JP2003197281A - Photoelectric conversion element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photoelectric conversion element having a superior photoelectric conversion characteristic. <P>SOLUTION: This is the photoelectric conversion element using at least one kind of merocyanine pigment shown in the formula 1 or 2 as the photoelectric conversion material. A<SB>1</SB>and A<SB>2</SB>parts are coupling groups for forming a heterocyclic ring to form a 5 to 7 membered ring, and may have a substituent. B<SB>1</SB>part represents a divalent conjugated double bond group, and it may be aliphatic or cyclic. R<SB>1</SB>to R<SB>8</SB>show alkyl groups and X<SB>1</SB>and X<SB>3</SB>respectively show O, S, Se, hydrocarbon group, and substituted amino group. X<SB>2</SB>and X<SB>4</SB>show O, S, dicyanomethylene group, carboxyl-cyanomethylene group, n1 and n2 are integers of 0 to 2, and carbon-carbon double bond may be either E type or Z type. <P>COPYRIGHT: (C)2003,JPO

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a melody having a specific structure.
For photoelectric conversion elements using an anine dye as a photoelectric conversion material
It is about. [0002] A large amount of CO generated by the use of fossil fuels
_Two Global warming due to global warming and energy demand accompanying population growth
The escalation is a major issue related to the survival of mankind.
Recently, infinite and clean energy free of harmful substances
The use of solar energy, which is a source of energy, is being vigorously studied.
The ones that are currently in practical use as sunlight are
Powered by residential, remote or portable electronics
Certain single crystal silicon, polycrystalline silicon, amorphous silicon
Recon and cadmium telluride and indium selenide
An inorganic compound solar cell such as copper may be used. [0003] However, it is used in solar cells.
Silicon must be of very high purity.
The purification process required a lot of energy and complicated processes
High manufacturing costs. As a result, existing commercial
PV systems have higher power generation costs than
In the end there was a problem. In addition, for the user
There are also disadvantages such as a long G-payback time. On the other hand, it is easy to increase the area in order to reduce the price.
Many solar cells using organic materials have been proposed so far.
ing. Work with p-type organic semiconductors as organic solar cells
Schottky-type photoelectric conversion for bonding small function metals
Element, p-type organic semiconductor and n-type inorganic semiconductor, or p-type
Hetero-junction bonding organic semiconductor and electron-accepting organic compound
There are junction type photoelectric conversion elements, etc., and organic
Synthetic dyes such as chlorophyll and perylene as semiconductors
Pigment, conductive polymer material such as polyacetylene, or
These composite materials are available.
Thickened by thin film method or dipping method
It is composed of Their conversion efficiency is as low as 1% or less.
There were many problems and the durability was poor. 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
That an inexpensive photoelectric conversion element can be provided,
In addition, the absorption of the used dye extends over a wide visible light range.
And effectively convert sunlight with a large visible light component to electricity
It is possible. On the other hand, improvements in dye-sensitized photoelectric conversion elements are required.
One of the important points is that lute dyes, which are very expensive
Ium complex dyes. This expensive ruthenium color
Development to change element to less expensive organic dye is desired
However, organic dyes have low adsorptivity to titanium dioxide,
Since the amount of adsorption is often small, it is not possible to obtain high sensitization efficiency.
Not. 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, the above-mentioned general formula (1),
Emits at least one of the dyes represented by (2)
This has been achieved by using it as an electricity conversion material. [0009] In the general formula (1) or (2), A
₁ , A _Two Is a linking group necessary to form a heterocyclic ring.
Represents a heterocyclic ring forming a 5- to 7-membered ring, and has a substituent
May be. B ₁ Part represents a divalent conjugated double bond group,
It may be linear or cyclic. R ₁ ~ R ₈ Is al
X represents a kill group; ₁ , X _Three Are oxygen and sulfur, respectively
, A selenium atom, a hydrocarbon group, and a substituted amino group. X
_Two , X _Four Represents an oxygen atom, a sulfur atom, a dicyanomethylene group,
Indicates a carboxyl-cyanomethylene group. n1 and n2 are
An integer of 0 to 2, wherein the carbon-carbon double bond is an E-type,
May be any of Z type. DETAILED DESCRIPTION OF THE INVENTION Here, A ₁ , A _Two As a specific example of the department
Pyridine ring, benzothiazole ring, benzoxa
Zole ring, benzoselenazole ring, 1-ethylbenzi
A midazole ring, a 3,3-dimethylindolenine ring, etc.
Can be mentioned. R ₁ ~ R ₈ A specific example of
And alkyl groups such as an ethyl group and an isopropyl group.
be able to. Also, R ₁ ~ R ₈ May have a substituent
Good examples include methoxy and ethoxy groups.
Allyls such as alkoxy, phenyl, naphthyl, etc.
Group, carboxyl group, sulfonyl group, phosphoryl group,
Hydroxamic acid groups may be mentioned. X ₁ , X _Three Utensils
Examples include oxygen, sulfur, selenium, and methylene.
2,2-propylene, 1,1-cyclohexylene
Which hydrocarbon groups, methylamine, ethylamine, benzyl
List amino groups such as ruamine and phenylamine
Can be. X _Two , X _Four Examples of the oxygen atom, sulfur source
, Dicyanomethylene group, carboxyl-cyanomethyle
Group. B ₁ The following are specific examples of the section
(3) to (12).
However, the present invention is not limited to these. Embedded image Specific examples of the dye according to the present invention include:
Although A-01 to 27 shown below can be mentioned,
It is not limited to these. Embedded image Embedded image 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 may be 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, a conductive film made of ITO or FTO is
Conductive glass deposited on a substrate is particularly preferred. In order to reduce the resistance of the transparent conductive support,
It is preferable to use metal leads,
The material is aluminum, copper, silver, gold, platinum, nickel, etc.
Metals are preferred. Metal leads are deposited on a transparent support,
Installed by sputtering etc., and put ITO or FTO on it
Or metal lead on transparent conductive layer
There is a way to do that. 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 a semiconductor layer on a 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 liquid prepared by
The binder resin is formed by dispersing in water or an organic solvent.
You. As the binder resin used, styrene, vinyl acetate
Acrylate, methacrylate, etc.
Vinyl compound polymers and copolymers, silicone resins,
Phenoxy resin, polysulfone resin, polyvinyl butyral
Resin, polyvinyl formal resin, polyester tree
Fat, cellulose ester resin, cellulose ether tree
Fat, urethane resin, phenol resin, epoxy resin,
Recarbonate resin, polyarylate resin, polyamide
Resin, polyimide resin, or the like can be used. 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 coating method of the obtained 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, and 1 to 30 μm
Is 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. At that time
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 device of the present invention is
The merocyanine dyes represented by the general formulas (1) and (2) are
Used as a conversion material. In adsorbing the dye, a condensing agent may be used in combination.
No. Condensing agents physically or chemically color the inorganic surface.
Catalyzes that may bind
Any that works stoichiometrically and favorably shifts the chemical equilibrium
There may be. Further, a thiol or
May add a hydroxy compound. Solvents for dissolving the dye include acetone and methyl.
Such as ethyl ketone or methyl isobutyl ketone
Ketone solvent, ethyl formate, ethyl acetate, or acetic acid
ester solvents such as n-butyl, diethyl ether,
Methoxyethane, tetrahydrofuran, dioxolan,
Alternatively, ether solvents such as dioxane, N, N-dimethyl
Tylformamide, N, N-dimethylacetamide,
Or amide solvents such as N-methyl-2-pyrrolidone,
Dichloromethane, chloroform, bromoform, iodide
Methyl, dichloroethane, trichloroethane, triclo
Roethylene, chlorobenzene, o-dichlorobenzene,
Fluorobenzene, bromobenzene, iodobenzene,
Or a halogenated hydrocarbon such as 1-chloronaphthalene
System solvent, n-pentane, n-hexane, n-octane,
1,5-hexadiene, cyclohexane, methylcyclo
Hexane, cyclohexadiene, benzene, toluene,
o-xylene, m-xylene, p-xylene, ethylbenzene
Hydrocarbon solvents such as benzene and cumene
These can be used alone or as a mixture of two or more.
Can be used. 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
In addition, this adsorption may be performed with stirring.
No. Stirrer, ball
Mills, paint conditioners, sand mills, atlas
Itter, disperser, or ultrasonic dispersion
However, the present invention is not limited to these. Required for adsorption
The time for performing is preferably 5 seconds or more and 1000 hours or less,
10 seconds or more and 500 hours or less, more preferably 1 minute or more
Above, 150 hours are more preferable. 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
Iodine, 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 temperature
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
Adding basic compounds such as 2,2-lutidine and the like
Can also. 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. When 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 derived from acid or fumaric acid, butadie
, 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'-azobi
(2,4-dimethylvaleronitrile), dimethyl-
2,2'-azobis (2-methylpropionate) and the like
Peroxides such as azo initiators and benzoyl peroxide
Initiators and the like are preferred. The amount of addition of these polymerization initiators,
0.01 to 20 parts by mass based on the total amount of monomers is preferred
And 0.1 to 10 parts by mass is more preferable. Electrolyte gelled by polymer crosslinking reaction
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 an electron transport material, 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, there are 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 resin used is
0.001 to 20 parts by mass is preferable for 1 part by mass of the substance to be sent.
Preferably, the amount is 0.01 to 5 parts by mass or less. 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 the shape of a circle. 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
To prevent leakage of liquid 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. The thickness of the counter electrode is not limited, but is 3 nm.
-10 μm is preferred. In order for light to reach the photosensitive layer, the above-described conduction 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
Metal, conductive oxide
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 with reference to examples.
However, the present invention is not limited to these. Example 1 3 g of titanium oxide (P-25, Nippon Aerosil Co., Ltd.)
0.2 g of tilacetone, a surfactant (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
Was coated on a FTO glass support using a wire bar to a film thickness of 1
It was applied so as to have a thickness of 0 μm. After application, 1 hour at 100 ° C
And then bake in air at 450 ° C. for 30 minutes
A semiconductor electrode was manufactured. The merocyanine represented by the exemplified compound (A-02)
Dissolve 0.05 g of nin dye in 100 ml of ethanol
Was. The semiconductor electrode prepared above was added to this solution at room temperature for 15 minutes.
It was immersed for a time and subjected to an adsorption treatment. 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
50 which cuts light of 400 nm or less by UV-39
mW / cm ^Two A high intensity xenon lamp was applied. The result
As a result, the open-circuit voltage is 0.60 V and the short-circuit current density is 4.5 mA / c.
m ^Two , Form factor 0.54, conversion efficiency 2.9%, good value
showed that. Examples 2 to 8 The exemplified compounds (A-02) were changed to the exemplified compounds shown in Table 1.
A photoelectric conversion element was fabricated in the same manner as in Example 1 except for the change.
It was manufactured and evaluated. Table 1 shows the results. [Table 1] Embedded image Comparative Example 1 The exemplified compound (A-02) was changed to the compound shown in (13).
A photoelectric conversion element was manufactured in the same manner as in Example 1 except for the above.
And evaluated. As a result, the open circuit voltage is 0.15V,
Flow density 0.5mA / cm ^Two , Form factor 0.37, conversion effect
The rate was as low as 0.055%. Comparative Example 2 The exemplified compound (A-02) was changed to the compound shown in (14).
A photoelectric conversion element was manufactured in the same manner as in Example 1 except for the above.
And evaluated. As a result, open-circuit voltage 0.44V, short-circuit voltage
Flow density 0.32 mA / cm ^Two , Form factor 0.43, transformation
The efficiency was as low as 0.12%. 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)

1. A photoelectric conversion element comprising at least one merocyanine dye represented by the following general formula (1) or (2) as a photoelectric conversion material. Embedded image (In the general formula (1) or (2), A ₁ and A ₂ parts are a linking group necessary for forming a heterocyclic ring, and represent a heterocyclic ring forming a 5- to 7-membered ring; B ₁ part represents a divalent conjugated double bond group, may be linear or cyclic, R _{1 to} R ₈ represent an alkyl group, and X ₁ , X ₃ represents an oxygen atom, a sulfur atom, a selenium atom, a hydrocarbon group, or a substituted amino group, and X ₂ and X ₄ represent an oxygen atom, a sulfur atom, a dicyanomethylene group, and a carboxyl-cyanomethylene group. n2 is an integer of 0 to 2, and the carbon-carbon double bond may be any of E-type and Z-type.)