JP2003264010A - Photoelectric transducer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photoelectric transducer superior in a photoelectric conversion characteristic. <P>SOLUTION: At least one kind of pigment shown in the formula 1 is used as the photoelectric conversion material. R<SB>1</SB>shows an aryl group and a heterocyclic residual group, and they may have substituents, respectively. R<SB>2</SB>, R<SB>3</SB>, and R<SB>4</SB>show a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a heterocyclic residual group, and they may have substituents, respectively. R<SB>5</SB>shows a substituting group having an acidic group, and A part shows a heterocyclic ring to form a 5-membered to 7-membered ring together with an amino group to substitute a carbonyl group and R<SB>5</SB>. n shows an integer of 0 to 2 and m shows an integer of 1 to 3. A carbon-carbon double bond may be either of E-type or Z-type. <P>COPYRIGHT: (C)2003,JPO

Description

Description: BACKGROUND OF THE INVENTION [0001] The present invention relates to a compound represented by the general formula (1):
Photoelectric conversion device using dyes used as photoelectric conversion materials
It is about. [0002] Atmospheric carbon generated by the use of fossil fuels
O _Two Global warming due to increasing concentrations, and accompanying population growth
Increasing energy demand is a problem that extends to the survival of mankind
Has been recognized. Recently, infinite and no emission of harmful substances
The use of sunlight is being vigorously studied. This clean
Is currently being put to practical use by utilizing solar energy
Are monocrystalline silicon, polycrystalline silicon,
Morphous silicon and cadmium telluride and selenium
Inorganic solar cells such as indium copper bromide. [0003] However, these solar cells have
Silicon needs to be of very high purity.
Of course, the purification process is complicated, the number of processes is large, and
Manufacturing costs are high. In this way, photovoltaic power generation using inorganic materials
In terms of cost and long payback to users,
And there were problems with its spread. On the other hand, solar cells using organic materials have hitherto
Many have been proposed. As an organic solar cell, p-type
A shot for joining an organic semiconductor and a metal with a low work function
Toky type photoelectric conversion element, p-type organic semiconductor and n-type inorganic semiconductor
Body or p-type organic semiconductor and electron-accepting organic compound
There are heterojunction type photoelectric conversion elements, etc.
Chlorophyll, Perilet
Conductive dyes such as synthetic dyes and pigments, polyacetylene, etc.
Material, or their composite materials, etc.
By vacuum evaporation, casting, dipping, etc.
It is composed of a thin film. Organic materials are low
Although there are advantages such as easy storage and large area, conversion efficiency is still high.
Is often as low as 1% or less and has poor durability
There were also problems. Under these circumstances, Nature (Vol. 353, P7
37, 1991) and U.S. Pat.No. 4,492,721.
In addition, photoelectric conversion elements using dye-sensitized semiconductor fine particles
And solar cells were revolutionary. This document requires
Essential materials and manufacturing techniques are also disclosed. was suggested
The battery is powered by a ruthenium complex called the Grettzel type.
Titanium oxide porous thin film spectrally sensitized by
Wet solar cell. The advantage of this method is titanium oxide
It is not necessary to purify inexpensive oxide semiconductors such as
It is inexpensive and extends over a wide visible light range.
Being able to effectively convert sunlight with a large visible light component to electricity
It is. On the other hand, a very expensive ruthenium complex is required.
It is used and needs improvement. Expensive ruthenium complex
It is desirable to change the body to cheap organic dyes such as cyanine
However, organic dyes have low adsorptivity to titanium oxide,
There is also a problem with stability, leading to a high sensitizing effect.
Not in. SUMMARY OF THE INVENTION An object of the present invention is to provide a high quality
It is an object of the present invention to provide a photoelectric conversion element having a function. [0008] The present inventors have achieved the above object.
As a result of intensive studies to achieve this, it is shown by the general formula (1).
Of at least one dye to be used as a photoelectric conversion material
That was achieved by: [0009] In the general formula (1), R ₁ Is aryl
Group, represents a heterocyclic residue, each having a substituent
Good. R _Two , R _Three , R _Four Is hydrogen atom, alkyl group, alcohol
Represents a xy group, an aryl group, or a heterocyclic residue.
