JP2015233110A - Dye for dye-sensitized solar batteries, semiconductor layer, and dye-sensitized solar battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a dye for dye-sensitized solar batteries which has a superior photoelectric conversion property; a semiconductor layer having a superior photoelectric conversion efficiency and increased in its sensitivity by such a dye for dye-sensitized solar batteries; and a dye-sensitized solar battery arranged by use of such a semiconductor layer.SOLUTION: A dye for dye-sensitized solar batteries comprises a material expressed by the general formula (1). A semiconductor layer is increased in its sensitivity by the dye. A dye-sensitized solar battery comprises the semiconductor layer.

Description

  The present invention relates to a dye for a dye-sensitized solar cell, a semiconductor layer, and a dye-sensitized solar cell.

  Global warming due to the increase in carbon dioxide concentration caused by the use of large amounts of fossil fuels, and the increase in energy demand accompanying population growth are recognized as problems related to the survival of humankind. Therefore, in recent years, the use of sunlight that does not generate infinite and harmful substances has been energetically studied. Examples of solar energy that is currently used as a clean energy source include residential single crystal silicon, polycrystalline silicon, amorphous silicon, and inorganic solar cells such as cadmium telluride and indium copper selenide.

  However, these inorganic solar cells also have drawbacks. For example, a silicon system is required to have a very high purity. Naturally, the purification process is complicated, the number of processes is large, and the manufacturing cost is high. In addition, there is a demand for weight reduction and the like, and in particular, it is disadvantageous in terms of long payback to the user, and there has been a problem in the spread.

  On the other hand, many solar cells using organic materials have been proposed. As an organic solar cell, a Schottky photoelectric conversion element that joins a p-type organic semiconductor and a metal having a low work function, a p-type organic semiconductor and an n-type inorganic semiconductor, or a p-type organic semiconductor and an electron-accepting organic compound are joined. There are heterojunction photoelectric conversion elements, and organic semiconductors used are synthetic dyes and pigments such as chlorophyll and perylene, conductive polymer materials such as polyacetylene, or composite materials thereof. These are thinned by a vacuum deposition method, a casting method, a dipping method, or the like to form a battery material. Although organic materials have advantages such as low cost and easy area enlargement, photoelectric conversion efficiency is often as low as 1% or less, and there is a problem that durability is poor.

  Under such circumstances, a solar cell exhibiting good characteristics has been reported by Dr. Gretzell of Switzerland (see, for example, Non-Patent Document 1). This document also discloses materials and manufacturing techniques necessary for battery fabrication. This solar cell is called a dye-sensitized solar cell or a Gretzel solar cell, and is a wet solar cell using a titanium oxide porous thin film spectrally sensitized with a ruthenium complex (hereinafter referred to as Ru complex) as a working electrode. The advantage of this method is that it is not necessary to purify inexpensive semiconductors such as titanium oxide to high purity, so that the manufacturing cost can be reduced compared to the inorganic solar cells described above, and the available light is in the visible light region. Because it is widespread, it is possible to effectively convert sunlight, which has a high energy intensity in the visible light region, into electricity.

  However, since noble metal Ru, which has resource limitations, is used, there is a possibility that a problem may occur in the stable supply of the Ru complex when a dye-sensitized solar cell is put into practical use. In addition, due to this resource limitation, the Ru complex itself is expensive, and there may be a problem in terms of cost during mass production. In order to solve such a problem, various proposals have been made for the purpose of changing at least part of the Ru complex to a cheaper organic dye. For example, various merocyanine dyes, cyanine dyes, 9-phenylxanthene dyes, coumarin dyes, and the like have been disclosed. However, these are considerably inferior to Ru complexes in photoelectric conversion characteristics, and are practical. Most of them were poor (see, for example, Patent Documents 1 to 4).

  Recently, organic dyes having high performance comparable to Ru complexes are being disclosed as dye-sensitized solar cell dyes (see, for example, Patent Documents 5 to 16), but practical solar cells are manufactured. From the viewpoint, further improvement is required.

JP 11-238905 A JP 2001-76773 A Japanese Patent Laid-Open No. 10-92477 International Publication No. 2002/045199 Pamphlet International Publication No. 2004/011555 Pamphlet JP 2005-19252 A JP 2006-286609 A JP 2007-48672 A JP 2007-48680 A JP 2007-95584 A JP 2007-115673 A JP 2008-16383 A JP 2008-71648 A International Publication No. 2010/016612 Pamphlet JP 2008-204785 A JP 2013-35936 A

Nature, 353, 737 (1991)

  The subject of this invention is providing the pigment | dye for dye-sensitized solar cells which has the outstanding photoelectric conversion characteristic, the semiconductor layer and dye-sensitized solar cell which have the outstanding photoelectric conversion efficiency.

  As a result of intensive studies, the present inventor used a dye for a dye-sensitized solar cell represented by the general formula (1) (hereinafter referred to as “dye”), a semiconductor layer sensitized with the dye, and the semiconductor layer. The above-mentioned problem could be solved by the dye-sensitized solar cell.

In the general formula (1), X represents an oxygen atom or a sulfur atom. R ₁₁ and R ₁₂ represent a hydrogen atom or an alkyl group, and both may combine to form a cyclopentane ring or a cyclohexane ring. L ₁₁ represents a methine group unit. A represents an organic residue having at least one acidic group having a pKa of less than 6 and having an atomic group necessary for forming a dye structure.

