JPH1174003A - Photosensitizer for photoelectric conversion material, photoelectric conversion material, method for producing the same, and photoelectric conversion device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photo-electric converting material which exerts a high efficiency and has excellent durability. SOLUTION: A photo-electric converting material includes a semiconductor and a photo-sensitivity intensifying pigment to be attached to the semiconductor, wherein the pigment is a phthalocyanine derivative, dioxadine derivative, or indigo derivative having at least one interlocking radical and at least one hydrophobic radical selected from a group consisting of one-valent substitutional and non-substitutional aliphatic series hydrocarbon radical and one-valent substitutional and non-substitutional aliphatic cyclic hydrocarbon radical. The hydrophobic radical should preferably be an alkyl radical having 3-12 carbon atoms. Interlocking radical is carboxyl radical, sulfonic radical, sulfono radical, etc. In manufacturing the photo-electric converting material, the pigment is dissovled in a hydrophobic and/or non-proton solvent. The semiconductor is immersed in a pigment solvent for attaching the pigment to the semiconductor.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoelectric conversion material, a method for producing the same, a photoelectric conversion device, and a photosensitizer for use therein, and more particularly to a photoelectric conversion material used for a photoelectric conversion element such as a photovoltaic cell. And its manufacturing method.

[0002]

2. Description of the Related Art A photoelectric conversion material is a material that converts light energy into electric energy. When light is irradiated to the photoelectric conversion material, electrons bound in the material can move freely by light energy, and free electrons and holes are generated. If the generated free electrons and holes are efficiently separated, electric energy can be continuously extracted from light energy in the photoelectric conversion material. Such a photoelectric conversion material is used for, for example, a solar cell.

In recent years, wet-type solar cells using photosensitizing dyes and having high conversion efficiency have attracted widespread attention. Such a wet solar cell mainly includes, for example, a semiconductor electrode, a counter electrode, and an electrolyte layer sandwiched between the electrodes. In a semiconductor electrode which is a photoelectric conversion material, a photosensitizing dye having an absorption spectrum in a visible light region is attached to a semiconductor surface. In such a battery, when the semiconductor electrode is irradiated with light, electrons are generated on the electrode side, and the electrons move through the electric circuit to the counter electrode. The electrons transferred to the counter electrode are carried by ions in the electrolyte and return to the semiconductor electrode. Such a process is repeated to extract electric energy.

Japanese Patent Laid-Open Publication No. Hei 1-220380 discloses a solar cell in which a photosensitizing dye such as a transition metal complex is attached to the surface of a metal oxide semiconductor. In the method for manufacturing a solar cell, the metal oxide semiconductor is immersed in an aqueous solution containing a photosensitizing dye at room temperature, whereby the photosensitizing dye is attached to the surface of the semiconductor.

[0005] International Publication No. WO91 / 16719
JP-A-5-504033 discloses a photovoltaic cell in which a photosensitizer is applied on a titanium dioxide layer doped with metal ions or boron. In this photovoltaic cell, the photosensitizer comprises an unsubstituted or substituted transition metal complex in which the ligand is a bidentate, tridentate or tridentate polypyridyl compound, and at least one ligand comprising a mononuclear cyano-containing compound. Including transition metal complexes, including pyridyl compounds. In such a photovoltaic cell manufacturing method, the titanium dioxide semiconductor layer is placed in an ethanol solution containing the photosensitizer, whereby the photosensitizer is deposited on the semiconductor layer.

[0006] International Publication No. WO94 / 05025
Discloses a photovoltaic cell in which a photosensitizer selected from a fluorescent whitening compound and a phthalocyanine compound is attached to a titanium dioxide layer. In such a photovoltaic cell manufacturing method, the photosensitizer is dissolved in ethanol, and the resulting ethanol solution is used to attach the photosensitizer to the titanium dioxide layer.

JP-A-7-249790 discloses a method of manufacturing a photoelectric conversion material used for a solar cell, in which a liquid containing a semiconductor and a photosensitizing dye is heated and refluxed to apply the photosensitizing dye to the surface of the semiconductor. Disclosed is adsorption. This publication discloses, as photosensitizing dyes, metal phthalocyanines such as copper phthalocyanine and titanyl phthalocyanine, chlorophyll, hemin, ruthenium, osmium, iron or ruthenium described in JP-A-1-220380 and JP-A-5-504033. It discloses that zinc complexes, metal-free phthalocyanines, cyanine dyes, merocyanine dyes, xanthene dyes and triphenylmethane dyes can be used. The publication also discloses that in the production of a photoelectric conversion material, water, alcohol, toluene or dimethylformamide can be used as a liquid for dissolving a photosensitizing dye therein. on the other hand,
This publication discloses a glass plate having cis- (SCN) ₂ -bis (2,2′-bipyridyl-4,4′-dicarboxylate) ruthenium (II) dissolved in ethanol and having a titanium oxide film in this ethanol solution. Is shown, and only a specific example in which a dye is adsorbed on a titanium oxide film by heating and refluxing an ethanol solution is shown. This publication does not support at all whether photosensitizing dyes other than the ruthenium complex are actually useful for photoelectric conversion materials. Also,
The publication does not provide any information as to whether solvents other than ethanol can actually be used to dissolve the photosensitizing dye in the production of the photoelectric conversion material.

[0008]

In spite of the fact that an ethanol solution of a photosensitizing dye has been used for the actual production of a photoelectric conversion material in the above-mentioned prior art, the present inventors have proposed such an ethanol solution. It has been found that the solution is not always suitable for attaching the photosensitizing dye to the semiconductor. We have found that hydrophilic solvents such as ethanol can contain relatively high amounts of water, and such water reacts with active sites on the semiconductor surface to hinder the adsorption of the dye, and the required amount of the dye is added to the semiconductor surface. Can not be fixed strongly. When the amount of the dye fixed to the semiconductor decreases, the photoelectric conversion efficiency of the obtained photoelectric conversion material decreases. In addition, the present inventors have found that a hydrophilic solvent such as ethanol, which easily absorbs moisture in the air, causes water to be adsorbed on the semiconductor surface during the manufacturing process, thereby shortening the life of the semiconductor. .

Therefore, in order to eliminate the influence of water as described above, a step of removing water from the hydrophilic solvent is required. However, even if the present inventors performed the dehydration step, the hydroxyl groups of ethanol could react with the active sites on the semiconductor surface and interfere with the adsorption of the dye, making it difficult to adsorb the required amount of the dye, It was thought that the strong adsorption of the dye could be prevented.

On the other hand, International Publication No. WO94 / 05
Since the various phthalocyanine derivatives described in No. 025 are hardly soluble in general organic solvents, it was considered that it was difficult to adsorb a desired amount of the phthalocyanine derivative to a semiconductor in a molecular state. Many photosensitizing dyes were found to be hardly soluble in organic solvents. It has been found that a material having a high photoelectric conversion efficiency cannot be obtained when a solution containing a dye at a sufficient concentration cannot be obtained due to adsorption to a semiconductor.