It may have a substituent. R _Five Is a substituent having an acidic group
A represents a carbonyl group and R _Five Amino to replace
And a heterocyclic ring which forms a 5- to 7-membered ring together with the group. n is 0
The integer of 2 and m show the integer of 1-3. Carbon-carbon double bond
In this case, either the E type or the Z type may be used. DETAILED DESCRIPTION OF THE INVENTION Here, R ₁ As a specific example,
Aryl group such as phenyl group, naphthyl group, furyl group,
List heterocyclic residues such as enyl and indolyl groups.
Can be. Also, R ₁ May have a substituent,
Specific examples of the substituent include a methyl group, an ethyl group,
Alkyl group such as propyl group, methoxy group, ethoxy group, etc.
Alkoxy groups, halogen atoms such as chlorine and bromine, dimethyl
Diamino group such as diamino group, diphenylamino group,
The above-mentioned aryl group and the above-mentioned heterocyclic ring can be exemplified.
You. R _Two , R _Three , R _Four Specific examples of the hydrogen atom
Alkyl group, the above-mentioned alkoxy group, the above-mentioned aryl
And the above-mentioned heterocyclic residue. Also, R
_Two , R _Three , R _Four May have a substituent, and the substituent
Specific examples of the above-mentioned alkyl group, the above-mentioned alkoxy
Si group, halogen atom described above, di-substituted amino group described above,
The aryl group described above and the heterocyclic ring described above can be exemplified.
R _Five Specific examples of carboxymethyl groups
Sulfo groups such as boxyalkyl group and sulfonylpropyl group
Examples include phonylalkyl groups, phosphate groups, and hydroxamic acid groups.
I can do it. Specific examples of the part A include the following (2)
To (9).
It is not limited to these. Embedded image Next, specific examples of the dye according to the present invention will be described with reference to A-
1 to A-22, but not limited to these.
It is not specified. Embedded image Embedded image Embedded image Embedded image Embedded image The photoelectric conversion element of the present invention comprises a conductive support,
Semiconductor sensitized by a dye placed on a conductive support
It consists of a body layer, a charge transfer layer and a counter electrode. The photosensitive layer has a single-layer structure
However, a laminated structure may be used, and the design is made according to the purpose. Ma
In addition, the boundary between the conductive layer and the photosensitive layer of the conductive support,
At the boundary of this element, such as the boundary of the moving layer,
May be mutually diffused or mixed. The conductive support is a support such as a metal.
Conductive material or conductive material on the surface
Use a glass or plastic support with an electrical layer
Can be. In the latter case, the conductive agent is platinum,
Metals such as gold, silver, copper, and aluminum; carbon;
Indium-tin composite oxide (hereinafter abbreviated as "ITO")
Metal oxides such as tin oxide doped with fluorine
(Hereinafter abbreviated as “FTO”). Conductivity
The support has a transparency of transmitting 10% or more of light.
And more preferably 50% or more transmission.
No. Among them, the conductive layer made of ITO or FTO
Conductive glass deposited on a substrate is particularly preferred. For the purpose of lowering the resistance of the transparent conductive substrate, gold
A metal lead may be used. Metal lead wire material is Al
Metals such as minium, copper, silver, gold, platinum and nickel are preferred.
New Metal leads are deposited on a transparent substrate and sputtered
It can be set up with a
Alternatively, there is a method of installing metal leads on the transparent conductive layer.
You. As the semiconductor, silicon, germanium
In addition to single semiconductors such as, metal chalcogenides
Compound semiconductor or perovskite structure
And the like can be used. Metal calco
Genide is preferably titanium, tin, zinc, iron, or titanium.
Ngustene, zirconium, hafnium, strontium
, Indium, cerium, yttrium, lanthanum,
Oxides of vanadium, niobium or tantalum, cad
Sulfidation of Mium, Zinc, Lead, Silver, Antimony, Bismuth
Material, cadmium, lead selenide, cadmium tellurium
And the like. Other compound semiconductors include zinc,
Phosphides such as gallium, indium, cadmium, etc.
Lium arsenide, copper-indium-selenide, copper-indium
And sulfides. Also, the perovskite structure
As the compound having the structure, strontium titanate,
Calcium titanate, sodium titanate,
And lithium and potassium niobate. The semiconductor used in the present invention may be a single crystal.
It may be polycrystalline. Single crystal is preferred for conversion efficiency
However, polycrystals are preferred in terms of manufacturing costs, securing raw materials, etc.
And the particle size of the semiconductor is 4 nm or more and 1 μm or less.
Is preferred. Method for forming semiconductor layer on conductive support
As a dispersion or colloidal solution of semiconductor fine particles
There are a method of coating on a conductive support, a sol-gel method, and the like.