  The dye represented by the general formula (1) has excellent photoelectric conversion characteristics. By sensitizing with this dye, a semiconductor layer and a dye-sensitized solar cell having excellent photoelectric conversion efficiency are obtained. Can do.

The dye of the present invention is described in detail below. In the general formula (1), X represents an oxygen atom or a sulfur atom. R ₁₁ and R ₁₂ are each a hydrogen atom or an alkyl group (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, A pentadecyl group, etc.), which may be linked to form a cyclopentane ring or a cyclohexane ring. Among them, preferred are those in which they are linked to form a cyclopentane ring or a cyclohexane ring, and particularly preferred are those in which both are linked to form a cyclopentane ring.

L ₁₁ represents a methine group unit. The methine group unit is specifically composed of a methine chain having an odd number of carbon atoms, and the number of carbon atoms is preferably 1 or 3, and a monomethine group having 1 carbon atom is particularly preferable.

  A represents an organic residue having at least one acidic group having a pKa of less than 6 and having an atomic group necessary for forming a dye structure. Examples of the acidic group having a pKa of less than 6 include a carboxy group, a sulfo group, a sulfino group, a sulfeno group, a phosphono group, and a phosphinico group. Among these, a carboxy group is particularly preferable. The acidic group having a pKa of less than 6 may be a free acid, and a salt (for example, ammonium salt such as ammonium salt, trimethylammonium salt, triethylammonium salt, tetra-n-butylammonium salt, lithium salt, Alkali metal salts such as sodium salts and potassium salts).

  Moreover, as an example of the organic residue which has an atomic group required in order to form the pigment | dye structure of A, the thing like the structure shown below is mentioned as a preferable example, for example.

In the general formula (2), R ₂₁ is an aliphatic group having an acidic group having a pKa of less than 6 as a substituent (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group). Group, octyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, alkyl group such as pentadecyl group, alkenyl group such as allyl group, butenyl group, alkynyl group such as propargyl group, benzyl group, phenethyl group, phenylpropyl group , Phenylbutyl group, 1-naphthylmethyl group, aralkyl group such as 2-naphthylmethyl group, etc.) and aromatic group (for example, phenyl group, tolyl group, naphthyl group, etc.). Among them, preferred is an alkyl group having 4 or less carbon atoms having an acidic group having a pKa of less than 6 as a substituent, and more preferred is an alkyl group having 2 or less carbon atoms having a carboxy group as a substituent. A carboxymethyl group is particularly preferred. This carboxy group may be either a free acid or a salt as described above.

In the general formula (3), R ₃₁ is an aliphatic group having the acidic group having a pKa of less than 6 as a substituent (synonymous with the aliphatic group of R ₂₁ ), an aromatic group (the aromatic of R ₂₁ Represents the same meaning). Note The _{R 31} has the same meaning as _{R 21} in the general formula (2).

R ₃₂ is an aliphatic group (synonymous with the aliphatic group of R ₂₁ ), an aromatic group (synonymous with the aromatic group of R ₂₁ ), a heterocyclic group (eg, indolyl group, pyridyl group, furyl group, thienyl group). Etc.). If possible, these may be substituted with various known substituents such as alkoxy, aryloxy, alkylthio, arylthio, hydroxy, carboxy, alkoxycarbonyl, aryloxycarbonyl, halogen atoms, etc. May be. Preferred among R ₃₂ described above are linear or branched alkyl groups having no substituents having 1 to 14 carbon atoms, aralkyl groups having 7 to 15 carbon atoms in total, and those having 3 to 18 carbon atoms. It is a linear alkyl group substituted at the end with a carboxy group, and in particular, a linear or branched alkyl group having no substituent having 6 to 12 carbon atoms, an aralkyl group having 7 to 10 carbon atoms in total A linear alkyl group in which a terminal having 5 to 15 carbon atoms is substituted with a carboxy group is particularly preferable. This carboxy group may be either a free acid or a salt as described above.

In the general formula (4), R ₄₁ is an aliphatic group having the acidic group having a pKa of less than 6 as a substituent (synonymous with the aliphatic group of R ₂₁ ), an aromatic group (the aromatic of R ₂₁ Represents the same meaning). R ₄₁ has the same meaning as R ₂₁ in the general formula (2).

R ₄₂ and R ₄₃ are an aliphatic group (synonymous with the aliphatic group of R ₂₁ ), an aromatic group (synonymous with the aromatic group of R ₂₁ ), a heterocyclic group (synonymous with the heterocyclic group of R ₃₂ ). Represents. Note The _{R 42} has the same meaning as _{R 32} in the general formula (3).

R ₄₃ is preferably an aliphatic group having 6 or less carbon atoms. Among them, an alkyl group having 3 or less carbon atoms is particularly preferable.

  In the general formula (5), M is a cation capable of forming a salt with a hydrogen atom or a carboxy group (for example, ammonium cation such as ammonium, trimethylammonium, triethylammonium, tetra-n-butylammonium, lithium, sodium, potassium, etc. Represents an alkali metal cation).

