JP2007231171A - Sensitizing dye monomer, sensitizing dye polymer, photoelectric conversion material, semiconductor electrode and photoelectric transducer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sensitizing dye with excellent sensitizing effect and adsorption stability, and a high performance photoelectric transducer using it. <P>SOLUTION: A sensitizing dye polymer synthesized using a sensitizing dye monomer shown by general formula (1) is used as the sensitizing dye of the photoelectric transducer material (wherein R<SB>1</SB>represents H or the like, X represents a bivalent connecting group such as -O-, HTU represents a bivalent charge transporting group and SDU represents a univalent sensitizing dye). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a sensitizing dye monomer, a sensitizing dye polymer, a photoelectric conversion material, a semiconductor electrode, and a photoelectric conversion element.

Global warming due to the increase in CO ₂ concentration caused by the use of a large amount of fossil fuel, and the increase in energy demand accompanying population increase are recognized as problems related to the existence of human beings. For this reason, in recent years, the use of sunlight that is infinite and does not generate harmful substances has been energetically studied. What is currently put into practical use as sunlight, which is a clean energy source, includes 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 that payback to the user is long, and there is 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 the like, 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, there are many problems in that conversion efficiency is low at 1% or less, and durability is poor.

  Under such circumstances, a solar cell exhibiting good characteristics has been reported by Dr. Gretzell of Switzerland (see Non-Patent Document 1). This document also discloses materials and manufacturing techniques necessary for battery fabrication. The proposed battery 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 as a working electrode. The advantage of this method is that it is not necessary to purify an inexpensive oxide semiconductor such as titanium oxide to high purity, and therefore, it is inexpensive and more usable light extends over a wide visible light region, so that a solar with a large amount of visible light components is used. It is that light can be effectively converted into electricity.

On the other hand, ruthenium complexes with limited resources are used as sensitizing dyes, so when this solar cell is put to practical use, the supply of ruthenium complexes is in danger. Moreover, since this ruthenium complex is expensive, this problem can be solved if it can be changed to an inexpensive organic dye. Merocyanine dyes, cyanine dyes, and 9-phenylxanthene dyes have been reported as dyes for this battery (see, for example, Patent Documents 1 to 3). However, these sensitizing dyes do not provide a high sensitizing effect, and also have a problem in stability over time due to low adsorption stability to titanium oxide.
JP 11-238905 A JP 2001-76773 A Japanese Patent Laid-Open No. 10-92477 Nature, 353, 737 (1991)

  An object of the present invention is to provide a sensitizing dye excellent in sensitizing effect and adsorption stability, and a high-performance photoelectric conversion element using the same.

  As a result of intensive studies to achieve the above object, the present inventors have conducted sensitization including a structural unit represented by the general formula (10) derived from a sensitizing dye monomer represented by the general formula (1). By using as a sensitizing dye at least one of a dye polymer or a sensitizing dye polymer containing a structural unit represented by the general formula (10) and a structural unit represented by the general formula (11), I was able to achieve my purpose.

In the general formula (1), R ¹ represents a hydrogen atom or a lower alkyl group, X represents a divalent connecting group, and HTU (abbreviation of “Hole Transfer Unit”) represents a charge transporting divalent group. , SDU (abbreviation of “Sensitizing Dye Unit”) represents a monovalent sensitizing dye group.

In the general formulas (2) to (6), R ^{2 to} R ⁸ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom.

In the general formulas (7) to (9), A ^{1 to} A ⁶ represent an oxygen atom, a sulfur atom, or NR ¹⁵ , and R ¹⁵ represents an alkyl group that may have a substituent. B ^{1 to} B ⁹ represent an oxygen atom or a sulfur atom. R ^{9 to} R ¹⁴ represent an alkyl group which may have a substituent, R ⁹ has a carboxylic acid group as a substituent, and one or more carboxylic acid groups among R ¹⁰ and R ¹¹ It has as a substituent and has at least one carboxylic acid group as a substituent among R ^{12 to} R ¹⁴ .

In the general formula (10), R ¹ , X, HTU, and SDU represent the same as in the general formula (1).

In the general formula (11), R ¹⁶ represents a hydrogen atom or a lower alkyl group, and Y represents a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group or an amino group.