An object of the present invention is to provide a photoelectric conversion material having a relatively high photoelectric conversion efficiency.

A further object of the present invention is to provide a method for easily and inexpensively producing a photoelectric conversion material having a relatively high photoelectric conversion efficiency.

It is a further object of the present invention to provide a photoelectric conversion device such as a solar cell using a material having a relatively high photoelectric conversion efficiency.

A further object of the present invention is to provide a method for producing a photoelectric conversion material which can eliminate the above-mentioned effects of water and hydroxyl groups.

A further object of the present invention is to provide a photoelectric conversion material which is actually useful by using a dye whose usefulness has not been demonstrated in the prior art.

A further object of the present invention is to provide a practically useful photosensitizer for a photoelectric conversion material which is easily dissolved in an organic solvent, and to provide a photoelectric conversion material using such a photosensitizer. It is to be.

[0017]

According to the present invention, a dye functioning as a photosensitizer is dissolved in one or more kinds of hydrophobic and / or aprotic solvents.
Contacting a solvent containing the dye with a semiconductor to attach the dye to the semiconductor, thereby providing a method for producing a photoelectric conversion material. If an aprotic solvent is used for dissolving the dye, it is possible to prevent the hydroxyl groups of the solvent from reacting with the active sites on the semiconductor surface. If a hydrophobic solvent is used to dissolve the dye, the above-mentioned effect of water can be further minimized.

In the present invention, a photosensitizer having high solubility in a hydrophobic and / or aprotic solvent is preferably used. Such a photosensitizer is selected from the group consisting of at least one interlocking group, a monovalent substituted and unsubstituted aliphatic hydrocarbon group and a monovalent substituted and unsubstituted alicyclic hydrocarbon group. It is composed of an organic compound dye having at least one hydrophobic group or an organic metal compound dye. It is preferable that such a hydrophobic group does not constitute a group directly binding to a metal in the dye. Such a hydrophobic group is preferably an alkyl group having 3 to 12 carbon atoms. Here, the interlocking group refers to a group having a function of providing electrical coupling between a coloring group of a dye and a conduction band of a semiconductor. Dyes are generally attached to the surface of the semiconductor via interlocking groups. Regarding the interlocking group, International Publication No. WO91 / 1671
No. 9 and the corresponding Japanese Translation of PCT International Publication No. 5-504033 are incorporated herein by reference. In the present invention, the interlocking group can be at least one selected from the group consisting of a carboxyl group, a hydroxyalkyl group, a hydroxyl group, a sulfonic acid group, a carboxyalkyl group, a mercapto group, and a phosphono group.

According to the present invention, there is provided a semiconductor and a photosensitizer attached to the semiconductor, wherein the photosensitizer comprises at least one interlocking group and at least one hydrophobic group as described above. A photoelectric conversion material comprising an organic compound dye or an organometallic compound dye having the formula: In this photoelectric conversion material, the semiconductor is preferably titanium oxide. The semiconductor can be in the form of particles or a film.

According to the present invention, the above-mentioned organic compound dye or organometallic compound dye having at least one interlocking group and at least one hydrophobic group is dissolved in a hydrophobic and / or aprotic solvent. A method for producing a photoelectric conversion material, comprising the steps of: contacting a solvent containing the dye with a semiconductor to attach the dye to the semiconductor.

According to the present invention, there is provided a photoelectric conversion device including the above-described photoelectric conversion material and an electrode electrically connected to the photoelectric conversion material. For example, according to the present invention, there is provided a solar cell including the above-described photoelectric conversion material, a conductive film, and an electrolyte sandwiched between the photoelectric conversion material and the conductive film.

According to the present invention, a photoelectric conversion device is provided, the device comprising a first conductive layer, a semiconductor layer formed on the first conductive layer, and at least a semiconductor layer formed on the semiconductor layer. A layer comprising the photosensitizer having one interlocking group and at least one hydrophobic group; an electrolyte layer provided on the layer comprising the photosensitizer; and a second conductive layer in contact with the electrolyte layer And The first conductive layer and / or the second conductive layer can be light transmissive. The semiconductor layer is preferably made of titanium oxide.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a semiconductor to which a photosensitizing dye is attached (adsorbed or bonded) is not particularly limited, and includes a semiconductor generally used for a photoelectric conversion material. And known semiconductors such as zinc oxide, tungsten oxide, barium titanate, strontium titanate, and cadmium sulfide. In the present invention, one or more of these semiconductors can be selected. Titanium oxide is a more preferred semiconductor material in terms of stability and safety. The titanium oxide used in the present invention includes various narrowly defined titanium oxides such as anatase-type titanium oxide, rutile-type titanium oxide, amorphous titanium oxide, metatitanic acid, and orthotitanic acid; and titanium hydroxide, hydrous titanium oxide and the like. Is included. The semiconductor can be in the form of particles, films, or the like. In particular, it is preferable to form a semiconductor film such as a titanium oxide film on the conductive support.

When a semiconductor film is formed on a substrate, for example, a glass substrate, a plastic substrate, or the like can be used, and a transparent substrate is particularly preferably used. The semiconductor film can be formed on a substrate by various known methods. Specifically, such a method includes a method in which a suspension containing semiconductor particles is applied to a substrate, followed by drying and / or baking, and a method in which a semiconductor or a semiconductor using a necessary source gas is used. The method includes a method of forming a film, a PVD method using a solid material, an evaporation method or a sputtering method, a sol-gel method, and the like. The thickness of the semiconductor film to be formed is not particularly limited, but is preferably about 0.1 to 50 μm.

As the semiconductor particles, commercially available particles of a single semiconductor or a compound semiconductor having an appropriate average particle diameter, for example, in the range of 1 nm to 2000 nm can be used. The semiconductor particles can be used by suspending them in an appropriate solvent. Such solvents include glyme solvents such as ethylene glycol monomethyl ether,
It includes alcohols such as isopropyl alcohol, alcohol-based mixed solvents such as isopropyl alcohol / toluene, and water. The suspension of semiconductor particles is applied to a substrate, dried and fired. The temperature, time, atmosphere, and the like necessary for drying and baking can be appropriately adjusted according to the type of substrate and semiconductor particles used. For example, drying and baking are performed under air or an inert gas atmosphere.
This can be performed at a temperature in the range of about 0 to 800 ° C. for about 10 seconds to 12 hours. Drying and baking may be performed once at a single temperature, or may be performed twice or more at different temperatures.

A source gas used for CVD or the like for forming a semiconductor film can be a single gas containing an element constituting a semiconductor, or a mixture of two or more gases. A solid material used for PVD or the like for forming a semiconductor film can be a single solid containing an element constituting a semiconductor, a combination of a plurality of solids, or a solid of a compound.