In the general formula (6), R ₆₁ is an aliphatic group having the acidic group having a pKa of less than 6 as a substituent (synonymous with the aliphatic group of R ₂₁ ), an aromatic group (the aromatic of R ₂₁ Represents the same meaning). Note The _{R 61} has the same meaning as _{R 21} in the general formula (2).

In the general formula (7), R ₇₁ is an aliphatic group having the acidic group having a pKa of less than 6 as a substituent (synonymous with the aliphatic group of R ₂₁ ), an aromatic group (the aromatic of R ₂₁ Represents the same meaning). Note The _{R 71} has the same meaning as _{R 21} in the general formula (2).

R ₇₂ represents an aliphatic group (synonymous with the aliphatic group of R ₂₁ ), an aromatic group (synonymous with the aromatic group of R ₂₁ ), or a heterocyclic group (synonymous with the heterocyclic group of R ₃₂ ). Of these, an aliphatic group having 6 or less carbon atoms or a phenyl group is preferable.

In the general formula (8), R ₈₁ is an aliphatic group (synonymous with the aliphatic group of R ₂₁ ), an aromatic group (synonymous with the aromatic group of R ₂₁ ), a heterocyclic group (the R ₃₂ Represents the same as the heterocyclic group. Of these, an alkyl group having 6 or less carbon atoms or a phenyl group is preferable. In addition, when R ₈₂ described below is not a carboxy group, R ₈₁ must have an acidic group (preferably a carboxy group) having a pKa of less than 6 as a substituent.

R ₈₂ represents an aliphatic group (synonymous an aliphatic group of the _{R 21),} an aromatic group (synonymous to the aromatic group of the _{R 21),} a Hajime Tamaki (synonymous to the heterocyclic group of said _{R 32),} a carboxy group Represents. Of these, an alkyl group or carboxy group having 4 or less carbon atoms is preferred, and a carboxy group is particularly preferred. A particularly preferable combination of R ₈₁ and R ₈₂ described above is an alkyl group or phenyl group having 6 or less carbon atoms, in which R ₈₁ does not have an acidic group having a pKa of less than 6, and R _82. Is a carboxy group.

In the general formula (9), R ₉₁ is an aliphatic group having the acidic group having a pKa of less than 6 as a substituent (synonymous with the aliphatic group of R ₂₁ ), an aromatic group (the aromatic of R ₂₁ Represents the same meaning). This R ₉₁ is synonymous with R ₂₁ in the general formula (2).

R ₉₂ represents an aliphatic group (synonymous with the aliphatic group of R ₂₁ ), an aromatic group (synonymous with the aromatic group of R ₂₁ ), or a heterocyclic group (synonymous with the heterocyclic group of R ₃₂ ). R ₉₂ has the same meaning as R ₇₂ in the general formula (7).

In the general formula (10), R ₁₀₁ represents an aliphatic group having the acidic group having a pKa of less than 6 as a substituent (synonymous with the aliphatic group of R ₂₁ ), an aromatic group (the aromatic of R ₂₁ Represents the same meaning). In addition, this R ₁₀₁ is synonymous with R ₂₁ in the general formula (2).

R ₁₀₂ represents an aliphatic group (synonymous an aliphatic group of the _{R 21),} aromatic group (synonymous to the aromatic group of the _{R 21),} a Hajime Tamaki (synonymous to the heterocyclic group of said _{R 32).} This R ₁₀₂ is synonymous with R ₃₂ in the general formula (3).

In the general formula (11), R ₁₁₁ is an aliphatic group having the acidic group having a pKa of less than 6 as a substituent (synonymous with the aliphatic group of R ₂₁ ), an aromatic group (the aromatic of R ₂₁ Represents the same meaning). R ₁₁₁ has the same meaning as R ₂₁ in the general formula (2).

R ₁₁₂ represents an aliphatic group (synonymous with the aliphatic group of R ₂₁ ), an aromatic group (synonymous with the aromatic group of R ₂₁ ), or a heterocyclic group (synonymous with the heterocyclic group of R ₃₂ ). R ₁₁₂ has the same meaning as R ₃₂ in the general formula (3).

R ₁₁₃ represents an aliphatic group (synonymous an aliphatic group of the _{R 21),} an aromatic group (synonymous to the aromatic group of the _{R 21),} a Hajime Tamaki (synonymous to the heterocyclic group of said _{R 32).} R ₁₁₃ has the same meaning as R ₇₂ in the general formula (7).

  Among the above-mentioned A, those more preferable in the present invention are those represented by the general formula (2), the general formula (3), the general formula (4), and the general formula (5), and among them, the general formula What is shown by (3) is especially preferable.

  In the general formula (1) described in detail above, the molecular structure may further have a substituent well known in the art.

Note the double bond linking site of the general formula (1) in _{L 11} and A, further general formula (3), the general formula (4), the general formula (10), the double bond of the heterocyclic rings in formula (11) In the linking site, Z-type and E-type geometric isomers may be generated in each site, but in the present invention, any combination of these geometric isomers may be used. In addition, when L ₁₁ is a methine group unit having 3 or more carbon atoms, isomers of geometric structures for each carbon double bond (cis type, trans type) may be generated, but in the present invention, Any combination of these geometric isomerisms may be used.