You. As a method for producing the dispersion, the sol-gel described above is used.
Method, method of mechanical grinding with a mortar, etc., grinding with a mill
Method while dispersing, or when synthesizing a semiconductor
Precipitated as fine particles in a solvent and used as is
And the like. Mechanical grinding or grinding using a mill
In the case of a dispersion prepared by
German or semiconductor fine particles and binder resin
It is formed by dispersing in organic solvent. As the binder resin used
Styrene, vinyl acetate, acrylic acid ester,
Polymers and copolymers of vinyl compounds such as acrylates
Polymer, silicone resin, phenoxy resin, polysulfo
Resin, polyvinyl butyral resin, polyvinyl formal
Resin, polyester resin, cellulose ester tree
Fat, cellulose ether resin, urethane resin, phenol
Resin, epoxy resin, polycarbonate resin, polya
Uses related resin, polyamide resin, polyimide resin, etc.
Can be. Preferred solvents are water, methanol,
Alcohol such as ethanol or isopropyl alcohol
Coal solvents, acetone, methyl ethyl ketone, or
Is a ketone solvent such as methyl isobutyl ketone,
, Ethyl acetate, or esters such as n-butyl acetate
System solvent, diethyl ether, dimethoxyethane, tetra
Hydrofuran, dioxolan, or dioxane
Ether solvent, N, N-dimethylformamide, N,
N-dimethylacetamide or N-methyl-2-
Amide solvents such as pyrrolidone, dichloromethane, chloro
Form, bromoform, methyl iodide, dichloroeta
, Trichloroethane, trichloroethylene, chloroform
Benzene, o-dichlorobenzene, fluorobenzene,
Lomobenzene, iodobenzene, or 1-chlorona
Halogenated hydrocarbon solvents such as phthalene, n-pentane
, N-hexane, n-octane, 1,5-hexadiene
Cyclohexane, methylcyclohexane, cyclohexane
Xadiene, benzene, toluene, o-xylene, m-
Xylene, p-xylene, ethylbenzene, or
Examples include hydrocarbon solvents such as men. these
Is used alone or as a mixture of two or more solvents
Can be. The method for applying the resulting dispersion is as follows:
La method, dip method, air knife method, blade method, wire
Slide hopper method, extrusion method,
Curtain method, spin method, or spray method is preferred
No. Further, the semiconductor layer need not be limited to a single layer.
No. Multi-layer coating of dispersions of semiconductor particles with different particle sizes
Of different types of semiconductors, resins, and additives
It is also possible to apply multiple coating layers. Also, apply once
Multilayer coating is an effective means when the film thickness is insufficient with a cloth.
You. Generally, as the thickness of the semiconductor layer increases,
Light capture because the amount of supported dye per unit projected area also increases
Rate increases, but the diffusion distance of generated electrons also increases.
In addition, the recombination of electric charges increases. Therefore, the semiconductor layer
Is preferably 0.1 to 100 μm, more preferably 1 to 30 μm.
More preferred. The semiconductor fine particles were coated on a conductive support.
After that, heat treatment may or may not be performed.
Contact and improvement of coating strength and adhesion to substrate
From the above point, it is preferable to perform a heat treatment. In that case
The heat treatment temperature is preferably 40 to 700 ° C, and 100 to 60 ° C.
0 ° C. is more preferred. The heat treatment time is 5 minutes to 20 minutes.
Time is preferred, and 10 minutes to 10 hours is more preferred. Was
However, heat treatment must be performed at a temperature below which the support is not damaged.
It is necessary to use a polymer film for the support.
It is not preferable because it causes chemical conversion. Semiconductor fine particles can adsorb many dyes.
Those having a large surface area are preferred. Therefore, the semiconductor layer
The surface area in the state where is coated on the support is
And preferably at least 10 times, and at least 100 times
More preferably, there is. The dye in the photoelectric conversion element of the present invention is
Using a dye represented by the general formula (1) as a photoelectric conversion material
You. As a method for adsorbing a dye on a semiconductor layer,
Is to prepare semiconductor fine particles in the dye solution or dye dispersion.
Immerse the working electrode containing the dye solution or dispersion
It is possible to use a method in which a liquid is applied to a semiconductor layer and adsorbed.
it can. In the former case, dipping, dip, roller,
The air knife method can be used, and in the latter case,
Wire bar method, slide hopper method, extrude
Use the coating method, curtain method, spin method, spray method, etc.
be able to. In adsorbing the dye, a condensing agent may be used in combination.
No. Condensing agents physically or chemically color the inorganic surface.
Have a catalytic action that is thought to bind element, or
Act stoichiometrically to shift chemical equilibrium in an advantageous manner
Any of these may be used. Furthermore, thio-
Or a hydroxy compound may be added. Solvents for dissolving the dye include water and methanol.
Water, ethanol, or isopropyl alcohol
Alcoholic solvents, acetone, methyl ethyl ketone,
Or ketone solvents such as methyl isobutyl ketone, formic acid
S, such as ethyl, ethyl acetate, or n-butyl acetate
Ter solvents, diethyl ether, dimethoxyethane,
Trahydrofuran, dioxolan, or dioxane
Ether solvents such as N, N-dimethylformamide,
N, N-dimethylacetamide or N-methyl-
Amide solvents such as 2-pyrrolidone, dichloromethane,
Loroform, bromoform, methyl iodide, dichloroe
Tan, trichloroethane, trichloroethylene, chloro
Benzene, o-dichlorobenzene, fluorobenzene,
Bromobenzene, iodobenzene, or 1-chloro
Halogenated hydrocarbon solvents such as naphthalene, n-penta
, N-hexane, n-octane, 1,5-hexadiene
Cyclohexane, methylcyclohexane, cyclohexane
Xadiene, benzene, toluene, o-xylene, m-
Xylene, p-xylene, ethylbenzene, or
Mention may be made of hydrocarbon solvents such as men.
Can be used alone or as a mixture of two or more
You. Using these, the temperature at which the dye is adsorbed and the temperature
Therefore, the temperature is preferably from -50 ° C to 200 ° C. Ma
This adsorption may be performed with stirring. Stir
When using a stirrer, ball mill, pay
Conditioner, sand mill, attritor, de
Disperser, or ultrasonic dispersion, etc.,
It is not limited to these. Time required for adsorption
Is preferably 5 seconds or more and 1000 hours or less, and 10 seconds or less.
Above, 500 hours or less is more preferable, and 1 minute or more, 150
Time is more preferred. As the charge transfer layer of the present invention, a redox couple
Electrolyte dissolved in organic solvent, redox couple in organic solvent
Gel electrolysis in which a dissolved liquid is impregnated in a polymer matrix
Decomposition, molten salt containing redox couple, solid electrolyte, organic
A hole transport material or the like can be used. The electrolytic solution used in the present invention comprises an electrolyte,
It is preferable to be composed of a medium and an additive. Preferred
Electrolytes are lithium iodide, sodium iodide and iodide
Metals such as potassium, cesium iodide, calcium iodide
Iodide-iodine combination, tetraalkylammonium
Nium iodide, pyridinium iodide, imidazo
Iodine of quaternary ammonium compounds such as lium iodide
Salt-iodine combination, lithium bromide, sodium bromide
, Potassium bromide, cesium bromide, calcium bromide, etc.
Metal bromide-bromine combination, tetraalkylammonium
Quaternary ammonium bromide, pyridinium bromide, etc.
Bromine salts of ammonium compounds-bromine combinations, ferro
Cyanate-ferricyanate, ferrocene-ferrici
Metal complexes such as ammonium ions, sodium polysulfide, aluminum
Sulfur compounds such as kirthiol-alkyl disulfide
Products, viologen dyes, hydroquinone-quinone, etc.
It is. The above-mentioned electrolytes are mixed
It may be. As an electrolyte, it is in a molten state at room
Can also be used. When using this molten salt
Does not need to use a solvent. The electrolyte concentration in the electrolyte is 0.05 to
20M is preferable, and 0.1-15M is more preferable. Electric
Solvents used for dissolution include ethylene carbonate,
Carbonate solvents such as propylene carbonate,
Heterocyclic compounds such as tyl-2-oxazolidinone;
Sun, diethyl ether, ethylene glycol dialki
Ether solvents such as toluene, methanol, ethanol
, Polypropylene glycol monoalkyl ether, etc.