  The photoelectric conversion material means all parts constituting an element that converts light into electric energy, such as a material constituting a conductive support, a material constituting a semiconductor electrode, an electrolyte, and a material constituting a counter electrode. To do. By adsorbing and supporting a dye that absorbs light in the visible region on a semiconductor electrode that does not have photoelectric conversion capability in the visible region, the photoelectric conversion capability of the semiconductor electrode can be expanded to the visible region. The dye used in is called a sensitizing dye. In the present invention, the term “dye” simply means the same as this sensitizing dye.

  A sensitizing dye polymer containing a structural unit represented by the general formula (10) derived from the sensitizing dye monomer represented by the general formula (1) according to the present invention, or represented by the general formula (10). By using a sensitizing dye polymer containing a structural unit and the structural unit represented by the general formula (11), photoelectric conversion that exhibits excellent conversion efficiency and is excellent in adsorption stability of the sensitizing dye to the semiconductor electrode. A conversion element can be obtained.

Specific examples of R ^{1 in} the general formulas (1) and (10) include a hydrogen atom or a lower alkyl group such as a methyl group, an ethyl group, and a butyl group. Specific examples of the divalent connecting group X in the general formula (1) and the general formula (10) include an oxygen atom, a sulfur atom, and NR ¹⁷ (R ¹⁷ is a hydrogen atom or a lower group such as a methyl group, an ethyl group, or a butyl group). Represents an alkyl group), 1,4-phenylene group, 4,4'-biphenylene group, 1,6-pyrenylene group, arylene group such as 1,8-pyrenylene group, alkylene such as methylene group, ethylene group, propylene group Oxyethylene group, ethylenedioxy group, 3-thiapentane-1,5-diyl group, 1,2-diphenylethylene-4,4'-diyl group, 1,2- Examples thereof include divalent groups such as diphenoxyethylene-4,4′-diyl group, transstilbene-4,4′-diyl group, 1,4-xylylene group, and 1,3-xylylene group.

Specific examples of the charge transporting divalent group, HTU in the general formulas (1) and (10), are generally known as “charge transport materials” (Charge Transport Material = CTM) in the field of electrophotographic photoreceptors. Examples thereof include divalent groups formed by removing two hydrogen atoms from the compound, and more specifically, divalent groups represented by general formulas (2) to (6). Here, specific examples of the substituents R ^{2 to} R ⁸ in the general formulas (2) to (6) include a hydrogen atom, a lower alkyl group such as a methyl group, an ethyl group, and a butyl group, a methoxy group, an ethoxy group, and a propyloxy group. And a lower alkoxy group such as a group, or a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

Specific examples of the monovalent sensitizing dye group and SDU in the general formulas (1) and (10) include a part of the skeleton of a compound known as “merocyanine sensitizing dye” in the field of photochemistry. A monovalent group obtained via a methine group on a divalent carbon atom, more specifically, a monovalent group represented by general formulas (7) to (9), and the like. In the general formulas (7) to (9), A ^{1 to} A ⁶ represent an oxygen atom, a sulfur atom, or NR ¹⁵ , and R ¹⁵ represents a methyl group, an ethyl group, a t-butyl group, an n-octyl group, or a methoxymethyl. Represents an alkyl group which may have a substituent, such as a group, 2-cyanoethyl group, carboxymethyl group, 2-carboxyethyl group, 3-phenoxypropyl group. B ^{1 to} B ⁹ represent an oxygen atom or a sulfur atom. R ^{9 to} R ¹⁴ are methyl group, ethyl group, t-butyl group, n-octyl group, methoxymethyl group, 2-cyanoethyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 3-phenoxy group. Represents an alkyl group which may have a substituent, such as propyl group and 4-chlorobutyl group, and R ⁹ has a carboxylic acid group as a substituent, and one or more of R ¹⁰ and R ¹¹ It has a carboxylic acid group as a substituent, and has one or more carboxylic acid groups as substituents among R ^{12 to} R ¹⁴ .

Specific examples of R ¹⁶ in the general formula (11) include a hydrogen atom or a lower alkyl group such as a methyl group, an ethyl group, or a butyl group. Specific examples of Y include hydroxyl group, methyl group, ethyl group, butyl group, octyl group, dodecyl group, isopentyl group, 2-methoxyethyl group, cyclohexyl group, 3-chloropropyl group, 4-hydroxybutyl group and the like. Alkyl groups, methoxy groups, ethoxy groups, propyloxy groups, 2-methoxyethoxy groups, 2- (4-chlorobutoxy) ethoxy groups and other alkoxy groups, amino groups, methylamino groups, ethylamino groups, isopropylamino groups, An amino group such as a phenylamino group or 4-methoxyphenylamino group is represented.