When R ₁₂ and R ₁₃ in the general formula (1) are both alkyl groups, the carbon atoms at the 2-position and 3-position of the indoline ring to which R ₁₂ and R ₁₃ are respectively bonded are asymmetric carbons, There is a possibility that stereoisomers at each site may be generated, but in the present invention, any combination of these stereoisomers may be used.

  Specific examples of the dye of the present invention in the case where A in the general formula (1) is represented by the general formula (2) will be given below, but the present invention is not limited thereto.

  Next, specific examples of the dye of the present invention when A in the general formula (1) is represented by the general formula (3) will be given, but the present invention is not limited to these examples.

  Next, specific examples of the dye of the present invention when A in the general formula (1) is represented by the general formula (4) will be given, but the present invention is not limited to these examples.

  Next, specific examples of the dye of the present invention when A in the general formula (1) is represented by the general formula (5) will be given, but the present invention is not limited to these examples.

  Next, specific examples of the dye of the present invention in the case where A in the general formula (1) is represented by the general formula (6) to the general formula (11) will be given, but the present invention is not limited thereto.

  These compounds can be easily synthesized with reference to synthesis methods described in, for example, JP-A-8-269345 and WO 2004/011555.

  The dye-sensitized solar cell includes a conductive support, a semiconductor layer (semiconductor electrode) sensitized with a dye provided on the surface of the conductive support, a charge transfer layer, and a counter electrode. The semiconductor layer of the present invention is a semiconductor layer sensitized with the dye represented by the general formula (1). The dye-sensitized solar cell of the present invention has a semiconductor layer sensitized with the dye represented by the general formula (1). The semiconductor layer may be a single layer structure or a stacked structure, and is designed according to the purpose. In addition, at the boundary of this element such as the boundary between the conductive layer and the semiconductor layer of the conductive support, the boundary between the semiconductor layer and the moving layer, the constituent components of each layer may diffuse or mix with each other.

  As the conductive support, there can be used a support made of glass or plastic having a conductive layer containing a conductive agent on its surface, such as a metal having a conductive property in itself. In the latter case, the conductive agent is a metal oxide such as platinum, gold, silver, copper, aluminum or the like, carbon or indium-tin composite oxide (hereinafter abbreviated as “ITO”), fluorine-doped tin oxide or the like. And the like (hereinafter abbreviated as “FTO”). The conductive support preferably has a transparency that transmits light of 10% or more, and more preferably transmits 50% or more. Among these, conductive glass in which a conductive layer made of ITO or FTO is deposited on glass is particularly preferable.

  For the purpose of reducing the resistance of the transparent conductive support, a metal lead wire may be used. Examples of the material of the metal lead wire include metals such as aluminum, copper, silver, gold, platinum, and nickel. A metal lead wire is placed on a transparent conductive support by vapor deposition, sputtering, pressure bonding, etc., and ITO or FTO is provided thereon, or a metal lead wire is placed on a transparent substrate having conductivity on the surface. There is.

  Examples of the semiconductor contained in the semiconductor layer include a single semiconductor such as silicon and germanium, a compound semiconductor typified by a metal chalcogenide, or a compound having a perovskite structure. 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, bismuth. And sulfides, cadmium, selenide of lead, telluride of cadmium, and the like. Other compound semiconductors are preferably phosphides such as zinc, gallium, indium, cadmium, gallium arsenide, copper-indium-selenide, copper-indium-sulfide, and the like. As the compound having a perovskite structure, strontium titanate, calcium titanate, sodium titanate, barium titanate, potassium niobate and the like are preferable.

  The semiconductor used in the present invention may be single crystal or polycrystalline. From the viewpoint of photoelectric conversion efficiency, a single crystal is preferable, but from the viewpoint of manufacturing costs, securing raw materials, etc., a polycrystal is preferable. The particle size of the semiconductor is preferably 2 nm or more and 1 μm or less.

  As a method of forming a semiconductor layer on a conductive support, there are a method of applying a dispersion or colloidal solution of semiconductor fine particles on a conductive support, a sol-gel method, and the like. As a method for producing a dispersion, a sol-gel method, a method of mechanically pulverizing with a mortar, a method of dispersing while pulverizing using a mill, or a fine particle in a solvent when synthesizing a semiconductor, The method of using it as it is is mentioned.

  In the case of a dispersion prepared by mechanical pulverization or pulverization using a mill, the dispersion is prepared by dispersing at least semiconductor fine particles alone or a mixture of semiconductor fine particles and a resin in water or an organic solvent. Resins used include polyalkyleneoxy compounds, polymers and copolymers of vinyl compounds such as styrene, vinyl acetate, acrylic acid esters, methacrylic acid esters, silicone resins, phenoxy resins, polysulfone resins, polyvinyl butyral resins, polyvinyl resins. Formal resin, polyester resin, cellulose ester resin, cellulose ether resin, urethane resin, phenol resin, epoxy resin, polycarbonate resin, polyarylate resin, polyamide resin, polyimide resin and the like can be mentioned.

  As the medium for dispersing the semiconductor fine particles, alcohol media such as water, methanol, ethanol, or isopropyl alcohol, ketone media such as acetone, acetylacetone, methyl ethyl ketone, or methyl isobutyl ketone, ethyl formate, ethyl acetate, or n-acetate Ester media such as butyl, ether media such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxolane, or dioxane, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, or N-methyl-2-pyrrolidone Medium, dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o-dichlorobenzene, fluoro Halogenated hydrocarbon media such as benzene, bromobenzene, iodobenzene or 1-chloronaphthalene, n-pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, methylcyclohexane, cyclohexadiene, benzene, Examples thereof include hydrocarbon-based media such as toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, and cumene. These can be used alone or as a mixed medium of two or more.