Alcohol solvents, acetonitrile, benzonitrile
Nitrile solvents such as dimethyl sulfoxide, sulfora
Preferred are aprotic polar solvents such as butane. Also, t-
Butylpyridine, 2-picoline, 2,6-lutidine and the like
Basic compounds can also be added. In the present invention, the electrolyte is polymer-added,
Gelling agent, polymerization containing polyfunctional monomers, polymer
Gelation by a method such as cross-linking reaction
You. Preferred gel for gelation by polymer addition
Polyacrylonitrile, polyvinyl fluoride
Nilidene and the like can be mentioned. Oil gelling agent added
Preferred gelling agents when gelling by
Dibenzylden-D-sorbitol, cholesterol inducer
Conductor, amino acid derivative, trans- (1R, 2R)-
Alkyl amide derivatives of 1,2-cyclohexanediamine
, Alkyl urea derivative, N-octyl-D-glucone
Amidobenzoate, double-headed amino acid derivative, quaternary anne
Monium derivatives and the like. In the case of polymerizing with a polyfunctional monomer,
Preferred monomers include divinylbenzene and ethylene.
Glycol dimethacrylate, ethylene glycol dia
Acrylate, diethylene glycol dimethacrylate,
Triethylene glycol dimethacrylate, Pentaery
Thritol triacrylate, trimethylolpropane
Triacrylate and the like can be mentioned. In addition,
Acrylic acid such as rilamide and methyl acrylate and α-
Esters and amides derived from alkyl acrylic acid
, Maleic acid such as dimethyl maleate and diethyl fumarate
Esters and butadiene derived from acid and fumaric acid
, Diene such as cyclopentadiene, styrene, p-
Such as chlorostyrene and sodium styrenesulfonate
Aromatic vinyl compounds, vinyl esters, acrylonitrile
, Methacrylonitrile, vinyl containing nitrogen-containing heterocycle
Compound, vinyl compound having quaternary ammonium salt, N
-Vinyl formamide, vinyl sulfonic acid, vinylidene
Fluoride, vinyl alkyl ethers, N-phenyl
It may contain a monofunctional monomer such as lumaleimide. Mo
The multifunctional monomer accounts for 0.5 to 70
% By mass is preferable, and 1.0 to 50% by mass is more preferable.
No. The above-mentioned monomers are obtained by radical polymerization.
Can be polymerized. Gel electrolyte that can be used in the present invention
Monomer for heating, light, electron beam or electrochemical
Radical polymerization is possible. Crosslinked polymer is heated
The polymerization initiator used when formed is 2,2
'-Azobisisobutyronitrile, 2,2'-azobis
(2,4-dimethylvaleronitrile), dimethyl-2,
Azo such as 2'-azobis (2-methylpropionate)
Initiator, peroxide initiator such as benzoyl peroxide
Agents and the like are preferred. The amount of these polymerization initiators added is
0.01 to 20% by mass based on the total amount of the mer is preferable,
0.1-10 mass% is more preferable. The electrolyte is gelled by the crosslinking reaction of the polymer.
When the reaction is carried out, a polymer containing a reactive group necessary for the crosslinking reaction
It is desirable to use a mer and a crosslinking agent together. Crosslinkable
Preferred examples of the reactive group include pyridine, imidazo
, Thiazole, oxazole, triazole, morph
And nitrogen-containing heterocycles such as phosphorus, piperidine and piperazine.
Preferred crosslinking agents are halogenated alkyl
Aralkyl, sulfonic acid ester, acid-free
For nitrogen atoms in hydrates, acid chlorides, isocyanates, etc.
And a bifunctional or higher functional reagent capable of electrophilic reaction.
Wear. Using an inorganic solid compound instead of an electrolyte
In case, copper iodide, copper thiocyanate, etc. are cast and applied
Method, spin coating, dipping, electrolytic plating, etc.
Can be introduced inside the electrode. In the present invention, an organic electrode is used instead of the electrolyte.
Cargo transport materials can be used. Positive for charge transport materials
There are hole transport materials and electron transport materials. As an example of the former,
For example, Japanese Patent Publication No. 34-5466 discloses
Xadiazoles, as shown in JP-B-45-555 and the like.
Triphenylmethanes, Japanese Patent Publication No. 52-4188
Pyrazolines described in Japanese Patent Application Publication No. Sho 55-4
Hydrazones disclosed in JP 2380
Oxadia disclosed in JP-A-56-123544 and the like.
Zoles are disclosed in JP-A-54-58445.
Tetraarylbenzidines, JP-A-58-6544
No. 0 or JP-A-60-98437.