A photosensitizing dye is attached to the surface of the obtained semiconductor. Prior to the attachment of the dye, a treatment for activating the surface of the semiconductor may be performed as necessary. In the step of attaching the photosensitizing dye to the semiconductor, the dye is
One or more hydrophobic solvents, aprotic solvents,
Dissolved in hydrophobic and aprotic solvents or mixtures thereof.

The hydrophobic solvent used in the present invention includes, for example, halogenated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride; aliphatic hydrocarbons such as hexane and cyclohexane; and aromatic hydrocarbons such as benzene, toluene and xylene. Aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; ethyl acetate, butyl acetate,
Esters such as ethyl benzoate and the like, and combinations thereof. The aprotic solvent used in the present invention,
For example, ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether, diisopropyl ether and dimethoxyethane; nitrogen compounds such as acetonitrile, dimethylacetamide and hexamethylphosphoric triamide; sulfur compounds such as carbon disulfide and dimethyl sulfoxide Phosphorus compounds such as hexamethylphosphoramide, and combinations thereof. The hydrophobic and aprotic solvents used in the present invention include, for example, halogenated aliphatic hydrocarbons such as chloroform, methylene chloride and carbon tetrachloride; aliphatic hydrocarbons such as hexane and cyclohexane; benzene, toluene, xylene and the like. And esters such as ethyl acetate, butyl acetate and ethyl benzoate, and combinations thereof. In the present invention, it is more preferable to use a hydrophobic solvent. Especially,
Aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, aromatic hydrocarbons and halogenated aromatic hydrocarbons are more preferred hydrophobic solvents.

In the production method according to the present invention, the photosensitizing dye is dissolved in a hydrophobic and / or aprotic solvent. Such dyes include metal-free phthalocyanine dyes; cyanine dyes; merocyanine dyes; xanthene dyes such as rose bengal and rhodamine B; triphenylmethane dyes such as malachite green and crystal violet; copper phthalocyanine and titanyl phthalocyanine; Metal phthalocyanine, chlorophyll, hemin, or a complex containing at least one of ruthenium, osmium, iron and zinc (Japanese Patent Application Laid-Open No. 1-220380, W.
O91 / 16719 and corresponding Japanese translation of PCT application No. Hei 5-5
No. 04023).

The dye used as a photosensitizer in the present invention has an absorption spectrum in the visible light region and, if necessary, in the infrared light region. Therefore, the dye generally has a maximum absorption wavelength λmax between 400 nm and 1000 nm (400 nm <λmax <1
000 nm).

On the other hand, in a preferred embodiment, the present invention provides
International Publication No. WO 91/16719 and JP-A-5-504033 corresponding thereto and International Publication No. It is directed to the use of photosensitizing dyes other than those disclosed in WO 94/05025. The dye disclosed in this publication has poor light stability. For example, it has been found that an adsorbed solution of a ruthenium bipyridine dye is decomposed by room light. The present inventors have found that a material having a relatively high photoelectric conversion efficiency can be obtained by using a dye having a relatively high solubility in a hydrophobic and / or aprotic solvent. Dyes preferably used in the present invention include, for example, an azo-based structure, a quinone-based structure,
Quinone imine structure, quinacridone structure, squarylium structure, cyanine structure, merocyanine structure, triphenylmethane structure, xanthene structure, porphine structure, phthalocyanine structure, perylene structure, indigo structure, naphthalocyanine structure , An oxazine-based structure, or an anthraquinone-based structure. Therefore, azo dyes and their derivatives, quinone derivatives, quinone imine dyes and their derivatives, quinacridone pigments and their derivatives, squalilium dyes and their derivatives, cyanine dyes and their derivatives, merocyanines and their derivatives, triphenylmethane dyes and their derivatives,
Xanthene dyes and derivatives thereof, porphine derivatives (porphyrins), phthalocyanines and derivatives thereof, perylene derivatives, indigoid dyes and derivatives, naphthalocyanines and derivatives thereof, oxazine dyes and derivatives thereof, and anthraquinone dyes and derivatives thereof are preferably used. Can be

A dye having a metal complex structure has a high quantum yield and good durability against light, and is therefore suitable for a photoelectric conversion material. Metal complexes include Cu, Ni, Fe, C
o, V, Sn, Si, Ti, Ge, Cr, Zn, Ru,
Mg, Al, Pb, Mn, In, Mo, Y, Zr, N
b, Sb, La, W, Pt, Ta, Ti, Ir, Pd,
Os, Ga, Tb, Eu, Rb, Bi, Se, As, S
c, Ag, Cd, Hf, Re, Au, Ac, Tc, T
e, Rh, and the like. Considering environmental issues and wastewater treatment in the manufacturing process, Cu, Al, Fe,
Metal complexes containing Ti, Mg, Si, Zn, Sn or Ga are preferred. In particular, a metal phthalocyanine complex and a metal-free phthalocyanine structure can exhibit high photoelectric conversion efficiency and have excellent durability, and thus are more preferable as a chromophore of a photosensitizing dye for a solar cell.

In a more preferred embodiment according to the present invention,
The photosensitizing dye is at least one interlocking group and at least one hydrophobic group selected from the group consisting of a monovalent substituted and unsubstituted aliphatic hydrocarbon group and a monovalent substituted and unsubstituted alicyclic hydrocarbon group. And wherein the hydrophobic group does not constitute a group that directly binds to a metal in the dye. The interlocking group is
Generally, it serves to strongly fix the dye to the semiconductor. Interlocking groups include, for example, carboxyl groups, hydroxyalkyl groups, hydroxyl groups, sulfonic acid groups,
It can be selected from the group consisting of a carboxyalkyl group, a mercapto group and a phosphono group. The hydrophobic group of the dye serves to enhance the solubility of the dye in a hydrophobic and / or aprotic solvent. The substituted or unsubstituted aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms. A substituted or unsubstituted alicyclic hydrocarbon group has 3 to 12
, And more preferably 5 to 12 carbon atoms. By making the number of carbon atoms of these hydrocarbon groups 3 or more, the solubility of the dye in a hydrophobic and / or aprotic solvent can be significantly improved. On the other hand, it is preferable that the number of carbon atoms be 12 or less in consideration of the fact that when the number of carbon atoms of these hydrocarbon groups increases, the distance between the dye molecules attached to the semiconductor surface increases. In particular, the dye used in the present invention preferably has an alkyl group. The alkyl group has 3 carbon atoms.
-20, preferably 3-15, more preferably 3-12, straight or branched chain alkyl groups. Alkyl groups are, for example, methyl, ethyl,
Including propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl and the like. The substituents for the hydrocarbon groups described above preferably include halogens such as, for example, F, Cl, Br and the like. Dyes can have one or more hydrophobic groups.

The dyes more preferably used in the present invention are shown below. Phthalocyanines represented by the formula (I) or (II) and derivatives thereof.