  Examples of the dispersion application method include a roller method, a dip method, an air knife method, a blade method, a wire bar method, a slide hopper method, an extrusion method, a curtain method, a spin method, and a spray method.

  The semiconductor layer may be a single layer or multiple layers. In the case of multiple layers, a dispersion of semiconductor fine particles having different particle diameters can be applied in multiple layers, or different types of semiconductors, and application layers having different compositions of resins and additives can be applied in multiple layers. In addition, when the film thickness is insufficient with a single coating, the multilayer coating is an effective means.

  In general, as the thickness of the semiconductor layer increases, the amount of supported dye increases per unit projected area and the light capture rate increases. However, the diffusion distance of the generated electrons also increases, and the recombination of charges also increases. End up. Therefore, the film thickness of the semiconductor layer is preferably 0.1 to 100 μm, and more preferably 1 to 30 μm.

The semiconductor fine particles may or may not be heat-treated after being coated on the conductive support. However, heat treatment is preferred from the viewpoints of electronic contact between fine particles, improvement in coating film strength, and improvement in adhesion to the support. Further, microwave irradiation, press treatment, or electron beam irradiation may be performed. These treatments may be performed alone or in combination of two or more. In the heat treatment, the heating temperature is preferably 40 to 700 ° C, more preferably 80 to 600 ° C. The heating time is preferably 5 minutes to 50 hours, and more preferably 10 minutes to 20 hours. Microwave irradiation may be performed from the semiconductor layer forming side of the semiconductor electrode or from the back side. Although there is no restriction | limiting in particular in irradiation time, It is preferable to carry out within 1 hour. The press treatment is preferably performed at 9.8 × 10 ⁶ N / m ² or more, and more preferably at 9.8 × 10 ⁷ N / m ² or more. The pressing time is not particularly limited, but is preferably within 1 hour.

  The semiconductor fine particles preferably have a large surface area so that many dyes can be adsorbed. For this reason, it is preferable that the surface area in the state which coated the semiconductor layer on the support body is 10 times or more with respect to a projection area, and it is more preferable that it is 100 times or more.

  The dye-sensitized solar cell dye represented by the general formula (1) of the present invention may be used alone or in combination of two or more. In addition, for the purpose of reducing the amount of Ru used in a dye-sensitized solar cell that also uses a ruthenium (Ru) complex, the dye of the present invention and a Ru complex may be used in combination. Other merocyanine dyes, cyanine dyes, 9-phenylxanthene dyes, coumarin dyes, phthalocyanine dyes, naphthalocyanine dyes and the like may be used in combination.

  The semiconductor layer of the present invention is a semiconductor layer sensitized with the dye represented by the general formula (1). As a method for adsorbing the dye to the semiconductor layer (sensitizing method), a method of immersing a working electrode containing semiconductor fine particles in a dye solution or a dye dispersion, or applying a dye solution or a dispersion to the semiconductor layer A method of adsorption can be used. In the former case, dipping method, dipping method, roller method, air knife method, etc. can be used, and in the latter case, wire bar method, slide hopper method, extrusion method, curtain method, spin method, spray method, etc. Can be used.

  When adsorbing the dye, a condensing agent may be used in combination. The condensing agent may be either catalytically acting that physically or chemically binds the dye to the inorganic surface, or one that acts stoichiometrically to favorably shift the chemical equilibrium. . Further, a thiol or hydroxy compound may be added as a condensation aid.

  The medium for dissolving or dispersing the dye is water, methanol, ethanol, alcohol medium such as isopropyl alcohol, ketone medium such as acetone, methyl ethyl ketone, or methyl isobutyl ketone, ethyl formate, ethyl acetate, or n-butyl acetate. Ester media such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxolane, or dioxane, nitrile media such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide, or N Amide media such as methyl-2-pyrrolidone, dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenze , O-dichlorobenzene, fluorobenzene, bromobenzene, iodobenzene, or halogenated hydrocarbon media such as 1-chloronaphthalene, n-pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, methyl Examples thereof include hydrocarbon media such as cyclohexane, cyclohexadiene, benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, and cumene. These can be used alone or in admixture of two or more.

  The temperature for adsorbing the dye is preferably -50 ° C or higher and 200 ° C or lower. Further, the adsorption may be performed while stirring. Examples of the stirring method include, but are not limited to, a stirrer, a ball mill, a paint conditioner, a sand mill, an attritor, a disperser, and ultrasonic dispersion. The time required for adsorption is preferably from 5 seconds to 1000 hours, more preferably from 10 seconds to 500 hours, and even more preferably from 1 minute to 150 hours.

  In the present invention, when the dye is adsorbed on the semiconductor layer, a steroidal compound may be used in combination and co-adsorbed.

  Specific examples of the steroidal compound include those shown in E-1 to E-10 below. The amount of the steroidal compound is preferably 0.01 to 1000 parts by mass and more preferably 0.1 to 100 parts by mass with respect to 1 part by mass of the pigment.