And other stilbenes. That
Among them, the charge transport material used in the present invention is particularly
JP-A-60-24553, JP-A-2-96767
Gazette, JP-A-2-183260, and JP-A-2
Hydrazones disclosed in JP-A-226160,
JP-A-2-51162 and JP-A-3-7566.
The stilbenes disclosed in Japanese Patent Publication No. 0 are particularly preferred.
These may be used alone or as a mixture of two or more.
Can be used. On the other hand, as the electron transporting substance, for example,
Ranyl, tetracyanoethylene, tetracyanoquinodime
Tan, 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-trinitro
Dibenzothiophene or 1,3,7-trinitro
And dibenzothiophene-5,5-dioxide. This
These electron transport materials may be used alone or as a mixture of two or more.
Can be used as Further, a sensitizer for further increasing the sensitizing effect is provided.
To add certain electron-withdrawing compounds.
You. As the electron-withdrawing compound, for example, 2,3-di
Chloro-1,4-naphthoquinone, 1-nitroanthraki
Non-, 1-chloro-5-nitroanthraquinone, 2-
Quinones such as loloanthraquinone and phenanthrenequinone
Aldehydes such as 4-nitrobenzaldehyde, 9
-Benzoylanthracene, indandione, 3,5-
Dinitrobenzophenone or 3,3 ', 5,5'
Ketones such as tetranitrobenzophenone, anhydrous lid
Acid anhydrides such as phosphoric acid and 4-chloronaphthalic anhydride;
Phthalalmalononitrile, 9-anthrylmethylidenema
Lononitrile, 4-nitrobenzalmalononitrile,
Or 4- (p-nitrobenzoyloxy) benzalma
Cyano compounds such as lononitrile;
Do, 3- (α-cyano-p-nitrobenzal) phthalic
Or 3- (α-cyano-p-nitrobenzal)
Phthalide such as -4,5,6,7-tetrachlorophthalide
And the like. Using these charge transport materials, a charge transfer layer
When forming, it is preferable to use a resin together,
Styrene resin, polyvinyl acetal resin, polysulfo
Resin, polycarbonate resin, polyester resin,
Phenylene oxide resin, polyarylate resin,
Krill resin, methacrylic resin, phenoxy resin, etc.
Can be Among these, polystyrene resin, polyvinyl
Luacetal resin, polycarbonate resin, polyester
Resin and polyarylate resin are excellent. Also these
Resin is used alone or as a copolymer.
Can be used. Among these resins, tension, bending,
Some have weak mechanical strength such as compression. Improve this property
In order to be able to add substances that give plasticity
You. Specifically, phthalic acid esters (for example, DOP, DOP
BP, etc.), phosphate esters (eg, TCP, TOP
Etc.), sebacate, adipate, nitro
Lil rubber, chlorinated hydrocarbons, and the like. These things
Quality can adversely affect properties if added too much
The ratio is preferably 20% or less based on the binder resin.
No. In addition, antioxidants and anti-curl agents etc. as required
Can be added. The amount of the resin used is 1 mass of the charge transport material.
0.001 to 20 parts by mass, preferably 0.01 to 20 parts by mass,
1 to 5 parts by mass or less is more preferable. Resin ratio too high
Sensitivity decreases, and the ratio of resin becomes too low.
May cause deterioration of the repetition characteristics and loss of the coating film.
You. The method of forming the charge transfer layer can be roughly divided into two types.
The law can be considered. One is semiconductor fine particles carrying a sensitizing dye.
The counter electrode is first stuck on the element containing layer, and the liquid
This is a method of sandwiching a charge transfer layer in a shape. The other is half
Method of directly providing a charge transfer layer on a layer containing conductive fine particles
It is. In this case, the counter electrode will be newly added
Become. In the former case, the method of sandwiching the charge transfer layer
And the normal pressure process using the capillary phenomenon caused by immersion etc.
Vacuum process that replaces gas phase with liquid phase at a pressure lower than normal pressure
Seth. In the latter case, the wet charge transfer layer
In addition, a counter electrode is applied while it is still dry to prevent liquid leakage at the edge.
It is necessary to stop. In the case of gel electrolyte,
Is a method of solidifying by wet coating and polymerization
There is also. In that case, after drying and immobilizing,
You may. In addition to the electrolyte, a solution or organic solvent
The method of applying the electrolyte is as follows:
Dipping method, roller method, dipping
Method, air knife method, extrusion method, slide
Hopper method, wire bar method, spin method, spray method,
Examples include a casting method and various printing methods. The counter electrode is usually a conductor similar to the conductive support described above.
Although a support having an electrically conductive layer can be used,
In a configuration that ensures sufficient sealing, the support must be
Is not necessary. As a specific example of the material used for the counter electrode,
Platinum, gold, silver, copper, aluminum, rhodium, indium
Oxidation of metals such as metals, conductive metals such as carbon, ITO and FTO
Objects and the like. There is no limitation on the thickness of the counter electrode. In order for light to reach the photosensitive layer, the above-described light guide is required.
At least one of the conductive support and the counter electrode is substantially transparent.
I have to. In the photoelectric conversion element of the present invention,
The conductive support is transparent and sunlight is incident from the support side.
Is preferred. In this case, the opposite electrode reflects light
It is preferable to use materials such as metals and conductive oxides
Glass, plastic, or metal thin film
preferable. Regarding the application of the counter electrode, as described above, the charge transfer is performed.
On the moving layer and on the semiconductor fine particle layer
There are two cases. In either case, the type of counter electrode material and
Depending on the type of the charge transfer layer, the charge transfer layer or semiconductor
Coating, laminating, and steaming the counter electrode material on the body fine particle containing layer
It can be formed by a method such as attachment and bonding. Also,
If the charge transfer layer is a solid,
Form a counter electrode by applying a conductive material, such as coating, vapor deposition, or CVD.
Can be Next, the present invention will be described in more detail by way of examples.
However, the present invention is not limited to these. Example 1 3 g of titanium oxide (P-25 manufactured by Nippon Aerosil Co., Ltd.)
0.2 g of tilacetone, surfactant (manufactured by Aldrich)
Triton X-100) 0.3 g with 6.5 g of water
Dispersion treatment was performed for 6 hours using a conditioner. This dispersion
To a film thickness of 10 using a wire bar on an FTO glass substrate.
It was applied to a thickness of μm. After coating, at 100 ° C for 1 hour
Dried and then calcined in air at 450 ° C. for 30 minutes. The dye 0.0 represented by the exemplified compound (A-1)
5 g was dissolved in 50 ml of ethanol. To this solution,
The semiconductor electrode prepared in the above was immersed at room temperature for 15 hours,
Was applied. As the electrolytic solution, iodine 0.03M, tet
Ra-n-propyl ammonium iodide 0.5M
Mixture of ropylene carbonate / acetonitrile = 6/4
The solution dissolved in the liquid was used. Platinum on FTO for counter electrode
Was used. An electrolyte is immersed between both electrodes to form a photoelectric conversion element.
Produced. Here, from the working electrode side, cut filter made by Toshiba
10 cut light of 400 nm or less by UV-39
0mW / cm ^Two A high intensity xenon lamp was applied. That
As a result, the open-circuit voltage was 0.62 V, and the short-circuit current density was 7.2 mA /
cm ^Two Good, shape factor 0.60, conversion efficiency 2.68%
Value. Examples 2-6 Exemplified compounds (A-1) were changed to the dyes shown in Table 1
Except for the above, a device was prepared and evaluated in the same manner as in Example 1. That
Table 1 shows the results. [Table 1] As can be seen from the results in Table 1, the color of the present invention
It can be seen that the element shows good conversion efficiency. Embedded image Comparative Example 1 Exemplified compound (A-1) was changed to the compound shown in (10)
A device was prepared and evaluated in the same manner as in Example 1 except that
Was. As a result, the open-circuit voltage was 0.63 V and the short-circuit current density was 1.
6mA / cm ^Two , Form factor 0.38, conversion efficiency 0.38
%. As is clear from the above, according to the present invention,
To provide a photoelectric conversion element having good conversion efficiency
Can be.

Claims (1)

[Claims] At least one represented by the following general formula (1)
Characterized by using a kind of dye as a photoelectric conversion material
Photoelectric conversion element. Embedded image (In the general formula (1), R₁Is an aryl group or a heterocyclic ring
It represents a residue and each may have a substituent. R_Two,
R_Three, R_FourRepresents a hydrogen atom, an alkyl group, an alkoxy group,
And a heterocyclic residue, each having a substituent
It may be. R _FiveRepresents a substituent having an acidic group;
Is a carbonyl group and R_FiveWith the amino group substituting
A heterocyclic ring forming a 7-membered ring is shown. n is an integer of 0 to 2, m
Represents an integer of 1 to 3. The carbon-carbon double bond is E-form,
Or it may be any of the Z type. )