  Next, although the specific example of the sensitizing dye monomer of General formula (1) of this invention is given, this invention is not limited to these.

  Examples of the sensitizing dye polymer containing the structural unit represented by the general formula (10) of the present invention include polymerizing several to several hundred sensitizing dye monomers of the general formula (1). The following sensitizing dye polymers may be mentioned as specific examples, but the present invention is not limited to these.

  Furthermore, examples of the sensitizing dye polymer containing the structural unit represented by the general formula (10) and the structural unit represented by the general formula (11) of the present invention include those of the above general formula (1). Examples thereof include a sensitizing dye polymer obtained by copolymerizing several to several hundreds of a dye-sensitive monomer and a monomer represented by the following general formula (12). These polymers may be either a block polymer or a random polymer. Further, the other monomer to be copolymerized with the sensitizing dye monomer of the general formula (1) is not limited to the monomer represented by the general formula (12), and a double monomer having sufficient reactivity. Any monomer containing a bond can be used.

R ¹⁶ and Y in the general formula (12) represent the same as in the general formula (11).

  The following sensitizing dye polymer is mentioned as a specific example of the sensitizing dye polymer which consists of a structural unit represented by General formula (10) of this invention, and a structural unit represented by General formula (11). However, the present invention is not limited to these.

  The photoelectric conversion element of the present invention comprises a conductive support, a semiconductor layer coated on the conductive surface, a semiconductor electrode made of a dye adsorbed on the surface of the semiconductor layer, a charge transfer layer, and a counter electrode. 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 be diffused or mixed 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. (Hereinafter abbreviated as “FTO”) and the like. 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 installed on a transparent support by vapor deposition, sputtering, pressure bonding, or the like, and a method of providing ITO or FTO thereon, or a metal lead wire on a transparent conductive layer.

  As the semiconductor, a single semiconductor such as silicon or germanium, a compound semiconductor typified by a metal chalcogenide, a compound having a perovskite structure, or the like can be used. Metal chalcogenides include titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, or tantalum oxide, cadmium, zinc, lead, silver, antimony, bismuth. Sulfide, cadmium, lead selenide, cadmium telluride 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. As the conversion efficiency, a single crystal is preferable, but a polycrystal is preferable in terms of manufacturing cost, securing raw materials, and the like, and the particle size of the semiconductor is preferably 2 nm or more and 1 μm or less.

  As a method for 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. The dispersion can be prepared by the above-mentioned sol-gel method, a method of mechanically pulverizing with a mortar, etc., a method of dispersing while pulverizing using a mill, or a fine particle in a solvent when synthesizing a semiconductor. And a method of using it as it is.

  In the case of a dispersion prepared by mechanical pulverization or pulverization using a mill, it is formed 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 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 formal resins, polyester resins. , Cellulose ester resin, cellulose ether resin, urethane resin, phenol resin, epoxy resin, polycarbonate resin, polyarylate resin, polyamide resin, polyimide resin and the like.

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

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

  Furthermore, 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, from the viewpoint of improving the electronic contact between the particles and the strength of the coating film and the adhesion to the support, the heat treatment is performed. Is preferable. Furthermore, microwave irradiation, press treatment, or electron beam irradiation may be performed, and 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. The 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 10 ⁷ N or more, more preferably 10 ⁸ N. There is no particular limitation on the pressing time, but it is preferably performed within 1 hour.

  The semiconductor fine particles preferably have a large surface area so that many sensitizing 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 photoelectric conversion element of the present invention is a sensitizing dye polymer containing a structural unit represented by the general formula (10), or a structural unit represented by the general formula (10) and the structural unit represented by the general formula (11). A semiconductor layer in which a sensitizing dye polymer containing a unit is adsorbed and sensitized as a sensitizing dye to a semiconductor layer is used as a photoelectric conversion material.

  As a method of adsorbing a sensitizing dye to a semiconductor layer, a method of immersing a working electrode containing semiconductor fine particles in a dye solution or a dye dispersion, a method of applying a dye solution or a dispersion to a semiconductor layer and adsorbing the semiconductor layer. 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 sensitizing dye, a condensing agent may be used in combination. The condensing agent may be either one that has a catalytic action that is supposed to physically or chemically bind the dye to the inorganic surface, or one that acts stoichiometrically to favorably shift the chemical equilibrium. Furthermore, a thiol or a hydroxy compound may be added as a condensation aid.

  Solvents that dissolve or disperse the sensitizing dye are water, methanol, ethanol, alcohol solvents such as isopropyl alcohol, ketone solvents such as acetone, methyl ethyl ketone, or methyl isobutyl ketone, ethyl formate, ethyl acetate, or n acetate. Ester solvents such as butyl, ether solvents such as diethyl ether, dimethoxyethane, tetrahydrofuran, dioxolane, or dioxane, nitrile solvents such as acetonitrile and propionitrile, N, N-dimethylformamide, N, N-dimethylacetamide Amide solvents such as N-methyl-2-pyrrolidone, dichloromethane, chloroform, bromoform, methyl iodide, dichloroethane, trichloroethane, trichloroethylene, chlorobenzene, o Halogenated hydrocarbon solvents such as dichlorobenzene, fluorobenzene, bromobenzene, iodobenzene, or 1-chloronaphthalene, n-pentane, n-hexane, n-octane, 1,5-hexadiene, cyclohexane, methylcyclohexane, cyclo Examples thereof include hydrocarbon solvents such as hexadiene, benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, and cumene, and these can be used alone or as a mixture of two or more.

  The temperature at which these are used and the sensitizing dye is adsorbed is preferably -50 ° C or higher and 200 ° C or lower. Further, this 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 5 seconds or more and 1000 hours or less, more preferably 10 seconds or more and 500 hours or less, and further preferably 1 minute or more and 150 hours.

  In this invention, the sensitizing dye polymer containing the structural unit represented by General formula (10), or the structural unit represented by General formula (10) and the structural unit represented by General formula (11) is included. When adsorbing the sensitizing dye polymer, a steroidal compound may be used in combination.

  Specific examples of the steroid compound include those shown in (S-1) to (S-10). 0.01-1000 mass parts is preferable with respect to 1 mass part of pigment | dyes, and, as for the quantity of a steroid type compound, 0.1-100 mass parts is more preferable.

  After adsorbing the sensitizing dye, or after co-adsorbing the sensitizing dye and the steroid compound, a basic compound such as t-butylpyridine, 2-picoline, 2,6-lutidine, or phosphoric acid or phosphate ester Further, it may be dipped in an organic solvent containing an acidic compound such as alkyl phosphoric acid, acetic acid or propionic acid.

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

  The electrolytic solution used in the present invention is preferably composed of an electrolyte, a solvent, and an additive. Preferred electrolytes include metal iodide-iodine combinations such as lithium iodide, sodium iodide, potassium iodide, cesium iodide, calcium iodide, tetraalkylammonium iodide, pyridinium iodide, imidazolium iodide, and the like. Iodine salts of quaternary ammonium compounds-iodine combinations, metal bromides such as lithium bromide, sodium bromide, potassium bromide, cesium bromide, calcium bromide-bromine combinations, quaternary compounds such as tetraalkylammonium bromide, pyridinium bromide Bromine-bromine combinations of ammonium compounds, metal complexes such as ferrocyanate-ferricyanate, ferrocene-ferricinium ion, sulfur compounds such as sodium polysulfide, alkylthiol-alkyldisulfide, viologen Dye, hydroquinone - quinones, 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, aprotic polar solvents such as dimethyl sulfoxide and sulfolane are preferred. Further, basic compounds such as t-butylpyridine, 2-picoline, and 2,6-lutidine may be used in combination.

  In the present invention, the electrolyte can be gelled by a technique such as addition of a polymer, addition of an oil gelling agent, polymerization including polyfunctional monomers, or a crosslinking reaction of the polymer. Preferable polymers in the case of gelation by polymer addition include polyacrylonitrile, polyvinylidene fluoride and the like. Preferred gelling agents for gelation by adding an oil gelling agent include dibenzylden-D-sorbitol, cholesterol derivatives, amino acid derivatives, alkylamide derivatives of trans- (1R, 2R) -1,2-cyclohexanediamine, alkylureas Derivatives, N-octyl-D-gluconamide benzoate, double-headed amino acid derivatives, quaternary ammonium derivatives and the like can be mentioned.