  After adsorbing the dye, or after co-adsorbing the dye and the steroidal compound, a basic compound such as t-butylpyridine, 2-picoline, 2,6-lutidine, or phosphoric acid, phosphate ester, alkyl You may immerse in the organic solvent containing acidic compounds, such as phosphoric acid, an acetic acid, and propionic acid.

  As the charge transfer layer, an electrolytic solution in which a redox couple is dissolved in an organic solvent, a gel electrolyte in which a polymer matrix is impregnated with a liquid in which the redox couple is dissolved in an organic solvent, a molten salt containing a redox couple, a solid electrolyte, an inorganic A hole transport material, an organic hole transport material, or the like can be used.

  The electrolytic solution is preferably composed of an electrolyte, a solvent, and an additive. Preferred electrolytes are metal iodide-iodine combinations such as lithium iodide, sodium iodide, potassium iodide, cesium iodide, and calcium iodide, and quaternary compounds such as tetraalkylammonium iodide, pyridinium iodide, and imidazolium iodide. Iodine salt of ammonium compound-iodine combination, metal bromide-bromine combination such as lithium bromide, sodium bromide, potassium bromide, cesium bromide, calcium bromide, quaternary ammonium such as tetraalkylammonium bromide, pyridinium bromide Compound bromine salt-bromine combination, ferrocyanate-ferricyanate, metal complex such as ferrocene-ferricinium ion, sulfur compound such as sodium polysulfide, alkylthiol-alkyl disulfide , Viologen dye, hydroquinone - such as quinone, and the like. The above-mentioned electrolytes may be a single combination or a mixture. Further, a molten salt in a molten state at room temperature can also be used as the electrolyte. When this molten salt is used, it is not necessary to use a solvent.

  The electrolyte concentration in the electrolytic solution is preferably 0.05 to 20M, and more preferably 0.1 to 15M. Solvents used for the electrolyte include carbonate solvents such as ethylene carbonate and propylene carbonate, heterocyclic compounds such as 3-methyl-2-oxazolidinone, ether solvents such as dioxane, diethyl ether and ethylene glycol dialkyl ether, methanol, ethanol Alcohol solvents such as polypropylene glycol monoalkyl ether, nitrile solvents such as acetonitrile and benzonitrile, and aprotic polar solvents such as dimethyl sulfoxide and sulfolane are preferred. Moreover, you may use together basic compounds, such as t-butyl pyridine, 2-picoline, and 2, 6- lutidine.

  The electrolyte can be gelled by techniques such as polymer addition, oil gelling agent addition, polymerization including polyfunctional monomers, and polymer crosslinking reaction. Preferable polymers for gelation by addition of polymer include polyacrylonitrile, polyvinylidene fluoride, and the like. Preferred gelling agents for gelation by adding an oil gelling agent include dibenzylidene-D-sorbitol, cholesterol derivatives, amino acid derivatives, trans- (1R, 2R) -1,2-cyclohexanediamine alkylamide derivatives, alkyl Examples include urea derivatives, N-octyl-D-gluconamidobenzoate, double-headed amino acid derivatives, quaternary ammonium derivatives, and the like.

  Preferred monomers for polymerization with a polyfunctional monomer include divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, and the like. be able to. Furthermore, esters and amides derived from acrylic acid such as acrylamide and methyl acrylate and α-alkyl acrylic acid, esters derived from maleic acid and fumaric acid such as dimethyl maleate and diethyl fumarate, butadiene, cyclohexane Dienes such as pentadiene, aromatic vinyl compounds such as styrene, p-chlorostyrene, sodium styrenesulfonate, vinyl esters, acrylonitrile, methacrylonitrile, vinyl compounds having a nitrogen-containing heterocyclic ring, vinyls having a quaternary ammonium salt A monofunctional monomer such as a compound, N-vinylformamide, vinyl sulfonic acid, vinylidene fluoride, vinyl alkyl ethers, and N-phenylmaleimide may be contained. 0.5-70 mass% is preferable and the polyfunctional monomer which occupies for the monomer whole quantity has more preferable 1.0-50 mass%.

  The above-mentioned monomers can be polymerized by radical polymerization. The monomer for gel electrolyte that can be used in the present invention can be radically polymerized by heating, light, electron beam or electrochemical. The polymerization initiator used when the crosslinked polymer is formed by heating is 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl-2 Azo initiators such as 2,2'-azobis (2-methylpropionate), peroxide initiators such as benzoyl peroxide, and the like are preferable. The addition amount of these polymerization initiators is preferably 0.01 to 20% by mass and more preferably 0.1 to 10% by mass with respect to the total amount of monomers.

  When the electrolyte is gelled by a polymer crosslinking reaction, it is desirable to use a polymer containing a reactive group necessary for the crosslinking reaction and a crosslinking agent in combination. Preferable examples of the reactive group necessary for the crosslinking reaction include nitrogen-containing heterocycles such as pyridine, imidazole, thiazole, oxazole, triazole, morpholine, piperidine and piperazine. Preferred cross-linking agents include bifunctional or higher functional reagents capable of electrophilic reaction with nitrogen atoms such as alkyl halides, halogenated aralkyls, sulfonic acid esters, acid anhydrides, acid chlorides, and isocyanates.

  When an inorganic hole transport material is used instead of the electrolyte, copper iodide, copper thiocyanide, or the like can be introduced into the electrode by a casting method, a coating method, a spin coating method, a dipping method, or electrolytic plating.

  It is also possible to use an organic charge transport material instead of the electrolyte. Charge transport materials include hole transport materials and electron transport materials. Examples of the former include, for example, oxadiazoles shown in Japanese Patent Publication No. 34-5466, triphenylmethanes shown in Japanese Patent Publication No. 45-555, and Japanese Patent Publication No. 52-4188. Pyrazolines shown in JP-A-55-42380, hydrazones shown in JP-B-56-123544, oxadiazoles shown in JP-A-56-123544, etc., JP-A-54-58445 And tetrasylbenzidines disclosed in JP-A-58-65440, and stilbenes disclosed in JP-A-60-98437. Among them, examples of the charge transport material used in the present invention are shown in JP-A-60-24553, JP-A-2-96767, JP-A-2-183260, and JP-A-2-226160. Particularly preferred are the hydrazones described, and the stilbenes shown in JP-A-2-51162 and JP-A-3-75660. Moreover, these can be used individually or in mixture of 2 or more types.

  On the other hand, examples of the electron transport material include chloranil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4 , 5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 1,3,7-trinitrodibenzothiophene, or 1,3,7-trinitrodibenzothiophene-5,5-dioxide . These electron transport materials can be used alone or as a mixture of two or more.

  Furthermore, for the purpose of improving the charge transfer efficiency in the charge transfer layer, a certain kind of electron withdrawing compound can be added to the charge transfer layer. Examples of the electron-withdrawing compound include quinones such as 2,3-dichloro-1,4-naphthoquinone, 1-nitroanthraquinone, 1-chloro-5-nitroanthraquinone, 2-chloroanthraquinone, phenanthrenequinone, and 4-nitro. Aldehydes such as benzaldehyde, ketones such as 9-benzoylanthracene, indandione, 3,5-dinitrobenzophenone, or 3,3 ', 5,5'-tetranitrobenzophenone, phthalic anhydride, 4-chloronaphthalic anhydride Acid anhydrides such as terephthalalmalononitrile, 9-anthrylmethylidenemalononitrile, 4-nitrobenzalmalononitrile, or cyano compounds such as 4- (p-nitrobenzoyloxy) benzalmalononitrile, 3-benzalphthalide , 3- (α Cyano -p- Nitorobenzaru) phthalide, or 3- (alpha-cyano -p- Nitorobenzaru) -4,5,6,7 such phthalides such as tetrachloro phthalide can be cited.

  When forming a charge transfer layer using a charge transport material, a resin may be used in combination. When the resin is used in combination, polystyrene resin, polyvinyl acetal resin, polysulfone resin, polycarbonate resin, polyester resin, polyphenylene oxide resin, polyarylate resin, acrylic resin, methacrylic resin, phenoxy resin, and the like can be given. Among these, polystyrene resin, polyvinyl acetal resin, polycarbonate resin, polyester resin, and polyarylate resin are preferable. These resins may be used alone or as a copolymer in combination of two or more.

  There are two main methods for forming the charge transfer layer. One is a method in which a counter electrode is first bonded onto a semiconductor layer that has adsorbed a dye, and a liquid charge transfer layer is sandwiched between the gaps. The other is a method in which a charge transfer layer is provided directly on a semiconductor layer adsorbed with a dye. In the latter case, a counter electrode is newly provided on the charge transfer layer.

  In the former case, examples of the method for sandwiching the charge transfer layer include a normal pressure process using capillary action due to immersion and a vacuum process in which the gas phase is replaced with a liquid phase at a pressure lower than normal pressure. In the latter case, in the wet charge transfer layer, it is necessary to provide a counter electrode without being dried to prevent liquid leakage at the edge portion. In the case of a gel electrolyte, there is a method in which it is applied in a wet manner and solidified by a method such as polymerization. In that case, you may provide a counter electrode after drying and fixing. In addition to the electrolytic solution, the organic charge transport material solution and gel electrolyte can be applied in the same manner as the semiconductor layer and pigment application, as well as the immersion method, roller method, dipping method, air knife method, extrusion method, slide Examples include the hopper method, wire bar method, spin method, spray method, casting method, and various printing methods.

  The counter electrode can be used on a support having a conductive layer in the same manner as the substrate having conductivity on the surface, but the support is not necessarily required when the conductive layer itself has sufficient strength and sealing properties. Specific examples of the material used for the counter electrode include metals such as platinum, gold, silver, copper, aluminum, rhodium and indium, carbon compounds, and conductive metal oxides such as ITO and FTO. There is no particular limitation on the thickness of the counter electrode.

  In order for light to reach the semiconductor layer, at least one of the conductive substrate and the counter electrode on the surface holding the semiconductor layer must be substantially transparent. In the photoelectric conversion element of the present invention, a method in which the conductive substrate is transparent on the surface holding the semiconductor fine particle layer and sunlight is incident from the conductive substrate side holding the semiconductor layer is preferable. In this case, a material that reflects light is preferably used for the counter electrode, and a metal, glass, plastic, or metal thin film on which a conductive oxide is deposited is preferable.