[0035]

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[0036]

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Wherein A ₁ , A ₂ , A ₃ and A ₄ are
Each is selected from the group consisting of hydrogen, carboxyl group, hydroxyalkyl group, hydroxyl group, sulfonic acid group, carboxyalkyl group, mercapto group and phosphono group, provided that at least _one of A ₁ , A ₂ , A ₃ and A ₄ One is not a hydrogen atom and B ₁ , B ₂ , B ₃ and B ₄ are -R, -OR, -CH ₂ OR, -SR, -O
Selected from the group consisting of COR, -COR, -CONRR 'and -NRR' (wherein R and R 'are substituted and unsubstituted aliphatic hydrocarbon groups having 3 to 12 carbon atoms and substituted and unsubstituted aliphatic hydrocarbon groups). The same or different hydrophobic groups selected from the group consisting of cyclic hydrocarbon groups), n and m
Represents an integer of 0, 1, 2, 3, or 4, respectively.
However, n + m is 4 or less, and M represents two hydrogen atoms or an atom or a compound capable of forming a covalent bond or a coordinate bond with phthalocyanine.

In the formula (I) or (II), M is
Two hydrogen atoms, Cu, VO, Co, TiO, Fe, A
lCl, Mg, Sn, SnO, Pb, Zn or Si
(OR) ₂ wherein R is alkyl, preferably C _1-4
Alkyl, aryl, preferably C _7-12 aryl). Formula (I) or (I
The dyes represented by I) can be dissolved in hydrophobic and / or aprotic solvents at a concentration of 5 × 10 ⁻⁵ to 1 × 10 ⁻² mol / l.

Indigoid dyes represented by the formula (III) and derivatives thereof.

[0040]

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Wherein A ₅ is selected from the group consisting of —R and —COR (where R is a substituted or unsubstituted aliphatic hydrocarbon group having 3 to 12 carbon atoms and a substituted or unsubstituted And A ₆ is a group consisting of a carboxyl group, a hydroxyalkyl group, a hydroxyl group, a sulfonic acid group, a carboxyalkyl group, a mercapto group, and a phosphono group. Selected from).

A quinacridone pigment represented by the formula (IV) and a derivative thereof.

[0043]

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Wherein A ₅ and A ₆ are of the formula (III)
Is synonymous with). An oxazine dye represented by the formula (V) and a derivative thereof.

[0045]

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Wherein A ₅ and A ₆ are of the formula (III)
Is synonymous with). A cyanine dye represented by the formula (VI) and a derivative thereof.

[0047]

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Wherein A ₅ and A ₆ are of the formula (III)
Is synonymous with). A squarylium dye represented by the formula (VII) and a derivative thereof.

[0049]

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Wherein A ₅ and A ₆ are of the formula (III)
Is synonymous with). Anthraquinone dyes represented by the formula (VIII) and derivatives thereof.

[0051]

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(Where A ₁₁ , A ₁₂ , A ₁₃ , A ₁₄ , A ₁₅ ,
A ₁₆ , A ₁₇ and A ₁₈ represent hydrogen, Cl, Br, F,-
R, —OR, —NRR ′, and —NCOR (where R and R ′ are each independently a substituted or unsubstituted aliphatic hydrocarbon group having 3 to 12 carbon atoms and a substituted or unsubstituted alicyclic hydrocarbon group) And a carboxyl group, a hydroxyalkyl group, a hydroxyl group, a sulfonic acid group, a carboxyalkyl group, a mercapto group, and a phosphono group. , A _{11 to} A ₁₈ are the interlocking groups, and A ₁₁ to
_At least one of A ₁₈ is selected from the group consisting of —R, —OR, —NRR ′, and —NCOR).

Xanthene dyes represented by the formula (IX) and derivatives thereof.

[0054]

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(Wherein R ₁ is a hydrophobic group selected from the group consisting of substituted and unsubstituted aliphatic hydrocarbon groups having 3 to 12 carbon atoms and substituted and unsubstituted alicyclic hydrocarbon groups, A ₂₁ , A ₂₂ , A ₂₃ , A ₂₄ and A ₂₅ are hydrogen, C
l, Br, F, a carboxyl group, a sulfonic group, a carboxyalkyl group and a phosphono group, provided that at least one of A _{21 to} A ₂₅ is a carboxyl group, a sulfonic group, a carboxyalkyl group and a phosphono group. Selected from the group consisting of groups).

A metal complex represented by the formula (X).

[0057]

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(Where M is Ni, Pt and Cu)
X and Y are NH_Two, NH, S and
Selected from the group consisting of₃₁, A₃₂, A₃₃,
A₃₄, A ₃₅, A₃₆, A₃₇And A₃₈Is hydrogen, Cl, B
r, F, -R, -OR, -NRR ', -NCOR (here
Wherein R and R 'are substituted and unsubstituted 3-1 carbon atoms.
Aliphatic hydrocarbon groups and substituted and unsubstituted alicycles
Same or different selected from the group consisting of hydrocarbon groups
Hydrophobic group), carboxyl group, hydroxy
Sialkyl group, hydroxyl group, sulfonic acid group, carbo
Xyalkyl, mercapto and phosphono groups
From the group consisting of interlocking groups selected from
Selected, but A₃₁~ A₃₈At least one of the
A tarlocking group, and A₃₁~ A₃₈At least
One is -R, -OR, -NRR 'and -NCOR.
Selected from the group consisting of:

The photosensitizing dye used in the present invention may be selected from commercial products having a suitable interlocking group and a suitable hydrophobic group. However, in most cases, commercially available organic dyes do not have either or both of the required interlocking groups and the required hydrophobic groups. Therefore, it is preferable to obtain a photosensitizing dye by modifying a commercially available organic dye or an organic dye obtained by a conventional technique, or by using an appropriate synthetic scheme. Commonly available methods for modifying dyes include introducing one or both of the required interlocking groups and the required hydrophobic groups. Generally, when the obtained dye has an appropriate hydrophobic group, an appropriate interlocking group may be introduced into the dye. When a commonly available dye has a suitable interlocking group, a hydrophobic group can be introduced into it. On the other hand, an appropriate hydrophobic group and an interlocking group can be respectively introduced into commonly available dyes. In general, since the introduction reaction is performed in an organic solvent or a non-polar solvent, in consideration of the solubility of the dye in the solvent, it is preferable to introduce an interlocking group into a dye having a hydrophobic group or having a hydrophobic group. Is advantageous. On the other hand, a dye may be synthesized from an intermediate having a hydrophobic group and / or an interlocking group introduced. For example, after synthesizing a dye skeleton from an intermediate having a hydrophobic group introduced therein, it is preferable to introduce an interlocking group therein.

For example, a phthalocyanine derivative having an interlocking group and a hydrophobic group is preferably synthesized from an intermediate having a hydrophobic group, as described later.

One of the interlocking groups -COOH
Can be introduced into a dye or an intermediate thereof according to the following scheme.

