ and R ₂ are bonded to each other. And may form a cyclic structure, or may combine with R ₃ or R ₄ to form a cyclic structure, R _{7 to} R ₉ represent a hydrogen atom or a substituent, and n is an integer of 0 to 2. , N may be different from each other or may be bonded to each other to form a cyclic structure, R ₁₀ and R ₁₁ represent a substituent, R ₁₃ represents a hydrogen atom or a substituent, and Y Represents —O—, —S (O) _m — or —NR ₂₁ —, m represents an integer of 0 to 2, Z represents —NR ₂₁ — or —CR ₂₂ R ₂₃ —, and R _{21 to} R ₂₃ represents a hydrogen atom or a substituent, contains at least one —COOM group in the molecule, and M represents a hydrogen atom or a salt-forming cation.

The term _{R 1 ~R 8, R 21 ~R} 23, Y, Z, m, n and M are as in formula (1) synonymous.

Moreover, R < ₁₂ > -R < ₁₃ > is synonymous with General formula (5).

Furthermore, preferred groups _{R 1 ~R 8, R 21 ~R} 23, Y, Z, m, in the n and M are the same as in the general formula (1), preferred groups in R ₁₂ and R ₁₃ of the general formula (5 And a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, an amino group, an acylamino group, an alkoxy group, an alkenyl group, an alkoxycarbonyl group, a carboxyl group (meaning including —COOM), and the like. More preferred are a substituted or unsubstituted alkyl group, aryl group, alkenyl group, and carboxyl group.

<< Compound Represented by Formula (7) >>
Next, general formula (7) will be described.

In the general formula (7), R ₀₁ and R ₀₂ represent a hydrogen atom, an alkyl, an aryl group or a heterocyclic group, and R ₀₁ or R ₀₂ and R ₁ or R ₃ , R in the general formulas (1) to (6) ₀₁ or R ₀₂ and R ₂ or R ₄ in formulas (1) to (6) may be bonded to each other to form a cyclic structure.

In the general formula (7), examples of the aryl group represented by R ₀₁ or R ₀₂ include a phenyl group, a naphthyl group, a p-tolyl group, an m-chlorophenyl group, and an o-hexadecanoylaminophenyl group. .

In the general formula (7), the heterocyclic group represented by R ₀₁ or R ₀₂ can be a group derived from various conventionally known heterocyclic rings. Moreover, the hetero atom contained in this heterocyclic ring can be an oxygen atom, a sulfur atom, a nitrogen atom, etc., and the number of the hetero atoms contained in the ring is one or more (2-5) . When two or more heteroatoms are included in the ring, the heteroatoms may be the same or different. Further, the heterocyclic ring is condensed with a carbocyclic ring having 6 to 12 carbon atoms such as a benzene ring, a naphthalene ring or a cyclohexane ring, or another heterocyclic ring having 5 to 12 ring constituent elements (for example, a julolidine ring). May be. Specific examples of the heterocyclic ring include thiazole, benzothiazole, oxazole, benzoxazole, selenazole, benzoselenazole, indole, phenylxanthene, thiophene, furan, imidazole and the like.

R ₀₁ and R ₀₂ are preferably a hydrogen atom, an alkyl group, an aryl group or the like, more preferably an alkyl group or an aryl group, and the general formula (7) is represented by the general formulas (1) to (6). R ₂ or R ₃ is preferable, and in this case, R ₀₁ or R ₀₂ is bonded to R ₁ or R ₃ of the general formula (1) or R ₂ or R ₄ to form a 5- or 6-membered cyclic structure ( For example, it is preferable to form a pyrrolidine ring, a morpholine ring, a piperidine ring, a julolidine ring, etc.).

  Specific examples of the compounds represented by the general formulas (1) to (7) according to the present invention are shown below, but the present invention is not limited thereto.

  Examples of the compounds represented by the general formulas (1) to (7) according to the present invention include JP-A-6-135967, JP-A-6-211829, JP-A-6-306354, and JP-A-6. -329658, 2002-322169, J. Pat. Med. Chem. , 27 (9), 1127 (1984). Chem. Commu. , 11, 979 (2000), Synthesis, 2, 149 (1987), Can. J. et al. Chem. , 73 (9), 1506 (1995), etc., can be synthesized with reference to conventionally known methods.

  Although an example of a synthetic method is specifically shown below, other compounds can be synthesized in the same manner, and the synthetic method is not limited thereto.

Synthesis example 1
Synthesis of Exemplified Compound 14 1) Synthesis Route

2) Synthesis of Exemplified Compound 14 Toluene: 80 ml, morpholine: 0.98 g and intermediate 2: 0.78 g are added to intermediate 1: 3.49 g, and the mixture is heated under reflux for 2 hours. After completion of the reaction, the reaction solution was concentrated and recrystallized by adding 50 ml of acetonitrile to obtain 3.16 g of Exemplified Compound 14: It was identified by MASS, H-NMR, and IR spectrum, and confirmed to be the target product.

Synthesis example 2
Synthesis of Exemplary Compound 83 1) Synthesis route

2) Synthesis of Exemplified Compound 83 Addition of toluene: 100 ml, morpholine: 1.00 g and intermediate 4: 3.55 g to 2.99 g of Intermediate 3: Heat reflux reaction for 2 hours. After completion of the reaction, the reaction mixture was concentrated, purified by column with ethyl acetate / methanol solvent, and then recrystallized by adding acetonitrile to obtain Exemplary Compound 83 (4.59 g). It was identified by MASS, 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 (7), 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.

Further, the total content of each compound represented by the general formulas (1) to (7) 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 sensitizing treatment is performed using any one of the compounds represented by the general formulas (1) to (7) 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 (7) 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 (7) 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 (7) or using other sensitizing dye compounds in combination, 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 by including any 1 type of compound represented by the said General formula (1)-(7) about a semiconductor. 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 (7) 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 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.

  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, 5,350,644, 5,463,057, 5,525,440, JP-A-7-249750, JP 10-504512, World Patent 989/50393, etc. Ruthenium complex dyes are 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. 10-93118, 11-273754, JP-A 2000-106224, 2000-357809, 2001-52766, 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.

  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 (7) 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 to dissolve any one compound of the general formulas (1) to (7) 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 is baked in the solution containing any one compound of the general formulas (1) to (7) is such that the compound deeply enters the semiconductor layer (semiconductor film) and adsorbs it. From the viewpoint of sufficiently proceeding, sufficiently sensitizing the semiconductor, and suppressing degradation of the compound that is generated by decomposition of the compound in solution or the like 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.

  When immersed, the solution containing any one compound of the general formulas (1) to (7) may be used by heating to a temperature at which it does not boil as long as the compound does not decompose. 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.

  The photoelectric conversion element of the present invention is obtained by forming the semiconductor thin film on the conductive support 1 as shown in FIG. 1 using the plasma processing apparatus as described above, and then the general formula (1) according to the present invention. It is manufactured through a process of adsorbing any one compound represented by (7).

  Further, the surface area of the semiconductor thin film is increased, impurities on the surface of the semiconductor thin film are removed, the purity of the semiconductor is increased, and the semiconductor is formed from any one compound represented by the general formulas (1) to (7). 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 (7) 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 subjected to reduced pressure treatment or heat treatment to remove bubbles in the film, and any one compound represented by the general formulas (1) to (7) is converted into the 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 (7) is adsorbed to the semiconductor according to the present invention, it may be used alone or in combination. Furthermore, conventionally known sensitizing dye compounds (for example, U.S. Pat. Nos. 4,684,537, 4,927,721, 5,084,365, 5,350,644, No. 5,463,057, 5,525,440, JP-A-7-249790, JP-A-2000-150007, etc.) 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 types of dyes so that the wavelength range of photoelectric conversion can be widened and sunlight can be used as effectively as possible.

  The semiconductor for photoelectric conversion materials sensitized by using a plurality of compounds of any one of the general formulas (1) to (7) 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.

  For the adsorption treatment, a solution in which the compound is dissolved may be used at room temperature, or the solution may be heated 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
<< Production of Photoelectric Conversion Element 101 >>
A photoelectric conversion device as shown in FIG. 1 was produced as described below.

  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.

  Next, a solution in which 5 g of Exemplified Compound 1 was dissolved in 200 ml of methanol solution was prepared, and the above-mentioned film-like titanium oxide (semiconductor layer for photoelectric conversion material) was soaked with the support, and further 1 g of trifluoroacetic acid was added for over 2 hours. Sonication was applied. After the reaction, the film-like titanium oxide (semiconductor layer for photoelectric conversion material) was washed with chloroform and vacuum dried to prepare a photosensitive layer 2 (semiconductor for photoelectric conversion material).

  As the counter electrode 4, a transparent conductive glass plate coated with fluorine-doped tin oxide and further carrying platinum thereon is used, and the volume ratio is 1 between the conductive support 1 and the counter electrode 4. : A redox electrolyte in which tetrapropylammonium iodide and iodine were dissolved in a mixed solvent of acetonitrile / ethylene carbonate of 4 to a concentration of 0.46 mol / liter and 0.06 mol / liter, respectively. The charge transfer layer 3 was produced, and the photoelectric conversion element 1 was produced.

<< Preparation of Photoelectric Conversion Elements 102-130 >>: Present Invention Photoelectric conversion elements 102-130 were obtained in the same manner as in preparation of photoelectric conversion element 1, except that Exemplified Compound 1 was changed to the compounds shown in Table 1.

<< Preparation of Photoelectric Conversion Elements R1 and R2 >>: Comparative Example Photoelectric conversion elements R1 and R2 were obtained in the same manner as in the preparation of the photoelectric conversion element 1, except that the following comparison compounds R1 and R2 were used.

<< Preparation of Solar Cells SC-101 to SC-130 >>: After the side surface of the photoelectric conversion element 1 of the present invention is encapsulated with a resin, lead wires are attached to each of the solar cells SC-101 to SC-130 of the present invention. Lots were made one by one.

<< Production of Solar Cells SC-R1 and R2 >>: Comparative Example In the production of the above-described solar cell SC-1, solar cells SC-R1 and R2 were similarly manufactured except that comparative photoelectric conversion elements R1 and R2 were used. Three lots were prepared.

<< Evaluation of photoelectric conversion characteristics of solar cells >>
Solar cells SC-101 to SC-130 obtained above and solar cells SC-R1 and R2 are each 100 mW / m by solar simulator (manufactured by JASCO (JASCO), low energy spectral sensitivity measuring device CEP-25). The short-circuit current density Jsc (mA / cm ² ) and the open-circuit voltage value Voc (V) when irradiated with light having an intensity of ² were measured and shown in Table 1. The indicated value was the average value of the measurement results for three solar cells having the same configuration and production method.

From Table 1, the solar cell of the present invention exhibits higher photoelectric conversion characteristics than the comparison, and it is effective to use any one compound represented by the general formulas (1) to (7). I understand. In particular, it can be seen that the dyes represented by the general formulas (2), (4) and (6) are excellent. Moreover, the solar cells SC-101 to SC-130 of the present invention are excellent in stability because no decrease in photoelectric conversion efficiency is observed even after 100 hours of light irradiation of 100 mW / m ² by a solar simulator. Became clear.

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 (11)

The semiconductor for photoelectric conversion materials characterized by including the pigment | dye represented by following General formula (1).

(Wherein R _{1 to} R ₉ and R represent a hydrogen atom or a substituent, R ₁ and R ₂ , R ₂ and R ₃ , R ₃ and R _4, and R ₉ and R are bonded to each other to form a cyclic structure. N is an integer from 0 to 4, R _{6 to} R ₈ may be different from each other, and when n is 1 or more, they may be bonded to each other to form a cyclic structure. -O -, - S (O) m - or -NR ₂₁ - represents, m represents an integer of 0 to 2, Z is -NR ₂₁ - or -CR ₂₂ R ₂₃ - represents, R ₂₁ to R ₂₃ Represents a hydrogen atom or a substituent, contains at least one -COOM group in the molecule, and M represents a hydrogen atom or a salt-forming cation.) The semiconductor for photoelectric conversion materials characterized by including the pigment | dye represented by General formula (2).

(Wherein R _{1 to} R ₈ and R represent a hydrogen atom or a substituent, R ₁ and R ₂ , R ₂ and R _3, and R ₃ and R ₄ may be bonded to each other to form a cyclic structure; n is an integer of 0 to 4, R _{6 to} R ₈ may be different from each other, and when n is 1 or more, they may be bonded to each other to form a cyclic structure, and Y is —O—, — S (O) _m — or —NR ₂₁ —, m represents an integer of 0 to 2, Z represents —NR ₂₁ — or —CR ₂₂ R ₂₃ —, and R _{21 to} R ₂₃ represent a hydrogen atom or a substituent. Represents a group, and M represents a hydrogen atom or a salt-forming cation.) The semiconductor for photoelectric conversion materials characterized by including the pigment | dye represented by General formula (3).

(Wherein R _{1 to} R ₈ represent a hydrogen atom or a substituent, R ₁ and R ₂ , R ₂ and R ₃ and R ₃ and R ₄ may be bonded to each other to form a cyclic structure, and n is R is an integer of 0 to 4, R _{6 to} R ₈ may be different from each other, and when n is 1 or more, they may be bonded to each other to form a cyclic structure, and A is a 5- or 6-membered heterocyclic ring the stands, Y is -O -, - S (O) m - or -NR ₂₁ - represents, m represents an integer of 0 to 2, Z is -NR ₂₁ - or -CR ₂₂ R ₂₃ - represents, R _{21 to} R ₂₃ represent a hydrogen atom or a substituent, and at least one —COOM group is contained in the molecule, and M represents a hydrogen atom or a salt-forming cation.) The semiconductor for photoelectric conversion materials characterized by including the pigment | dye represented by General formula (4).

(Wherein R _{1 to} R ₈ represent a hydrogen atom or a substituent, R ₁ and R ₂ , R ₂ and R ₃ and R ₃ and R ₄ may be bonded to each other to form a cyclic structure, and n is R _{6 to} R ₈ may be different from each other, and when n is 1 or more, they may be bonded to each other to form a cyclic structure, and R ₁₀ and R ₁₁ may be substituted. Y represents —O—, —S (O) _m — or —NR ₂₁ —, m represents an integer of 0 to 2, Z represents —NR ₂₁ — or —CR ₂₂ R ₂₃ —, R ₂₁ to R ₂₃ represents a hydrogen atom or a substituent, at least one contains a -COOM group in a molecule, M represents a hydrogen atom or a salt-forming cation.) The semiconductor for photoelectric conversion materials characterized by including the pigment | dye represented by General formula (5).

(Wherein R _{1 to} R ₈ represent a hydrogen atom or a substituent, R ₁ and R ₂ , R ₂ and R ₃ and R ₃ and R ₄ may be bonded to each other to form a cyclic structure, and n is R _{6 to} R ₈ may be different from each other, and when n is 1 or more, they may be bonded to each other to form a cyclic structure, and B ₁ or B ₂ are each independently represents -CR ₁₃ = or -N = Te, R ₁₂ and R ₁₃ represents a substituent, Y is -O -, - S (O) m - or -NR ₂₁ - represents, m is 0 to 2 Represents an integer, Z represents —NR ₂₁ — or —CR ₂₂ R ₂₃ —, R _{21 to} R ₂₃ each represents a hydrogen atom or a substituent, contains at least one —COOM group in the molecule, and M represents hydrogen. Represents an atom or a salt-forming cation.) The semiconductor for a photoelectric conversion material according to claim 5, wherein the general formula (5) is a dye represented by the following general formula (6).

(Wherein R _{1 to} R ₈ represent a hydrogen atom or a substituent, R ₁ and R ₂ , R ₂ and R ₃ and R ₃ and R ₄ may be bonded to each other to form a cyclic structure, and n is R _{6 to} R ₈ may be different from each other, and when n is 1 or more, they may be bonded to each other to form a cyclic structure, and R ₁₂ and R ₁₃ represent a substituent. Y represents —O—, —S (O) _m — or —NR ₂₁ —, m represents an integer of 0 to 2, Z represents —NR ₂₁ — or —CR ₂₂ R ₂₃ —, R ₂₁ to R ₂₃ represents a hydrogen atom or a substituent, at least one contains a -COOM group in a molecule, M represents a hydrogen atom or a salt-forming cation.) In said general formula (1)-(6), R < ₂ > or R < ₃ > is following General formula (7), The semiconductor for photoelectric conversion materials of any one of Claims 1-6 characterized by the above-mentioned.

(In the formula, R ₀₁ and R ₀₂ represent a hydrogen atom, an alkyl, an aryl group or a heterocyclic group, and R ₀₁ or R ₀₂ and R ₁ or R ₃ , R ₀₁ or R in the general formulas (1) to (6)) ₀₂ and R ₂ or R ₄ in the general formulas (1) to (6) may be bonded to each other to form a cyclic structure.) 8. The semiconductor for a photoelectric conversion material according to claim 1, wherein Y is an oxygen atom and Z is —CR ₂₂ R ₂₃ — in the general formulas (1) to (6). .
(However, R ₂₂ and R ₂₃ represent a hydrogen atom or a substituent.) The semiconductor for photoelectric conversion materials according to any one of claims 1 to 8, wherein the semiconductor for photoelectric conversion materials is a metal oxide or a metal sulfide semiconductor. The photoelectric conversion element characterized by the layer containing the semiconductor for photoelectric conversion materials of any one of Claims 1-9 being provided on the electroconductive support body. A solar cell comprising the photoelectric conversion element according to claim 10, a charge transfer layer, and a counter electrode.

Images