  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 and the like. Dienes such as pentadiene, aromatic vinyl compounds such as styrene, p-chlorostyrene and sodium styrene sulfonate, vinyl esters, acrylonitrile, methacrylonitrile, vinyl compounds having a nitrogen-containing heterocyclic ring, vinyl having a quaternary ammonium salt A monofunctional monomer such as a compound, N-vinylformamide, vinylsulfonic acid, vinylidene fluoride, vinyl alkyl ethers, 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 An azo initiator such as 2,2'-azobis (2-methylpropionate) and a peroxide initiator such as benzoyl peroxide 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 crosslinkable reactive group include nitrogen-containing heterocycles such as pyridine, imidazole, thiazole, oxazole, triazole, morpholine, piperidine, piperazine, etc. Preferred crosslinking agents include alkyl halides, halogens Bifunctional or higher functional reagents capable of electrophilic reaction with nitrogen atoms such as aralkyl fluoride, sulfonic acid ester, acid anhydride, acid chloride, and isocyanate can be exemplified.

  When an inorganic solid compound 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, electrolytic plating, or the like.

  In the present invention, an organic charge transport material can be used instead of the electrolyte. Charge transport materials include hole transport materials and electron transport materials. Examples of the former include, for example, oxadiazoles disclosed in Japanese Patent Publication No. 34-5466, triphenylmethanes disclosed in Japanese Patent Publication No. 45-555, and Japanese Patent Publication No. 52-4188. Pyrazolines shown in the above, hydrazones shown in JP-B-55-42380, oxadiazoles shown in JP-A-56-123544, etc., JP-A-54-58445 And tetrasylbenzidines disclosed in JP-A No. 58-65440, and stilbenes disclosed in JP-A No. 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, 1,3,7-trinitrodibenzothiophene-5,5-dioxide, etc. . These electron transport materials can be used alone or as a mixture of two or more.

  Further, as a sensitizer that further increases the sensitizing effect, a certain kind of electron-withdrawing compound can be added. Examples of the electron-withdrawing compound include quinones such as 2,3-dichloro-1,4-naphthoquinone, 1-nitroanthraquinone, 1-chloro-5-nitroanthraquinone, 2-chloroanthraquinone, and phenanthrenequinone, 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- - Nitorobenzaru) phthalide, or 3- (alpha-cyano -p- Nitorobenzaru) -4,5,6,7 can be mentioned phthalides such as tetrachloro phthalide like.

  When forming a charge transfer layer using these charge transport materials, a resin may be used in combination. When 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 mentioned. 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 pasted on a semiconductor layer carrying a sensitizing dye, and a liquid charge transfer layer is sandwiched in the gap, and the other is a method in which a charge transfer layer is provided directly on the semiconductor layer. It is a method to do. 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 a capillary phenomenon 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, as a method of applying a solution or gel electrolyte of an organic charge transport material, as in the case of applying a dye to a semiconductor layer, a dipping method, a roller method, a dipping method, an air knife method, an extrusion method, Examples thereof include a slide hopper method, a wire bar method, a spin method, a spray method, a 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 conductive support described above, 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 sensitized semiconductor layer by adsorbing the sensitizing dye, at least one of the conductive support holding the semiconductor layer and the counter electrode must be substantially transparent. In the photoelectric conversion element of the present invention, a method in which the conductive support holding the semiconductor layer is transparent and sunlight is incident from the conductive support side 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 charge transfer layer by a technique such as coating, vapor deposition, or CVD.

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

Example 1
2 hours of titanium oxide (P-25 manufactured by Nippon Aerosil Co., Ltd.), 0.2 g of acetylacetone, and 0.3 g of surfactant (Triton X-100 manufactured by Aldrich) together with 6.5 g of water in a paint conditioner (manufactured by Red Devil) for 6 hours. Dispersion treatment was performed. 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 12 μm, dried at room temperature, and then fired at 100 ° C. for 1 hour and further at 550 ° C. for 1 hour.

  The sensitizing dye polymer (AP-2) exemplified in the present invention was dissolved in a mixed solution of t-butanol / acetonitrile (1/1) to prepare a dye solution having a concentration of 0.3 mM. In this dye solution, the previously produced semiconductor electrode was immersed at room temperature for 15 hours for adsorption treatment. The electrolyte is a lithium iodide 0.1M, iodine 0.05M, 1,2-dimethyl-3-n-propylimidazolium iodide 0.5M 3-methoxyacetonitrile solution, and the counter electrode is sputtered with platinum on a titanium plate. We used what we did.

An electrolytic solution was immersed between both electrodes to produce a photoelectric conversion element. Here, pseudo-sunlight generated from a solar simulator (AM1.5G, irradiation intensity 100 mW / cm ² ) is irradiated as a light source from the working electrode side, and evaluation is performed using an electrochemical measurement apparatus (SI-1280B) manufactured by Solartron. Went. As a result, an open circuit voltage of 0.59 V, a short circuit current density of 9.35 mA / cm ² , a shape factor of 0.61, and a conversion efficiency of 3.37% were shown.

  Furthermore, the adsorption stability of the sensitizing dye to the semiconductor electrode was evaluated. The sensitizing dye polymer (AP-2) exemplified in the present invention was dissolved in a mixed solution of t-butanol / acetonitrile (1/1) to prepare a dye solution having a concentration of 0.3 mM. In this dye solution, the previously produced semiconductor electrode was immersed at room temperature for 15 hours for adsorption treatment. Next, the semiconductor electrode adsorbed with the dye was immersed in 3-methoxyacetonitrile, which is an electrolyte solvent, and stored for 10 days under light shielding, sealing, and room temperature. The state of dye support on the semiconductor electrode after storage was visually observed. The results are shown in Table 3.

(Examples 2 to 13)
A device was prepared and evaluated in the same manner as in Example 1 except that the sensitizing dye polymer (AP-2) exemplified in the present invention was changed to the exemplified sensitizing dye polymer shown in Table 1. The results are shown in Table 1. Furthermore, the adsorption stability of the dye to the semiconductor electrode was evaluated in the same manner as in Example 1 except that (AP-2) was changed to the exemplified sensitizing dye polymer shown in Table 1. The results are shown in Table 3.

(Example 14)
The sensitizing dye polymer (ACP-3) exemplified in the present invention was dissolved in a mixed solution of t-butanol / acetonitrile (1/1) to prepare a dye solution having a concentration of 0.3 mM. The steroid compound (S-1) was dissolved in this dye solution at a concentration of 0.6 mM. Subsequently, the semiconductor electrode produced in Example 1 was immersed in this dye solution at room temperature for 15 hours to perform an adsorption treatment. The electrolyte is a lithium iodide 0.1M, iodine 0.05M, 1,2-dimethyl-3-n-propylimidazolium iodide 0.5M 3-methoxyacetonitrile solution, and the counter electrode is sputtered with platinum on a titanium plate. We used what we did.

An electrolytic solution was immersed between both electrodes to produce a photoelectric conversion element. Here, pseudo-sunlight generated from a solar simulator (AM1.5G, irradiation intensity 100 mW / cm ² ) is irradiated as a light source from the working electrode side, and evaluation is performed using an electrochemical measurement apparatus (SI-1280B) manufactured by Solartron. Went. As a result, an open circuit voltage of 0.58 V, a short circuit current density of 9.21 mA / cm ² , a form factor of 0.58, and a conversion efficiency of 3.10% were shown.

(Examples 15 to 25)
The sensitizing dye polymer (ACP-3) exemplified in the present invention was changed to the exemplified sensitizing dye polymer shown in Table 2, and the steroid compound (S-1) was changed to the exemplified compound shown in Table 3. Were fabricated and evaluated in the same manner as in Example 14. The results are shown in Table 2.

(Comparative Example 1)
A device was prepared and evaluated in the same manner as in Example 1 except that the sensitizing dye polymer (AP-2) exemplified in the present invention was changed to the compound shown in (R-1). As a result, the open circuit voltage was 0.43 V, the short-circuit current density was 7.71 mA / cm ² , the shape factor was 0.55, and the conversion efficiency was 1.82%, which were lower than the dye of the present invention. Further, the adsorption stability of the dye to the semiconductor electrode was evaluated in the same manner as in Example 1 except that (AP-2) was changed to the compound shown in (R-1). The results are shown in Table 3.

(Comparative Example 2)
A device was prepared and evaluated in the same manner as in Example 1 except that (AP-2) was changed to the compound shown in (R-2). As a result, the open circuit voltage was 0.45 V, the short-circuit current density was 7.81 mA / cm ² , the shape factor was 0.52, and the conversion efficiency was 1.83%, which were low values compared to the dye of the present invention. Further, the adsorption stability of the dye to the semiconductor electrode was evaluated in the same manner as in Example 1 except that (AP-2) was changed to the compound shown in (R-2). The results are shown in Table 3.

(Comparative Example 3)
A device was prepared and evaluated in the same manner as in Example 14 except that (AP-2) was changed to the compound shown in (R-3). As a result, the open-circuit voltage was 0.52 V, the short-circuit current density was 8.11 mA / cm ² , the shape factor was 0.53, and the conversion efficiency was 2.23%, which were low values compared to the dye of the present invention. Further, the adsorption stability of the dye to the semiconductor electrode was evaluated in the same manner as in Example 1 except that (AP-2) was changed to the compound shown in (R-3). The results are shown in Table 3.

(Comparative Example 4)
A device was prepared and evaluated in the same manner as in Example 1 except that (AP-2) was changed to the compound shown in (R-4). As a result, the open circuit voltage was 0.55 V, the short-circuit current density was 6.88 mA / cm ² , the shape factor was 0.59, and the conversion efficiency was 2.23%, which were low values compared to the dye of the present invention. Furthermore, the adsorption stability of the dye to the semiconductor electrode was evaluated in the same manner as in Example 1 except that (AP-2) was changed to the compound shown in (R-4). The results are shown in Table 3.

  As described above, a sensitizing dye polymer containing a structural unit represented by the general formula (10) of the present invention, synthesized using the sensitizing dye monomer of the general formula (1) of the present invention, or When a sensitizing dye polymer including the structural unit represented by the general formula (10) and the structural unit represented by the general formula (11) is used as a sensitizing dye of a photoelectric conversion material, In comparison, it has been found that it has extremely excellent characteristics such as high conversion efficiency and excellent adsorption stability.

  Examples of utilization of the present invention include photosensors that are sensitive to light of a specific wavelength, in addition to photoelectric conversion elements such as solar cells.

Claims (9)

A sensitizing dye monomer represented by the general formula (1).

(In the general formula (1), R ¹ represents a hydrogen atom or a lower alkyl group, X represents a divalent connecting group, HTU represents a charge transporting divalent group, and SDU represents a monovalent sensitization. Indicates a dye group.) The sensitizing dye monomer according to claim 1, wherein in the general formula (1), HTU contains at least one group selected from the groups represented by the general formulas (2) to (6).

(In the general formulas (2) to (6), R ^{2 to} R ⁸ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a halogen atom.) The sensitizing dye unit amount according to claim 1, wherein the SDU contains at least one group selected from sensitizing dye groups represented by the general formulas (7) to (9) in the general formula (1). body.

(In the general formula (7) ~ (9), A 1 ~A 6 is an oxygen atom, a sulfur atom or NR ^15,, R ¹⁵ is .B ¹ ~ representing an alkyl group which may have a substituent B ⁹ represents an oxygen atom or a sulfur atom, R ^{9 to} R ¹⁴ represent an alkyl group which may have a substituent, R ⁹ has a carboxylic acid group as a substituent, and R ¹⁰ and R ¹¹ And one or more carboxylic acid groups as substituents, and one or more carboxylic acid groups among R ^{12 to} R ¹⁴ as substituents.) The sensitizing dye polymer containing the structural unit represented by General formula (10) induced | guided | derived from the sensitizing dye monomer of any one of Claims 1-3.

(In General Formula (10), R ¹ , X, HTU, and SDU represent the same as in General Formula (1).) The structural unit represented by General formula (10) and the structural unit represented by General formula (11) derived from the sensitizing dye monomer of any one of Claims 1-3 are included. Sensitizing dye polymer.

(In the general formula (11), R ¹⁶ represents a hydrogen atom or a lower alkyl group, and Y represents a hydroxyl group or an optionally substituted alkyl group, alkoxy group or amino group.)   A photoelectric conversion material comprising at least one sensitizing dye polymer according to any one of claims 4 to 5.   6. A semiconductor electrode comprising a conductive support, a semiconductor layer coated on the conductive surface, and a sensitizing dye adsorbed on the surface of the semiconductor layer, as a sensitizing dye. A semiconductor electrode comprising at least one of the sensitizing dye polymers described above.   The semiconductor is titanium, tin, zinc, iron, copper, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, tantalum, cadmium, lead, silver, antimony, bismuth, molybdenum, aluminum, 8. The semiconductor electrode according to claim 7, comprising at least one metal chalcogenide selected from gallium, chromium, cobalt, and nickel.   A photoelectric conversion element using the semiconductor electrode according to claim 7 or 8.