[0062]

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In this scheme, AlCl ₃ is dissolved in carbon disulfide and cooled. Oxalyl chloride is slowly added to the solution. The coloring material dissolved in carbon disulfide is dropped into a carbon disulfide solution containing oxalyl chloride and AlCl ₃ under cooling. After a suitable reaction time, a product having one or more carboxyl groups is obtained via a suitable separation step. Such a scheme can be applied to the synthesis of the photosensitizing dye described above.

Specific examples of introduction of a carboxyl group for some of the above dyes are shown below.

According to the scheme shown in the following formula, a carboxyl group can be introduced into a phthalocyanine derivative having a suitable hydrophobic group.

[0066]

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The indigo derivative having a hydrophobic group introduced therein includes:
A carboxyl group can be introduced according to the following formula.

[0068]

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A carboxyl group can be introduced into a quinacridone derivative having a hydrophobic group introduced therein according to the following formula.

[0070]

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A carboxyl group can be introduced into an oxazine derivative (dioxazine derivative) into which a hydrophobic group has been introduced according to the following formula.

[0072]

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One of the interlocking groups —SO ₃ H
Can be introduced into a dye or an intermediate thereof according to the following scheme.

[0074]

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In this scheme, the raw materials are slowly added to concentrated sulfuric acid with stirring. After reacting at 80 ° C. for 1 hour, the reaction mixture is poured into ice water. Filter and neutralize the solid with aqueous alkali, filter and dry to obtain a product with one or more sulfonic acid groups. This reaction can also be applied to the synthesis of the photosensitizing dye described above.

In order to obtain a dye having a hydrophobic group such as an alkyl group or an intermediate therefor, a reaction represented by the following formula can be used.

[0077]

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[0078]

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[0079]

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In the present invention, the photosensitizing dye is dissolved in a hydrophobic and / or aprotic solvent. As the solvent, an appropriate organic solvent as described above is used. A solvent purified according to a conventional method is preferably used. Further, prior to use of the solvent, distillation and / or drying may be performed as necessary to obtain a higher purity solvent. In the present invention, the dye is 1 × 10 ⁻⁵ mol / liter or more,
Preferably, it can be dissolved in a hydrophobic and / or aprotic solvent at a concentration of 5 × 10 ⁻⁵ to 1 × 10 ⁻² mol / liter. The concentration of the dye in the solvent can be adjusted according to the dye to be used, the type of the solvent, the conditions for the dye attaching step, and the like.

To attach the dye to the semiconductor, a solution of the dye is contacted with the semiconductor. Attachment of the dye can be achieved by immersing the semiconductor in the dye solution or applying the dye solution to the semiconductor. In the immersion method, the dye solution is filled in an appropriate container capable of housing the semiconductor,
The entire semiconductor or only a desired portion of the semiconductor can be immersed in the solution and held for a predetermined time. For example, immersion can be performed at room temperature under atmospheric pressure. However, the temperature and pressure of the solution and the atmosphere can be changed as required without limitation. The immersion time can be, for example, about 5 minutes to 96 hours, but is not particularly limited. The immersion time can be adjusted according to the type of dye, solvent used, concentration of the solution, and the like. The immersion can be performed once or multiple times. According to the present invention, a solution containing a sufficient concentration of the dye can be obtained, so that a sufficient amount of the dye can be attached to the semiconductor by immersing the semiconductor in the dye solution. However, if necessary, a process for increasing the concentration of the dye existing on the semiconductor may be performed. After the dipping or coating step, drying may be performed as appropriate. The dye adsorbed on the semiconductor by the method described above functions as a photosensitizer that sends electrons to the semiconductor by light energy. Generally, the dye is fixed to the semiconductor via an interlocking group. The interlocking group provides an electrical bond that facilitates electron transfer between the excited state dye and the conduction band of the semiconductor.

The photoelectric conversion material according to the present invention comprises a solar cell,
It is applied to photoelectric conversion devices such as optical switching devices and sensors. According to the present invention, for example, a solar cell as shown in FIG. 1 is provided. In a solar cell, a transparent conductive film 6
A semiconductor layer 5 such as titanium oxide is formed on a support 7 such as a glass plate coated with. The photosensitizing dye 4 is attached to the surface of the semiconductor layer 5. The conductive film 6, the semiconductor layer 5, and the dye 4 are sequentially deposited on the support 7 to obtain an electrode. The counter electrode has a support 1 such as a glass plate and a transparent conductive film 2 coated on the support. The electrolyte 3 is filled between these electrodes to form a solar cell.
The dye is attached to the semiconductor layer formed on the support as described above to obtain a photoelectric conversion material. By combining the obtained photoelectric conversion material with a conductive film and an electrolyte, a solar cell as a photoelectric conversion device is obtained. The conductive film is not particularly limited, and is preferably made of, for example, a transparent conductive material such as ITO and SnO ₂ . The conductive film can be formed by an ordinary method. As the electrolyte, those generally used for wet solar cells can be preferably used.

When the dye in the solar cell is irradiated with sunlight, the dye absorbs light in the visible region and excites it. The electrons generated by this excitation move to the semiconductor layer 5 and then to the transparent conductive film 2 of the counter electrode through the transparent conductive film 6. The electrons transferred to the counter electrode reduce the oxidation-reduction system in the electrolyte 3. On the other hand, the dye 4, which has transferred electrons to the semiconductor, is in an oxidized state, which is reduced by an oxidation-reduction system in the electrolyte and returns to the original state. Through the flow of electrons in such a process,
Light energy is continuously converted to electrical energy.

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

[0085]

【Example】

Example 1 Preparation of Titanium Oxide Porous Membrane Commercially available titanium oxide particles (trade name: AM, manufactured by Teica Corporation)
4.0 g of T-600, anatase type crystal, average particle diameter of 30 nm, specific surface area of 50 m ^{2 /} g) were dispersed together with glass beads in 20 ml of ethylene glycol monomethyl ether with a paint shaker for 6 hours. Obtained. Next, the obtained titanium oxide suspension was applied to a glass plate by a doctor blade method, preliminarily dried at 300 ° C. for 30 minutes, and then baked at 500 ° C. for 40 minutes to obtain a titanium oxide film.

Preparation of Photosensitizer Phthalocyanine Derivative A phthalocyanine derivative was obtained according to the following synthesis scheme.

[0087]

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Dipentoxydinitrile benzene 0.75
g (2.5 mmol), pentyl dinitrile benzoate (0.6 g, 2.5 mmol), CuCl 0.1
24 g (1.26 mmol) was added to 20 ml of anhydrous 1-pentanol, refluxed while blowing argon gas,
After 0.76 g (5.0 mmol) of DBU was slowly added dropwise thereto, the mixture was refluxed for 7 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, K ₂ CO ₃ was added thereto, and the mixture was stirred overnight. The reaction mixture was filtered and the solvent in the filtrate was evaporated to give a blue solid. This solid was purified by column chromatography (methylene chloride: methanol). The product was recrystallized in 2-propanol to give 0.
5 g of a phthalocyanine derivative was obtained (yield: 45%).