  As described above, there are two types of coating of the counter electrode: when applied on the charge transfer layer and when applied on the semiconductor layer. In any case, the counter electrode material can be appropriately formed on the charge transfer layer or the semiconductor layer by a technique such as coating, laminating, vapor deposition, or bonding depending on the type of the counter electrode material or the type of the charge transfer layer. When the charge transfer layer is solid, the counter electrode can be formed directly on the conductive material by a method such as coating, vapor deposition, or chemical vapor deposition (CVD).

  EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to these at all.

(Synthesis Example 1: Synthesis of Dye D-16)
Intermediate A: 0.37 g, Intermediate B: 0.49 g, ammonium acetate 0.05 g, and acetic acid 40 ml were mixed and heated at a bath temperature of 120 ° C. for 5 hours. Subsequently, the mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with 30 ml of acetic acid, then 30 ml of water, and further 30 ml of methanol and dried to obtain 0.72 g of a crude product. This was purified by silica gel column chromatography (developing solvent: chloroform / methanol = 10/1 (volume ratio)) to obtain 0.66 g of Dye D-16. Absorption maximum: 527 nm (N, N-dimethylformamide solution).

(Synthesis Example 2: Synthesis of Dye D-23)
Intermediate C: 0.38 g, Intermediate D: 0.40 g, ammonium acetate 0.05 g, and acetic acid 40 ml were mixed and heated at a bath temperature of 120 ° C. for 5 hours. Subsequently, the mixture was cooled to room temperature, and the precipitated solid was collected by filtration, washed with 30 ml of acetic acid, then 30 ml of water, and further 30 ml of methanol and dried to obtain 0.70 g of a crude product. This was purified by silica gel column chromatography (developing solvent: chloroform / methanol = 10/1 (volume ratio)) to obtain 0.61 g of Dye D-23. Absorption maximum: 524 nm (N, N-dimethylformamide solution).

(Example 1)
<Preparation of dye-sensitized solar cell>
Paint conditioner (2 g titanium oxide (Nippon Aerosil Co., Ltd., trade name: P-25), 0.2 g acetylacetone, 0.3 g surfactant (trade name: Triton X-100, made by Aldrich Co.) together with 6.5 g water (Red Devil) for 6 hours. Further, 0.2 g of concentrated nitric acid, 0.4 ml of ethanol, and 1.2 g of polyethylene glycol (# 20,000) were added to 4.0 g of this dispersion to prepare a paste. This paste was applied onto an FTO glass substrate so as to have a film thickness of 10 μm, dried at room temperature, and then baked at 100 ° C. for 1 hour and further at 550 ° C. for 1 hour to obtain a semiconductor layer.

  The dye of the present invention shown in Table 1 and the dye of the following comparison were each dissolved in tetrahydrofuran to prepare a dye solution having a concentration of 0.3 mM. The steroid compound (E-1) was dissolved in this dye solution at a concentration of 0.6 mM. In the dye solution obtained as described above, the previously prepared dye-unadsorbed semiconductor layer was immersed for 4 hours at room temperature to perform an adsorption treatment, and a semiconductor layer (working electrode) sensitized with the dye was prepared. As the counter electrode, a titanium plate on which platinum was sputtered was used. Both electrodes were placed so as to face each other, and an electrolyte was injected between them to produce a dye-sensitized solar cell. The electrolyte was 3-methoxypropionitrile of lithium iodide 0.1M, iodine 0.05M, 1,2-dimethyl-3-n-propylimidazolium iodide 0.5M, 4-t-butylpyridine 0.05M. The solution was used.

<Evaluation of photoelectric conversion efficiency>
Pseudo sunlight (AM1.5G, irradiation intensity) generated from a solar simulator (manufactured by Yamashita Denso Co., Ltd., device name: YSS-40S) as a light source from the working electrode side of the dye-sensitized solar cell thus produced. 100mW / cm < ² >) was irradiated, and the photoelectric conversion characteristic was measured using the electrochemical measuring device (The solartron company make, apparatus name: SI-1280B). About the photoelectric conversion efficiency of each dye-sensitized solar cell produced using the present invention and the comparative dye obtained as described above, the relative value when the photoelectric conversion efficiency of the comparative dye C-1 is 100 As evaluated. The results are shown in Table 1.

  From the results in Table 1, it can be seen that the dye of the present invention exhibits excellent photoelectric conversion characteristics that surpass the comparative dyes of the prior art. In addition, the superiority of the particularly preferred embodiment of the present invention is apparent from the comparison of D-10, D-18, D-22, D-26 and other dyes of the present invention in Table 1.

  The dye for dye-sensitized solar cells of the present invention can be used for an optical sensor sensitive to light of a specific wavelength in addition to the dye-sensitized solar cell.

Claims (3)

A dye for a dye-sensitized solar cell represented by the following general formula (1).

(In General Formula (1), X represents an oxygen atom or a sulfur atom. R ₁₁ and R ₁₂ represent a hydrogen atom or an alkyl group, and both may be linked to form a cyclopentane ring or a cyclohexane ring. L ₁₁ represents a methine group unit, and A represents an organic residue having at least one acidic group having a pKa of less than 6 and having an atomic group necessary for forming a dye structure.   A semiconductor layer sensitized with the dye for a dye-sensitized solar cell according to claim 1.   A dye-sensitized solar cell having the semiconductor layer according to claim 2.