IR (KBr): 2940, 2870 (C
-H), 1095 (C-O), 1689 (C = O) cm
^-1 Elemental _{analysis: C 54 H 59 N 8 O} 8 Cu C H N calc (%) 64.3 5.60 11.1 Found (%) Preparation of 64.5 5.81 11.1 photoelectric conversion material The obtained phthalocyanine derivative was dissolved in chloroform. The concentration of this dye in the solution is 5 × 10 ^-4 mol / l
Met. Next, the glass plate coated with the titanium oxide film was kept in this solution for 30 minutes to allow the dye to adhere to the titanium oxide film. Thus, a photoelectric conversion material in which a dye was attached to the titanium oxide semiconductor film was obtained.

Preparation of Solar Cell The obtained photoelectric conversion material was used as one electrode, and a transparent conductive glass plate having a platinum layer was used as a counter electrode. 2
An electrolyte was inserted between the two electrodes and their sides were sealed with resin. A lead wire was attached to each electrode to obtain a solar cell. The electrolyte was prepared by dissolving tetrapropylammonium iodide and iodine at a concentration of 0.46 mol / l and 0.06 mol / l, respectively, in a mixed solvent of acetonitrile / ethylene carbonate (volume ratio 1: 4). did. When the obtained solar cell was irradiated with light (AM1.5 solar simulator) having an intensity of 100 W / m ² , η (conversion efficiency) of 5.4% was obtained. This result indicates that the solar cell according to the present invention is useful. Also, in the solar simulator, 1
Irradiation for 8 hours a day showed no decrease in conversion efficiency even after one year.

Comparative Example 1 In the preparation of a photoelectric conversion material, ethanol was used as a solvent,
A photoelectric conversion material and a solar cell were prepared in the same manner as in Example 1, except that the phthalocyanine represented by the following formula was used as a dye.

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When the obtained solar cell was irradiated with light of 100 W / m ^{2 in} a solar simulator,
An η of 1.1% was obtained.

Example 2 Synthesis of Photosensitizing Dye A phthalocyanine derivative was synthesized according to the following scheme.

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Synthesis of Intermediate b 80 ml of t-butanol and 10 ml of n-pentanol were placed in a 200 ml flask, and 2.5 g of potassium was added little by little with stirring. After the potassium was completely dissolved, 9.2 g (0.028 mol) of compound a was added thereto. The mixture was refluxed for 5 hours while stirring. After cooling the reaction mixture to room temperature, 50 ml of a 30% sodium chloride solution was added thereto and the reaction mixture was extracted with chloroform. After evaporating the chloroform, hexane was added to the residue and the mixture was filtered to remove insolubles. The filtrate was separated by column chromatography (hexane:
Ethyl acetate = 25: 1). As a result, the yellow liquid 4.7
g was obtained (yield: 50%).

NMR (CDCl ₃ ): δ = 7.64 (3
H); δ = 4.45 (s, 2H); δ = 3.46 (t,
2H); δ = 1.60 (m, 2H); δ = 1.28
(M, 4H); δ = 0.88 (t, 3H) Synthesis of phthalocyanine derivative c Intermediate b 3.4 g (0.01 mol), excess CuCN
(4.5 g, 0.05 mol) and DMF 20 ml
Was placed in a 50 ml flask and refluxed for 8 hours. After the mixture was returned to room temperature, 50 ml of aqueous ammonia was poured therein, and the mixture was stirred for 20 minutes and then filtered. The resulting solid was washed with water until neutral and then extracted with hexane. The resulting dark green solid was separated by column chromatography (chloroform) to give a blue solid c.
1.1 g were obtained (yield: 45%).

IR (KBr): ν = 2860/2940
cm ^-1 (CH); 1100 cm ^-1 (CO) Synthesis of phthalocyanine derivative d 0.15 g (1.1 mmol) of AlCl ₃ was dissolved in 10 ml of carbon disulfide and cooled to 10 ° C. Oxalyl chloride (0.14 g, 1.1 mmol) was slowly added thereto. 0.98 g (1 mmol) of the phthalocyanine derivative c previously dissolved in 5 ml of carbon disulfide is dropped into a solution containing AlCl ₃ and oxalyl chloride so that the liquid temperature does not exceed 10 ° C., and the mixture is reacted for 2 hours. And neutralized with hydrochloric acid and extracted with carbon tetrachloride. 0.58g
Was obtained (yield: 50%).

IR (KBr): ν = 2860/2940
cm ^-1 (CH); 1100 cm ^-1 (CO);
Preparation of 0 cm ^-1 (C = O) Photoelectric Conversion Material and Solar Cell A photoelectric conversion material and a solar cell were obtained in the same manner as in Example 1 except that the phthalocyanine derivative d was used as a photosensitizer. The obtained solar cell is 100
Irradiation with light having an intensity of W / m ² revealed that η was 4.7%.

Example 3 Synthesis of Photosensitizer A photosensitizer was synthesized according to the following scheme.

[0101]

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23.66 g of carbazole (0.16 mol
l), potassium hydroxide 14.45g (0.226mo
l), 30 g of water and 100 g of xylin were added to Dean-
The mixture was placed in a 500 ml four-necked flask equipped with a star apparatus and refluxed. After collecting about 30 g of water, the reaction solution was cooled to 90 to 100 ° C., and 33 g of hexyl bromide was obtained.
(0.2 mol) was added dropwise over about 25 minutes and then refluxed for 1 hour. 9-hexylcarbazole was obtained in a yield of 95%.

The temperature of the reaction solution was controlled at 70 ° C.
35.86 g (0.403 mol) of nitric acid and an equivalent amount of water were slowly added dropwise so that the internal temperature did not rise. Further, after reacting at this temperature for 1 hour, 86.7%
20 g (0.375 mol) of potassium hydroxide in water 50
It was dissolved in ml and added to the reaction solution. 3-Nitro-9-hexylcarbazole was obtained in 90% yield (GC analysis).

The temperature of the reaction solution was maintained at 60 ° C. or higher, 250 g of xylene was added, and the reaction solution was washed several times with 400 ml of hot water at about 70 ° C. 1.0 g of Pd-C (5%) was added to the reaction solution, which was reduced with hydrogen in an autoclave. The reaction mixture was filtered and the filtrate was evaporated, yielding 34.5 g of 3-amino-9-hexylcarbazole (yield: 90%).

NMR (CDCl ₃ ): δ = 6.54-
7.74 (m, 7H); δ = 4.10 (t, 2H); δ
= 3.35 (b, 2H) 3-amino-9-hexylcarbazole 20.3 g
(0.09 mol) and 10.3 g of triethylamine
Is added to 300 g of o-dichlorobenzene, and 25 to 35
At C, 15 g (0.61 mol) of chloranil were added thereto over 1 hour. The reaction was performed at 25 to 35 ° C for 1 hour. To the reaction mixture was added 12 g of benzenesulfonyl chloride (0.
067 mol) and refluxed for 2 hours. The solvent is evaporated and the residue is recrystallized in chloroform to give dioxazine 2
4 g were obtained (yield: 75%).

0.15 g (1.1 mmol) of AlCl ₃
Was dissolved in 10 ml of carbon disulfide and cooled to 10 ° C. Oxalyl chloride (0.14 g, 1.1 mmol) was slowly added thereto. 0.7 g (1 mmol) of dioxazine previously dissolved in 5 ml of carbon disulfide is added dropwise to a solution containing AlCl ₃ and oxalyl chloride so that the liquid temperature does not exceed 10 ° C., and the mixture is allowed to react for 2 hours. , Neutralized with hydrochloric acid and extracted with carbon tetrachloride. 0.45
g of dioxazine derivative was obtained (yield: 57%).

Preparation of Photoelectric Conversion Material and Solar Cell A photoelectric conversion material and a solar cell were obtained in the same manner as in Example 1, except that the obtained dioxazine derivative was used as a photosensitizer. When the obtained solar cell was irradiated with light having an intensity of 100 W / m ^{2 in} a solar simulator, η
Was 4.5%.

Example 4 An indigo derivative was obtained according to the following synthesis scheme.

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A carboxyl group was introduced using the same method as in the synthesis of the phthalocyanine derivative d. A photoelectric conversion material and a solar cell were obtained in the same manner as in Example 1, except that the indigo derivative was used as a photosensitizer. When the obtained solar cell was irradiated with light having an intensity of 100 W / m ^{2 in} a solar simulator, η was 4.1%.

Example 5 A dye represented by the following formula was used as a photosensitizer.

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The dye was dissolved in acetone at a concentration of 2 × 10 ^-4 mol / l. Except using this dye solution,
In the same manner as in Example 1, a photoelectric conversion material and a solar cell were prepared. When the obtained solar cell was irradiated with light having an intensity of 100 W / m ^{2 using} a solar simulator, η was 2.1%.

Comparative Example 2 A photoelectric conversion material and a solar cell were prepared in the same manner as in Example 5, except that methanol was used as a solvent for the dye solution. Η of the obtained solar cell was 1.1%.

Example 6 A titanium oxide suspension was prepared in the same manner as in Example 1. Next, the titanium oxide suspension was subjected to a doctor blade method,
Apply to glass plate with thickness of about 10μm,
Pre-dry for 0 minutes, then bake at 500 ° C for 40 minutes,
A titanium oxide film having a thickness of about 8 μm was obtained.

The phthalocyanine derivative was obtained according to the following synthesis scheme.

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The obtained dye was dissolved in acetonitrile at a concentration of 2 × 10 ^-4 mol / l. Next, using this dye solution, a photoelectric conversion material and a solar cell were prepared in the same manner as in Example 1. When the obtained solar cell was irradiated with light having an intensity of 100 W / m ^{2 in} a solar simulator, η was 4.1%.

Comparative Example 3 A dye represented by the following formula was dissolved in ethanol.
In the same manner as in Example 1, a photoelectric conversion material and a solar cell were obtained.

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When the obtained solar cell was irradiated with light of 100 W / m ^{2 in} a solar simulator,
η was 1.8%.

Example 7 A phthalocyanine derivative was obtained according to the following scheme.

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The obtained phthalocyanine derivative was added to 5 × 1
It was dissolved in hexane at a concentration of ^0-4 mol / l. Using this solution, a photoelectric conversion material and a solar cell were obtained in the same manner as in Example 6. When the obtained solar cell was irradiated with light having an intensity of 100 W / m ^{2 by} a solar simulator, η was 2.7%.

Example 8 A phthalocyanine derivative was obtained according to the following synthesis scheme.

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The obtained phthalocyanine derivative was added to 5 × 10
Dissolved in ethyl acetate at a concentration of ^-4 mol / l. Using the obtained dye solution, a photoelectric conversion material and a solar cell were prepared in the same manner as in Example 6. When the obtained solar cell was irradiated with light having an intensity of 100 W / m ^{2 using} a solar simulator, η was 2.9%.

[0128]

In the present invention, the hydrophobic and / or aprotic solvent used for dissolving the photosensitizing dye can eliminate adverse effects of water and / or protons on the semiconductor surface. As a result, a sufficient amount of the dye adheres to the semiconductor surface. By removing factors that hinder the dye from adhering to the semiconductor surface, a material and a device with high photoelectric conversion efficiency can be obtained. The present invention can provide a highly efficient photoelectric conversion material and device at a low cost in a simple process. Also, according to the present invention, photosensitizing dyes having at least one interlocking group and at least one hydrophobic group are soluble in hydrophobic and / or aprotic solvents at relatively high concentrations. Such a dye having a hydrophobic group can be attached to the semiconductor at a high concentration using a suitable hydrophobic and / or aprotic solvent.
Therefore, the present invention can provide a photoelectric conversion material having high efficiency. Such a material is useful for various photoelectric conversion elements. In addition, the use of a hydrophobic solvent in the production of a photoelectric conversion material prevents entry of moisture and protects the semiconductor from moisture. As a result, a photoelectric conversion material having excellent durability can be obtained. The photoelectric conversion material according to the present invention is particularly useful for a solar cell, and can provide an inexpensive solar cell having high photoelectric conversion efficiency.

[Brief description of the drawings]

FIG. 1 is a diagram schematically showing a photoelectric conversion material and a solar cell formed according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Support 2 Transparent conductive film 3 Electrolyte 4 Dye 5 Semiconductor layer 6 Transparent conductive film 7 Support

Claims (14)

[Claims] 1. A photosensitizer for a photoelectric conversion material comprising at least one selected from the group consisting of an organic compound dye and an organometallic compound dye, wherein the organic compound dye and the organometallic compound dye are:
It has at least one interlocking group and at least one hydrophobic group selected from the group consisting of a monovalent substituted and unsubstituted aliphatic hydrocarbon group and a monovalent substituted and unsubstituted alicyclic hydrocarbon group. The hydrophobic group does not constitute a group that directly binds to a metal in the dye, and the organic compound dye and the organic metal compound dye include a transition metal complex containing a ligand having a pyridyl group, N , N, N ', N'-tetra C
Characterized in that none of the transition metal complex containing a ligand having a transition metal complex and di -C _1-4 alkyl glyoxime containing a ligand having _1-4 alkyl ethylene diamine, photoelectric conversion material for optical Sensitizer. 2. The photosensitizer for a photoelectric conversion material according to claim 1, wherein the dye is an organic compound containing no metal. 3. The dye includes an azo-based structure, a quinone-based structure, a quinonimine-based structure, a quinacridone-based structure, a squarylium-based structure, a cyanine-based structure, a merocyanine-based structure, a triphenylmethane-based structure, a xanthene-based structure, and a porphine-based structure. A compound having at least one structure selected from the group consisting of a phthalocyanine-based structure, a perylene-based structure, an indigo-based structure, a naphthalocyanine-based structure, an oxazine-based structure, and an anthraquinone-based structure. 3. The photosensitizer for a photoelectric conversion material according to 2. 4. The photosensitizer for a photoelectric conversion material according to claim 1, wherein the hydrophobic group is an alkyl group having 3 to 12 carbon atoms. 5. The method according to claim 1, wherein the interlocking group is at least one selected from the group consisting of a carboxyl group, a hydroxyalkyl group, a hydroxyl group, a sulfonic acid group, a carboxyalkyl group, a mercapto group and a phosphono group. The photosensitizer for a photoelectric conversion material according to any one of claims 1 to 4. 6. The dye of the formula:(Where A₁, A_Two, A_ThreeAnd A_FourAre each water
Hydrogen, carboxyl group, hydroxyalkyl group, hydroxy
Sil group, sulfonic acid group, carboxyalkyl group, merka
Selected from the group consisting of
A₁, A_Two, A_ThreeAnd A_FourAt least one of
Is not a hydrogen atom, but B₁, B_Two, B_ThreeAnd B_FourIs
-R, -OR, -CH_TwoOR, -SR, -OCOR,-
A group consisting of COR, -CONRR 'and -NRR'
Wherein R and R ′ are substituted and unsubstituted
An aliphatic hydrocarbon group having 3 to 12 carbon atoms,
Selected from the group consisting of unsubstituted and unsubstituted alicyclic hydrocarbon groups.
Are the same or different hydrophobic groups), n and m are
Represents an integer of 0, 1, 2, 3 or 4 respectively,
And n + m is 4 or less and M is two hydrogen sources
Or covalent or coordination bond with phthalocyanine
Represents an atom or compound which can be represented by the formula:(Where A₁, A_Two, A_Three, A_Four, B₁, B_Two, B_Three,
B_Four, N and m are as defined above);(Where A_FiveIs selected from the group consisting of -R and -COR.
(Wherein R is a substituted or unsubstituted 3-1 carbon atom)
Aliphatic hydrocarbon groups and substituted and unsubstituted alicycles
A hydrophobic group selected from the group consisting of hydrocarbon groups),
And A₆Is a carboxyl group, a hydroxyalkyl group,
Hydroxyl group, sulfonic group, carboxyalkyl
Group, selected from the group consisting of mercapto and phosphono groups
), The formula:(Where A_FiveAnd A₆Is as defined above), and the formula:(Where A_FiveAnd A₆Is as defined above), and the formula:(Where A_FiveAnd A₆Is as defined above), and the formula:(Where A_FiveAnd A₆Is as defined above), and the formula:(Where A₁₁, A₁₂, A₁₃, A₁₄, A_Fifteen, A₁₆, A₁₇You
And A₁₈Is hydrogen, Cl, Br, F, -R, -OR,-
NRR ', -NCOR (where R and R' are substituted
And an unsubstituted aliphatic hydrocarbon group having 3 to 12 carbon atoms
Group consisting of substituted and unsubstituted alicyclic hydrocarbon groups
The same or different hydrophobic groups selected)
Carboxyl group, hydroxyalkyl group, hydroxy
Group, sulfonic acid group, carboxyalkyl group, mercap
Group selected from the group consisting of
Selected from the group consisting of locking groups, provided that A₁₁~ A
₁₈At least one of the interlocking groups is
And A₁₁~ A₁₈At least one of -R, -O
Selected from the group consisting of R, -NRR 'and -NCOR
), The formula(Where R₁Is a substituted or unsubstituted C 3-12
Aliphatic hydrocarbon groups and substituted and unsubstituted alicyclic carbons
A hydrophobic group selected from the group consisting of hydride groups;_{twenty one},
A_{twenty two}, A_{twenty three}, A_{twenty four}And A_{twenty five}Is hydrogen, Cl, Br,
F, carboxyl group, sulfonic acid group, carboxyalkyl
Selected from the group consisting of
A_{twenty one}~ A_{twenty five}At least one is a carboxyl group, a sulfo
Acid groups, carboxyalkyl groups and phosphono groups.
And the formula:Wherein M is selected from the group consisting of Ni, Pt and Cu
X and Y are NH_Two, NH, S and Se
Selected from the group₃₁, A₃₂, A₃₃, A₃₄, A ₃₅,
A₃₆, A₃₇And A₃₈Is hydrogen, Cl, Br, F,-
R, -OR, -NRR ', -NCOR (where R and
And R 'are substituted and unsubstituted aliphatics having 3 to 12 carbon atoms.
Hydrocarbon groups and substituted and unsubstituted alicyclic hydrocarbons
A hydrophobic group selected from the group consisting of
Ruboxyl group, hydroxyalkyl group, hydroxyl
Group, sulfonic acid group, carboxyalkyl group, mercapto
Group selected from the group consisting of
Selected from the group consisting of a locking group, provided that A₃₁~ A₃₈
At least one of the interlocking groups is
And A₃₁~ A₃₈At least one of -R, -OR,-
Selected from the group consisting of NRR 'and -NCOR)
Represented by any one selected from the group consisting of
The photoelectric device according to any one of claims 1 to 5, which is characterized in that:
Photosensitizer for conversion materials. 7. A photoelectric conversion material comprising: a semiconductor; and the photosensitizer according to claim 1 attached to the semiconductor. 8. The photoelectric conversion material according to claim 7, wherein the semiconductor is titanium oxide. 9. The photoelectric conversion material according to claim 7, wherein the semiconductor is in the form of particles or a film. 10. A photoelectric conversion device comprising: the photoelectric conversion material according to claim 7; and an electrode electrically connected to the photoelectric conversion material. 11. The light according to claim 1, wherein the first conductive layer, a semiconductor layer formed on the first conductive layer, and light formed on the semiconductor layer. A photoelectric conversion device comprising: a layer made of a sensitizer; an electrolyte layer provided on the layer made of the photosensitizer; and a second conductive layer in contact with the electrolyte layer. 12. The photoelectric conversion device according to claim 11, wherein said semiconductor layer is made of titanium oxide. 13. A step of dissolving the photosensitizer according to any one of claims 1 to 6 in a hydrophobic and / or aprotic solvent, and a step of dissolving the solvent containing the photosensitizer in a semiconductor. And attaching the photosensitizer to the semiconductor by contacting the photosensitizer with the semiconductor. 14. a step of dissolving an organic photosensitizing dye in a hydrophobic and / or aprotic solvent; and a step of bringing the solvent containing the dye into contact with a semiconductor to attach the dye to the semiconductor. A method for producing a photoelectric conversion material, comprising: