JPH11176489A - Photoelectric conversion element and light-regenerating type photoelectrochemical battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoelectric conversion element having superior photoelectric converting characteristic and durability, while having little deterioration with a lapse of time by forming an element of the disk-like compound having a substituent group for reacting with a semiconductor as a photoreceptor and light or thermal energy or the charge transporting material containing the reactant thereof. SOLUTION: A photoelectric conversion element is formed of a discoid compound such as triphenylene derivative having a substituent group capable of reacting with a semiconductor and light or thermal energy to generate the combination coupling or the charge transporting material containing the reactant thereof. As a semiconductor, silicon having sensitivity increased by color element and a fine particular semiconductor such as metal chalcogenid is desirable. As the discoid compound, a compound expressed with a general formula An-k -D-(L-P)k (where P is a reactive substituent group, D is an (n)-functional group at the center, L is a group for connecting P and D or combination coupling, (n) is an integer of 3 to 8, (k) is an integer of 1-n, P is isocyanate group, amino group, acetylene group of the like, A is a substituent which does not contribute to the generation of reactive composition).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoelectric conversion element, and more particularly, to a photoelectric conversion element using a semiconductor and a light-regenerating solar cell.

[0002]

2. Description of the Related Art At present, single-crystal silicon solar cells, polycrystalline silicon solar cells, amorphous solar cells, and compound solar cells such as cadmium telluride and indium copper selenide have been put to practical use or mainly researched and developed for solar power generation. However, it is pointed out that it is necessary to overcome problems such as production costs, securing of raw materials, and long energy payback time in order to spread the technology. NATU
RE (Vol. 353, pp. 737-740, 1991) and JP-A-7-249790 describe a photoelectric conversion element using semiconductor fine particles sensitized by a dye (hereinafter abbreviated as a dye-sensitized photoelectric conversion element). ) Or materials and manufacturing techniques for making the same. However, since this element is a wet solar cell in which the electrical connection with the counter electrode is performed by an electrolyte solution, when used for a long time, the photoelectric conversion efficiency is significantly reduced due to the depletion of the electrolyte,
There is a concern that the device will not function as an element. In order to improve such concerns, it has been desired to develop a solid electrolyte, particularly a highly efficient organic charge transport material.

As a highly efficient organic charge transporting material, a liquid crystal compound has recently attracted attention because it has both a high degree of order in molecular arrangement and an easy area enlargement. Meanwhile, it is known that a discotic compound takes a liquid crystal phase called a discotic liquid crystal by introducing an appropriate side chain, and among them, a triphenylene derivative is well known.
They also report that large charge mobilities (particularly hole mobilities) are observed in the discotic liquid crystal phase of the compound. JP-A-7-306317, JP-A-8-27284 and JP-A-8-231470 disclose a technique of forming a thin film by polymerizing a discotic compound having a reactive group while maintaining a liquid crystal phase. .

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photoelectric conversion element and a light-reproducing photoelectrochemical cell having excellent photoelectric conversion characteristics and durability.

[0005]

As a result of intensive studies, the present inventor has found that the object of the present invention can be achieved as follows. (1) A photoelectric conversion element comprising a charge transport material containing a semiconductor and a discotic compound having a substituent capable of forming a chemical bond by reacting with light or heat energy or a reactant thereof. (2) The photoelectric conversion device according to (1), wherein the discotic compound contained in the charge transport material is represented by the following general formula (I).

[0006]

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In the formula, P represents a reactive substituent, D is at the center of the molecule, and a total of n substituents A and substituents (P-
L) represents an n-functional group radially arranged. (Nk) A each independently represents a substituent that does not contribute to the formation of the reaction composition, L each independently represents a group or a chemical bond connecting P and D, and n represents 3 to 8 Represents an integer, and k represents an integer from 1 to n. k Ps are each independently an isocyanate group, a thiocyanate group, an amino group, an alkylamino group, an arylamino group, a mercapto group, a formyl group, an acyl group, a hydroxyl group, a carboxyl group, a sulfo group, a phosphoryl group, a halocarbonyl group. , A halosulfonyl group, a halophosphoryl group, an acryloyl group, a methacryloyl group, a crotonyl group, a vinyloxy group, an epoxy group, an acetylene group, a propargyl group, an allenyl group, and a diacetylene group. (3) The photoelectric conversion element according to (1), wherein in the general formula (I), the reactive substituents P are each independently represented by any of the following polymerizable substituents M _{1 to} M _4. .

[0008]

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R ₁₁ , R ₁₂ , R ₃ of the substituents M ₁ , M ₂ , M _3
13 represents _{R 21, R 22, R 23} , R 31, R 32, R 33 each independently represent a hydrogen atom or an alkyl group. In the substituent M ₄ , R ₄₁ represents a hydrogen atom, an alkyl group, or an aryl group.
In the substituent M _1, m represents 0 or 1. (4) The photoelectric conversion device according to (1), comprising a compound represented by the following general formulas (II) to (V) or a polymer thereof.

[0010]

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In the general formulas (II) to (V), M₁ ~ M_Four Haichi
It is synonymous with general formula (I). X₁~ X _FourAre independently
Represents oxygen or sulfur. In general formula (II), triphenylene
R that binds to the ring₁ May be the same or different
Represents an alkyl group or an aryl group, at least
One is a substituent M₁ Having. In general formula (III),
Six Rs attached to the phenylene ring_Two Are the same but different
Represents an alkyl group or an aryl group, of which
At least one substituent M_Two Having. General formula (IV)
And six Rs bonded to the triphenylene ring_Three Is the same
Represents an alkyl group or an aryl group which may be different,
At least one of which is a substituent M_Three Having. General
In the formula (V), six Rs bonded to the triphenylene ring_Four Is
Alkyl or aryl groups which may be the same or different
Wherein at least one of them is a substituent M_Four Have
You. (5) The semiconductor is a fine particle semiconductor sensitized by a dye.
The photoelectric conversion element according to any one of (1) to (4),
Child. (6) Using the photoelectric conversion element described in (1) to (5)
A photoregenerative photoelectrochemical cell characterized in that:

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a photoelectric conversion element and a light-reproducing solar cell using a semiconductor of the present invention will be described in detail.

In the present invention, the semiconductor is a so-called photoreceptor, and plays a role of absorbing light to separate electric charges to generate electrons and holes. As the semiconductor, a so-called compound semiconductor represented by a metal chalcogenide (for example, an oxide, a sulfide, a selenide, or the like), a perovskite, or the like can be used in addition to a simple semiconductor such as silicon or germanium. The metal chalcogenide is preferably titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium or tantalum oxide, cadmium, zinc, lead, silver, antimony , Sulfides such as bismuth, selenides such as cadmium and lead, and tellurides of cadmium. Other compound semiconductors include phosphides such as zinc, potassium, indium and cadmium, gallium arsenide, copper-indium and selenium. And copper-indium-sulfide. Further, as the perovskite, preferably strontium titanate, calcium titanate, sodium titanate,
Examples include barium titanate and potassium niobate.

It is more preferable that the semiconductor used in the present invention
Specifically, specifically, Si, TiO_Two, SnO_Two, Fe_TwoO_Three, WO_Three, Zn
O, Nb_TwoO_Five, CdS, ZnS, PbS, Bi_TwoS_Three, CdSe, GaP,
InP, GaAs, CdTe, CnTnS_Two, CnTnSe_TwoAnd so on.
More preferably TiO_Two, ZnO, SnO_Two, Fe_TwoO_Three, WO_Three, Nb_TwoO
_Five, CdS, PbS, CdSe, InP, GaAs, CnTnS_Two, CnInSe _Two
And so on.

The semiconductor used in the present invention may be single crystal or polycrystal. Although a single crystal is preferable as the conversion efficiency, a polycrystal is preferable in terms of manufacturing cost, securing of raw materials, energy payback time, and the like, and a fine particle semiconductor having a nanometer to micrometer size is particularly preferable.

Further, the fine particle semiconductor is preferably used after being sensitized with a dye, and in that case, a metal oxide is preferable. Specifically, TiO ₂ , ZnO, SnO ₂ , Fe ₂ O ₃ ,
WO ₃ and Nb ₂ O ₅ are preferred, and TiO ₂ is more preferred.

Hereinafter, a photoelectric conversion element or a photoregeneration type photoelectrochemical cell of the present invention using semiconductor fine particles sensitized with a dye will be described in detail. The dye-sensitized photoelectric conversion device of the present invention comprises a conductive support, a layer of semiconductor fine particles having a dye adsorbed thereon (photosensitive layer), a charge transport layer made of a discotic compound, and a counter electrode. Preferably.

As the conductive support, a support such as a metal which has conductivity can be used, or a glass or plastic support having a conductive agent layer on its surface can be used. In the latter case, preferred conductive agents include metals (eg, platinum, gold, silver, copper, aluminum, rhodium,
Indium, etc.), carbon, or a conductive metal oxide (indium-tin composite oxide, tin oxide doped with fluorine, and the like). Among them, conductive glass in which a conductive layer made of tin dioxide doped with fluorine is deposited on a transparent substrate made of low-cost soda-lime float glass is particularly preferable. The conductive agent layer preferably has a thickness of about 0.02 to 10 μm. The lower the surface resistance of the conductive support, the better. The preferred range of the surface resistance is 100 Ω / cm ² or less, and more preferably 40 Ω / cm ² or less.

Preferably, the conductive support is substantially transparent. Substantially transparent means that the light transmittance is 10% or more, preferably 50% or more,
70% or more is particularly preferred. As the transparent conductive support, glass or plastic coated with a conductive metal oxide is preferable. The amount of the conductive metal oxide applied at this time is preferably 0.01 to 100 g per 1 m ² of a glass or plastic support.

The particle size of these semiconductor fine particles is preferably 5 to 200 nm as primary particles, and particularly preferably 8 to 1 nm, as an average particle size using a diameter when the projected area is converted into a circle.
Preferably it is 00 nm.

The method of coating the semiconductor fine particles on the conductive support includes a method of coating a dispersion or a colloid solution of the semiconductor fine particles on the conductive support, and a method of coating the precursor of the semiconductor fine particles on the conductive support. A method of coating and hydrolyzing with water in the air to obtain a semiconductor fine particle film, and the like can be given. Examples of a method for preparing a dispersion of semiconductor fine particles include a method of grinding in a mortar, a method of dispersing while grinding using a mill, and a method of precipitating and using fine particles in a solvent when synthesizing a semiconductor. . Examples of the dispersion medium include water and various organic solvents (eg, methanol, ethanol, dichloromethane, acetone, acetonitrile, ethyl acetate, etc.). At the time of dispersion, a polymer, a surfactant, an acid, a chelating agent, or the like may be used as a dispersing aid, if necessary. The semiconductor fine particles preferably have a large surface area so that many dyes can be adsorbed. Therefore, the surface area when the semiconductor fine particle layer is coated on the support is preferably 10 times or more, and more preferably 100 times or more with respect to the projected area. The upper limit is not particularly limited, but is usually 10
It is about 00 times.

In general, as the thickness of the layer of semiconductor fine particles increases, the amount of dye carried per unit projected area increases, so that the light capture rate increases. However, the diffusion distance of generated electrons increases, and the loss due to charge recombination also increases. growing. Therefore,
The semiconductor fine particle layer has a preferred thickness, but is typically 0.1 to 100 μm. When used as a photoregenerative photoelectrochemical cell, the thickness is preferably 1 to 30 μm, more preferably 3 to 20 μm. It is preferable that the semiconductor fine particles are applied to a support, then the particles are brought into electronic contact with each other, and baked to improve the strength of the coating film and the adhesion to the substrate. A preferable range of the firing temperature is 40 ° C. or more and less than 700 ° C. After firing,
For example, chemical plating using an aqueous solution of titanium tetrachloride or electrochemistry using an aqueous solution of titanium trichloride to increase the surface area of the semiconductor particles, increase the purity near the semiconductor particles, and increase the efficiency of electron injection from the dye into the semiconductor particles. A selective plating process may be performed. The coating amount of the semiconductor fine particles per 1 m ² of the support is 0.5 to 500 g, and more preferably 5 to 100 g.
Is preferred.

The dye used in the present invention is a metal complex dye or a metal complex dye.
And / or polymethine dyes are preferred. The dye is semiconductive
Suitable binding groups (interlocking gr
oup). A preferred linking group
COOH group, cyano group, PO _ThreeH_TwoGroup or oxy
, Dioxime, hydroxyquinoline, salicylate and
With π conductivity like α and α-keto enolate
And the like. Among them, COOH group, PO_ThreeH_TwoGroup is special
Preferred. When the dye used in the present invention is a metal complex dye,
Is preferably a ruthenium complex dye,
A dye represented by the following general formula (VI) is preferred. General formula (VI) (Y)_bRuBaBbBcb is 0 to 2, preferably 2. Ru is Rutheni
Um. Y is Cl, SCN, H_TwoO, Br, I, CN, -NCO,
And a ligand selected from SeCN. Ba, Bb,
Bc is independently selected from the following B-1 to B-8
Organic ligand.

[0024]

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[0025]

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Here, Ra represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, aralkyl group or aryl group having 1 to 12 carbon atoms (hereinafter referred to as C number). As the ruthenium complex dye used in the present invention,
For example, U.S. Patent Nos. 4,927,721 and 4,68.
4,537, 5,084,365, 5,35
0,644, 5,463,057, 5,52
And complex dyes described in JP-A-5-440 and JP-A-7-249790. Preferred specific examples of the metal complex dye used in the present invention are shown below, but the present invention is not limited thereto.

[0027]

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[0028]

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[0029]

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When the dye used in the present invention is a polymethine dye, a dye represented by the following formula (VII) or (VIII) is preferred. General formula (VII)

[0031]

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In the formula, Rb and Rf represent a hydrogen atom, an alkyl
A group, an aryl group, and a heterocyclic residue;
Represents an atom or a substituent. Rb to Rf are bonded to each other
To form a ring. X₁₁, X₁₂Is nitrogen, oxygen, sulfur
Represents yellow, selenium, tellurium. n ₁₁And n₁₃Is 0-2
An integer, n₁₂Represents an integer of 1 to 6. Formula (VII)
Compounds have a counterion depending on the overall molecular charge
You may. General formula (VIII)

[0033]

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In the formula, Za represents a group of nonmetal atoms necessary for forming a nitrogen-containing heterocyclic ring. Rg is an alkyl group or an aryl group. Q represents a methine group or a polymethine group necessary for the compound represented by the general formula (VIII) to form a methine dye. However, Za, Rg and Q are represented by the general formula (VII
Represents a group that enables the compound represented by I) to have at least one substituent represented by the general formula (IX). X ₁₃
Represents a charge-balancing counter ion, and n represents a number from 0 to 10 required to neutralize the charge of the molecule. General formula (IX)

[0035]

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In the formula, X ₁₄ represents an oxygen atom, a sulfur atom or an amino group, and m ₁ is 0 or 1. m ₂ and m ₃ are 0 or 1, and when m ₂ or m ₃ is 0, the substituent represented by the general formula (VIII) is negatively charged. Specific examples of such polymethine dyes are described in M. Okawara, T. Kitao,
Organic Colorants (Elsevie) by T. Hirasima, M. Matuoka
r) and so on.

Preferred specific examples of the polymethine dyes represented by formulas (VII) and (VIII) are shown below, but the present invention is not limited thereto.

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[0039]

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[0042]

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[0043]

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[0045]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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The compounds represented by the general formulas (VII) and (VIII) can be obtained from FM Harmer, "Heterocyclic Compounds-Complex Cyclic Compounds-Cyanine Soybeans and Relativized Compounds".
nds-Cyanine Dyes and Related Compounds), John Wiley & Sons-
New York, London, 1964, DM
DMSturmer, `` Complex Cyclic Compounds-Special Topics in Complex Cyclic Chemistry (Heterocyclic Compounds-Specia)
l topics in heterocyclic chemistry) ", Chapter 18,
Section 14, Sections 482-515, John Willie
John Wiley & Sons, New York, London, 1977, "Rodd's Chemistry of Carbon Compounds"
Carbon Compounds) '' 2nd.Ed.vol.IV, partB, 1977
Annual, Chapter 15, Chapters 369-422, Elsevier
Science Public Company, Inc. (Elsevie
r Science Publishing Company Inc.), New York, UK Patent No. 1,077,611, and the like.

For adsorbing the dye on the semiconductor fine particles, a method of dipping well-dried semiconductor fine particles in a dye solution for several hours is general. The dye may be adsorbed at room temperature or may be heated and refluxed as described in JP-A-7-249790. The dye may be adsorbed before or after the application of the semiconductor fine particles. Further, the semiconductor fine particles and the dye may be simultaneously applied and adsorbed. It is desirable that unadsorbed dye be removed by washing. In the case of firing the coating film, the dye adsorption is preferably performed after firing. It is particularly preferable that the dye is quickly adsorbed after the firing and before the water is adsorbed on the coating film surface. The dye adsorbed is 1
They may be used alone or in combination. When the application is a photoregeneration type photoelectrochemical cell, a dye to be mixed can be selected so that the wavelength range of photoelectric conversion is as wide as possible.

A colorless compound may be co-adsorbed for the purpose of reducing the interaction between dyes such as association. Examples of the hydrophobic raw compound to be co-adsorbed include steroid compounds having a carboxyl group (for example, cholic acid). After the dye is adsorbed, the surface of the semiconductor fine particles may be treated with amines. Preferred amines include pyridine, 4-tert-butylpyridine, polyvinylpyridine and the like. In the case of these liquids, they may be used as they are or may be used after being dissolved in an organic solvent. Next, the charge transport material containing the discotic compound of the present invention or a reactant thereof will be described in detail.

First, general formulas (I) to (I) of the present invention will be described below.
The compound represented by (V) will be described in detail. Here, when the compounds represented by the general formulas (I) to (V) have an alkyl group, an alkenyl group, a cycloalkyl group, an alkylene group and the like, these may be linear or branched unless otherwise specified. May be substituted. When the compounds represented by the general formulas (I) to (V) have an aryl group, a heterocyclic group, an arylene group (a divalent group) or the like, they may be condensed unless otherwise specified. It may be substituted.

The compound having a disc-shaped core used in the present invention will be described first. The morphological characteristics of the disk-shaped portion forming the mother nucleus portion (core portion) of the disk-shaped molecule can be expressed as follows, for example, for a hydrogen-substituted product as its original compound.

First, the size of the molecule is determined as follows. 1) Construct a nearly planar, preferably planar, molecular structure for the molecule. In this case, as the bond distance and bond angle, it is preferable to use standard values according to the orbital mixture. For example, the Chemical Society of Japan, the Chemical Handbook Revised 4th Edition, Basic Edition,
See Vol. II, Chapter 15 (Maruzen, 1993). 2) Using the structure obtained in 1) as an initial value, optimize the structure by a molecular orbital method or a molecular force field method. Examples of the method include Gaussian92, MOPAC93, CHARMm / QUANTA, and MM3, and preferably Gaussian92. 3) The center of gravity of the structure obtained by the structure optimization is moved to the origin, and the coordinate axis is set to the principal axis of inertia (the principal axis of the inertial tensor ellipsoid). 4) Each atom is given a sphere defined by a van der Waals radius, which describes the shape of the molecule. 5) Measure the length in the direction of each coordinate axis on the van der Waals surface, and let them be a, b, and c. When a disk-like form is defined using a, b, and c obtained by the above procedure, a ≧ b> c and a ≧ b ≧ a /
2, preferably a ≧ b> c and a ≧ b ≧ 0.7a. Further, it is preferable that b / 2> c.

Discotic compounds are described, for example, in Chemical Society of Japan,
Quarterly Chemistry Review No.22 "Chemistry of Liquid Crystal" Chapter 5, Chapter 10 2
Section (1994, Gakkai Shuppan Center), a research report by C. Destrade et al., Mol. Cryst. Liq. Cryst. 71, 117 (1981)
Chem., 96, 70 (1984), JMLehn et al., J. Chem. Soc. Chem.
Commun., 1794 (1985), J. Zhang, JSMoore et al., J. Am. Chem. Soc., 116, 2655 (1994)
And derivatives of the mother nucleus compound described in (1). For example, as the core compound D, a benzene derivative, a triphenylene derivative, a truxene derivative, a phthalocyanine derivative, a porphyrin derivative, an anthracene derivative, an azacrown derivative, a cyclohexane derivative, a β-diketone metal complex derivative, a hexaethynylbenzene derivative, a dibenzopyrene derivative, Coronene derivatives and derivatives of phenylacetylene macrocycle. Further, there may be mentioned cyclic compounds and their heteroatom-substituted isoelectronic structures described in “Chemical Review No. 15 New Aromatic Chemistry” (edited by The Chemical Society of Japan) (published by The University of Tokyo Press, 1977). Further, as in the case of the above-described metal complex, an assembly of a plurality of molecules may be formed by hydrogen bonding, coordination bond, or the like to form a disk-shaped molecule. Preferred examples of the mother nucleus compound D include triphenylene and truxene, and triphenylene is more preferred. Examples of the substituent capable of forming a chemical bond by reacting by applying light or heat energy to the compound of claim 1 include, for example, SR Sandler and
Written by SRSandler, W. Karo, Organic Functional Group Preparations
ic Functional Group Preparations) Volumes 1 and 2
Volume (Academic Press, New York, London
1968). Among them, preferred are a multiple bond, oxirane, and aziridine. More preferred are the research reports of RAMHikmet et al. [Macromolecules, 25, 4194 (1992)] and [Po
lymer, Volume 34, Issue 8, 1736 (1993)], DJBroer
[Macromolecules, 26, 1244 (1993)
Years)], a double bond, ie, an acryl group, a vinyl ether group and an epoxy group.

The compound of the first aspect of the present invention is more preferably represented by the general formula (I) of the second aspect.
In the general formula (I), D represents an n-functional group which is located at the center of the molecule and radially arranges a total of n substituents A and substituents (PL). D is preferably the mother nucleus of the discotic compound described above. In the general formula (I), A independently represents a substituent that does not contribute to the formation of the reaction composition, and is preferably a substituted or unsubstituted alkyl group or aryl group having a halogen atom, a nitro group, a cyano group, an alkoxy group, or the like. Aralkyl, alkylthio, arylthio, arylamino, alkylamino, alkoxy, aryloxy, alkoxycarbonyl, and benzoyloxy groups. In the general formula (I), n represents an integer of 3 to 8, and k represents an integer of 1 to n.

In the general formula (I), L represents a group linking the reactive substituent P and the discotic mother nucleus D, and is generally a linking group which is easier to relax volumetric strain caused by polymerization than a chemical bond or an oxy group. Is preferred. Specifically, preferably, the alkylene group has 1 to 18 carbon atoms (hereinafter referred to as C number), and 1 to 1 carbon atoms.
An alkyleneoxy group of 18; an alkylenethio group of 1 to 18 carbon atoms; an alkyleneamino group of 1 to 18 carbon atoms;
20 oligoethyleneoxy groups, alkyleneoxycarbonyl groups having 1 to 18 carbon atoms, phenylene groups having 6 to 26 carbon atoms, phenyleneoxy groups having 6 to 26 carbon atoms, 6 to 26 carbon atoms
Phenylenethio group, a C6-C26 phenyleneamino group, a C7-26 phenyleneoxycarbonyl group, and the like. Preferred examples of the linking group L will be specifically described below.

[0073]

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The linking group L is more preferably an alkylene group, an alkyleneoxy group, an alkylenethio group, an alkyleneoxycarbonyl group, a phenylene group, a phenyleneoxy group, or a phenyleneoxycarbonyl group. In the general formula (I), k reactive substituents P are each independently an isocyanate, thiocyanate group, amino group, alkylamino group, arylamino group, mercapto group, formyl group, acyl group, hydroxyl group, carboxyl group , Sulfo group, phosphoryl group, halocarbonyl group, halosulfonyl group, halophosphoryl group, acryloyl group, methacryloyl group, crotonyl group, vinyloxy group, epoxy group,
Represents an acetylene group, a propargyl group, an allenyl group, or a diacetylene group. It is preferable that the reactive substituents P in the general formula (I) are each independently represented by any of the polymerizable substituents M _{1 to} M ₄ .

[0075]

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R in the polymerizable substituents M ₁ , M ₂ and M _{3
11, R 12, R 13,} R 21, R 22, R 23, R 31, R 32, R 33
Each independently represents a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms (hereinafter referred to as C number), such as methyl, ethyl, n-propyl, i-propyl, t-butyl, butyl, pentyl, hexyl, octyl, 2-chloroethyl, 3-methoxyethyl, methoxyethoxyethyl), preferably a hydrogen atom or an unsubstituted linear alkyl group having 1 to 4 carbon atoms. R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ ,
Preferably, R ₂₂ , R ₂₃ , R ₃₁ , R ₃₂ and R ₃₃ are all hydrogen atoms. Although at M ₁ m represents 0 or 1, 1
Is more preferable.

In M _4, R ₄₁ is an optionally substituted alkyl group (preferably having 1 to 12 carbon atoms, for example, methyl, ethyl, propyl, i-propyl, t-butyl, butyl, pentyl, hexyl, octyl, cyclohexyl) , 2-ethylhexyl, 2-chloroethyl, 3-methoxyethyl, 2
-Hydroxyethyl, methoxyethoxyethyl, benzyl, allyl) or an optionally substituted aryl group (for example, phenyl having 1 to 18 carbon atoms, 1-naphthyl, 2-naphthyl, 4-propylphenyl, 4-ethoxyphenyl,
-Pentyloxyphenyl, 3-hydroxyphenyl,
4-biphenyl, 3-acetyloxyphenyl, 2-chlorophenyl), and preferably an unsubstituted linear alkyl group having 1 to 6 carbon atoms or a phenyl group. General formula (I)
Preferably, the discotic nucleus D is a triphenylene ring, and the compounds of the general formulas (II) to (II)
2,3,6,7,10,11-hexaalkoxytriphenylene or hexaaryloxytriphenylene represented by (V) is more preferable for achieving the object of the present invention.

Now, the compounds of the present invention represented by formulas (II) to (V) will be described in detail. M ₁ in the general formula (II), M _2, the general formula (IV) of M _3, M ₁ ~M ₄ synonymous of M ₄ each of the general formula (V) (I) of general formula (III) It is.

[0079] Formula (II) Although the X ₁ to X ₄ at ~ (V) each independently represent an oxygen or sulfur, X ₁ to X ₄ in six X ₁ to X ₄ are oxygen all sulfur Preferably, there is. In this case, X _{1 to} X ₄ are preferably all sulfur in terms of photovoltaic power, and preferably all oxygen in terms of photocurrent density. In the general formula (II), six R _{1 s} may be the same or different and represent an alkyl group or an aryl group which may be substituted, and at least one of them has a substituent M ₁ . Here, R ₁ is preferably an alkyl group, and it is preferable that all six R ₁ have M ₁ as a substituent and are all the same.

In the general formula (III), six R _{2 's} may be the same or different and each represents an alkyl group or an aryl group which may be substituted, at least one of which is a substituent M ₂
Having. Here, R ₂ is preferably an alkyl group, and it is preferable that all six R ₂ have M ₂ as a substituent and are all the same. 6 in general formula (IV)
One R ₃ represents an alkyl group or an aryl group which may be the same or different and may be substituted, at least one of which has a substituent M ₃ . Here, R ₃ is preferably an alkyl group, and it is preferable that all six R ₃ have M ₃ as a substituent and are all the same.

In the general formula (V), six R _{4 's} may be the same or different and each represents an alkyl group or an aryl group which may be substituted, at least one of which is a substituent M ₄
Having. Here, R ₄ is preferably an alkyl group, and it is preferable that all six R ₄ have M ₄ as a substituent and are all the same. General formula (II)
R ₁ to R ₄ at terminal substituent M ₁ ~M ₄ in which residues formed by substitution preferably having a C number of 1 to 12 which may be substituted alkylene group (V) or a C number 6 to 18, It is a phenylene group which may be substituted. In the present invention,-(CH ₂ ) ₂ OCH ₂ -or -C
H ₂ Ph-, -PhCH _2- and the like are also regarded as a substituted alkylene group, a substituted phenylene group and the like. Preferred examples of the residue are specifically described below.

[0082]

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R ₁ of the general formula (II) and R _{1 of} the general formula (III)
₂ , terminal substituents M ₁ , M ₂ and M at R ₄ in the general formula (V)
_The residue obtained by substituting ₄ preferably has 1 to 8 C atoms
Is an unsubstituted linear alkylene group, more preferably ethylene, propylene, butylene and hexylene.

The residue obtained by substituting the terminal substituent M ₃ with R _{3 in the} formula (IV) is preferably an unsubstituted linear alkylene group having 1 to 8 carbon atoms or a substituted alkylene group, more preferably Is ethylene, propylene, butylene,-(CH ₂ ) ₂ OCH
₂ -,-(CH ₂ ) ₃ OCH _2- and-(CH ₂ ) ₄ OCH _2- . The compounds of the present invention include compounds represented by the general formula (I) among the general formulas (II) to (V):
I), (III), and (V) are more preferable, and the general formulas (III),
(V) is more preferred, and formula (III) is particularly preferred.

Specific examples of the compounds represented by formula (I) or formulas (II) to (V) of the present invention are shown below, but the present invention is not limited thereto.

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[0087]

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[0090]

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[0092]

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[0098]

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[0100]

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Many of the compounds represented by formulas (I) to (V) of the present invention have a liquid crystal phase, particularly a columnar liquid crystal phase or a discotic nematic liquid crystal phase. The compounds represented by the general formulas (I) to (V) of the present invention may be used alone, or may be used in a mixture at any ratio.
It may be used by mixing with various compounds other than the present invention. For example, it may be a low molecule such as a surfactant, a synthetic polymer such as polycarbonate, a compound derived from a natural polymer such as a cellulose derivative, a liquid crystal property, or a non-liquid crystal property, and may be used as an ultraviolet curable resin or a thermosetting resin. Those that can form new bonds between or within molecules such as monomers,
Any material that cannot easily form a new bond, such as xylene, may be used. As a mixed composition, Japanese Patent Application No. Hei 6-97
443 and the discotic compounds described in Japanese Patent Application No. 7-41276, and further, the compounds described in Japanese Patent Application Nos. 7-110511, 7-221186, and 7-222785. May be included. The material of the present invention can be used after being molded into various shapes using a mold, for example, or in the form of a film. When the material of the present invention is used in the form of a film, it can be formed as a thin film on a support by a coating method such as evaporation, spin coating, dip coating, or extrusion coating. The film thickness is 0.
It is preferably 1 μm or more and 30 μm or less, more preferably 20 μm or less.

In coating, the compound is preferably in the form of a solution, and the solvent used is a solvent having a boiling point of 30 ° C. to 200 ° C. under atmospheric pressure, preferably 30 ° C. to 15 ° C.
The temperature is 0 ° C, more preferably 30 ° C to 130 ° C. Examples include 2-butanone, 2,4-dimethyl-3-pentanone, ethyl acetate, 1-butanol, fluorobenzene, 1,2-dimethoxyethane, acetone, methylene chloride and the like.

When the compound used in the present invention has a substituent capable of forming a new bond by polymerization or the like, a bond can be formed by heat or light. That is, in the present invention, the liquid crystal thin film is formed on a suitable support by a general coating method, in which at least one interface is in contact with the gas phase, and after drying, the disc is formed at a temperature within the liquid crystal phase formation temperature range. A desired thin film can be obtained by subjecting to heat treatment for a certain period of time while forming a tick nematic phase or discotic phase, followed by thermal polymerization or photocrosslinking polymerization, followed by cooling, followed by cooling.

In the present invention, the photopolymerization initiator is α
-Carbonyl compounds, acyloin ethers, aromatic acyloin compounds substituted with α-hydrocarbons, polynuclear quinone compounds, combinations of triarylimidazole dimers / p-aminophenyl ketone, acridine and phenazine compounds, oxadiazole compounds and the like. Can be In the present invention, the amount of the photoinitiator system in the range of 0.01% to 20% of the coating composition excluding the solvent is sufficient, and more preferably 0.5% to 5% to obtain good results.

For the polymerization of the epoxy group, allyldiazonium salts (hexafluorophosphate, tetrafluoroborate), diallyliodonium salts, group VIa allylonium salts (PF-6,
Allylsulfonium salts having anions such as AsF6 and SbF6) are preferably used. Light rays for polymerization include electron beam, ultraviolet ray, visible ray, infrared ray (heat ray).
Can be used as needed, but generally, ultraviolet rays are used. The light rays include low-pressure mercury lamps (germicidal lamps, fluorescent chemical lamps, brat lights), high-pressure discharge lamps (high-pressure mercury lamps, metal halide lamps), and short arc discharge lamps (ultra-high-pressure mercury lamps, xenon lamps, mercury xenon lamps). No.

[0106]

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When a bond is formed by heat, a substance for accelerating the reaction can be added. For example, a base such as a hydroxide (eg, sodium hydroxide,
Potassium hydroxide and ammonium hydroxide),
Alkoxides (eg, sodium methoxide, sodium ethoxide, potassium-t-butoxide), metal hydrides (eg, sodium hydride, calcium hydride), amines (eg, pyridine, triethylamine, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), tetramethylbutanediamine (TMBDA), 1,4-diaza [2,2,2] bicyclooctane (DABCO)), Carbonates (for example, sodium carbonate, potassium carbonate, sodium hydrogencarbonate) and acetates (for example, sodium acetate, potassium acetate).

Further, for example, metal compounds (for example, di-n-butyltin dilaurate, tin octoate, zinc acetylacetonate) can be mentioned. Acids, such as mineral acids (eg, sulfuric acid, hydrochloric acid), carboxylic acids (eg, chloroacetic acid, trifluoroacetic acid, salicylic acid and derivatives thereof), sulfonic acids (eg, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid).

The polymerization is preferably carried out under an inert gas (eg, argon, helium, nitrogen) from the viewpoint of the polymerization rate. Although the charge transport material of the present invention can be used as both a hole transport material and a charge transport material, it is more preferable to use it as a hole transport material.

The counter electrode serves as the positive electrode of the photoelectrochemical cell. The counter electrode is usually synonymous with the above-mentioned conductive support, but the support is not necessarily required in a configuration in which the strength is sufficiently maintained. However, having a support is advantageous in terms of hermeticity. In order for light to reach the photosensitive layer, at least one of the conductive support and the counter electrode described above must be substantially transparent.

Glass or plastic on which a metal or a conductive oxide is deposited can be used as the counter electrode of the photoregeneration type photoelectrochemical cell, and a metal thin film having a thickness of 1 μm or less, preferably 5 to 200 nm. It can also be formed by forming it by a method such as vapor deposition or sputtering so as to be thick. In the present invention, it is preferable that glass on which platinum is deposited or a metal thin film formed by deposition or sputtering is used as the counter electrode. The photosensitive layer is designed according to the purpose and may have a single-layer structure or a multilayer structure. The dye in one photosensitive layer may be one kind or a mixture of many kinds. Also,
In the photoregeneration type photoelectrochemical cell of the present invention, the side surface of the cell may be sealed with a polymer, an adhesive or the like in order to prevent oxidative deterioration of the components.

[0112]

EXAMPLES Hereinafter, the method for producing the photoelectric conversion element and the photoreproducing type photoelectrochemical cell of the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1 Preparation of Titanium Dioxide Dispersion Titanium dioxide (Nippon Aerosil Co., Ltd.
egussa P-25), 15 g of water, 1 g of a dispersant (manufactured by Aldrich, Triton X-100), 1 g, and 30 g of zirconia beads (manufactured by Nikkato) having a diameter of 0.5 mm were used. A sand grinder mill (manufactured by Imex) was used. 1500rpm
For 2 hours. The zirconia beads were removed from the dispersion by filtration.

Example 2 (Preparation of TiO ₂ electrode adsorbing dye (electrode A)) Conductive glass coated with fluorine-doped tin oxide (TCO glass manufactured by Asahi Glass cut into a size of 20 mm × 20 mm) The above dispersion was applied to the conductive surface side of (2) using a glass rod. At this time, an adhesive tape was stretched on a part (3 mm from the end) on the conductive surface side to form a spacer, and glass was lined up so that the adhesive tape came to both ends and applied eight sheets at a time. After application, the adhesive tape was peeled off and air-dried at room temperature for one day. Next, the glass was placed in an electric furnace (Matsufuru furnace FP-32, manufactured by Yamato Scientific) and fired at 450 ° C. for 30 minutes. After the glass was taken out and cooled, it was immersed in an ethanol solution of the dye of the present invention shown in Table 2 (3 × 10 ⁻⁴ mol / l) for 3 hours. The glass on which the dye was dyed was immersed in 4-tert-butylpyridine for 15 minutes, washed with ethanol and air-dried.

Example 3 (Synthesis of compounds D-62 and 64 of the present invention)

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[0117] 9.0 g (27.8 mmol) of 2,3,6,7,10,11-hexahydroxytriphenylene 1 synthesized by the method described in JP-A-7-306317, chloride 2
B50g (0.332mol), potassium carbonate 70.0g
(0.5 mol), 7.5 g (50 mmol) of sodium iodide
Was dissolved in 200 ml of dimethylacetamide and stirred at 120 ° C. for 6 hours. After cooling, water and ethyl acetate were added to carry out liquid separation, and the organic phase was washed twice with water. After drying over magnesium sulfate and concentrating, silica gel-ethyl acetate: hexane =
Purification by a 1: 1 → 2: 1 column gave 25.1 g (yield 89.7%) of hexaacetyloxy form 3B crystal.

17.2 g (17 mmol) of 3B was dissolved in 100 ml of ethanol, and sodium hydroxide 12.2 g was added thereto.
g (0.306 mol) in 30 ml of water was added and refluxed for 2 hours. After cooling, hydrochloric acid was added to adjust the pH to 10, then sodium chloride was added, and the mixture was extracted three times with ethyl acetate. After drying over magnesium sulfate and concentrating, 11.5 g of hexahydroxy form 4B crystals
(89.4%).

3.78 g (5 mmol) of 4B, 10.2 g (10.1 mmol) of triethylamine and 0.3 g of nitrobenzene were dissolved in 50 ml of dimethylacetamide and stirred under ice-cooling. Here, 5.43 g of acrylic acid chloride
(60 mmol) was slowly added dropwise, and the mixture was further stirred at 60 ° C. for 1 hour. Water and ethyl acetate were added for liquid separation, and the organic phase was washed twice with water and then concentrated in an open system. Purification by a silica gel-ethyl acetate: hexane = 1: 2 → 1: 1 column and crystallization from methanol gave 3.95 g (yield: 73.0%) of the target white crystal of D-64. NMR spectrum (CDCl ₃ , δ, ppm) 1.95-2.15 (24H, m, -C
H ₂ CH ₂ CH ₂ CH _2- ), 4.30 (24H, m, -OCH _2- ), 5.82 (6H, d, -CH =
CH ₂ ), 6.15 (6H, d of d, -CH = CH ₂ ), 6.44 (6H, d, -CH = C
H ₂ ), 7.86 (6H, S, aromatic) Phase transition temperature measurement by DSC and polarizing microscope Discotic liquid crystal phase → 56 ℃ → isotropic phase

The desired D-62 can be synthesized in exactly the same manner except that 2a is used instead of chloride 2b.

D-62, NMR spectrum (CDCl ₃ , δ, p
pm) 2.32 (12H, m, -CH 2 CH 2 CH 2 -), 4.35 (12H, m, -CH 2 O-),
_{4.50 (12H, m, -CH 2} O -), 5.85 (6H, d, -CH = CH 2), 6.18 (6H, t
of t, -CH = CH ₂ ), 6.47 (6H, d, -CH = CH ₂ ), 7.88 (6H, S, aroma
tic) Phase transition temperature measurement by DSC and polarization microscope Crystal phase → 76 ° C → Discotic liquid crystal phase → 83 ° C → Isotropic phase

Example 4 (Synthesis of Compound D-100 of the Present Invention)

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Triphenylene 11 4.0 g (17.5 mmo
l) 1.2 g of Fe was dissolved in 140 ml of nitrobenzene and stirred, and 25.2 g (0.158 mol) of bromine was added dropwise. The mixture was stirred at room temperature for 3 hours, and further heated and stirred at 205 ° C. for 4 hours. After cooling, 200 ml of ether was added, and the precipitated crystals were separated by filtration, washed with ether and acetone, and washed with 2,3,6,6.
Crystal of 7,10,11-hexabromotriphenylene 12
2.1 g (98.4% yield) was obtained.

Hexabromotriphenylene 12 7.0
g (10 mmol), 9.4 g of 2-mercaptoethanol (0.
12 mol), 12.9 g (0.115 mol) of potassium t-butoxide
With DMI (1,3-dimethyl-2-imidazolidinone)
It was dissolved in 300 ml and heated and stirred at 100 ° C. for 5 minutes under a nitrogen atmosphere. 1.2 g (1 mmol) of Pd (Pph ₃ ) ₄ was added thereto, and the mixture was further heated and stirred at 100 ° C. for 4 hours. After cooling, 600 ml of water was added, and the mixture was stirred under ice cooling to precipitate crystals, which were separated by filtration and washed with water. The crystals are treated with methanol: methylene chloride =
After dispersing in a 1: 4 mixed solvent, the mixture was separated by filtration, washed with methylene chloride, and 4.40 g of 2,3,6,7,10,11-hexa (2-hydroxyethylthio) triphenylene 13 crystals were obtained.
(64.2% yield).

Hexa (2-hydroxyethylthio) triphenylene 13 2.2 g (3.2 mmol), triethylamine 6.5 g (64 mmol) and nitrobenzene 0.5 g were dissolved in dimethylacetamide 30 ml and stirred under ice-cooling. 4.63 g (51.2 mmol) of acrylic acid chloride was slowly added dropwise thereto, and the mixture was further stirred at 60 ° C. for 1 hour. water,
Methylene chloride was added for liquid separation, and the organic phase was washed twice with water. After concentration in an open system, the residue was purified on a silica gel-methylene chloride: ethyl acetate = 10: 1 column, and crystallized from methanol to obtain 2.52 g of the objective white crystal of D-100.
(78.0% yield). NMR spectrum (CDCl ₃ , δ, ppm) 3.47 (12H, t, -SCH
_{2 -), 4.46 (12H,} t, -CH 2 O -), 5.83 (6H, d, -CH = CH 2), 6.12
(6H, toft, -CH = CH ₂ ), 6.47 (6H, d, -CH = CH ₂ ), 8.72 (6H, s,
aromatic) Measurement of phase transition temperature by DSC and polarization microscope Crystal phase → 89 ℃ → Discotic liquid crystal phase → 104 ℃ →
Isotropic phase

Example 5 (Formation of Hole Transport Layer (Method A)) The color-sensitized TiO ₂ electrode substrate prepared in Example 2 (2 cm
× 2 cm) on the compound D-62 of the present invention in ethyl acetate 20 wt.
% Solution was applied by spin coating at 1000 rpm to form a thin film of D-62. After drying, it was heated to 85 ° C. on a Mettler FP-82 hot stage to make it an isotropic phase, and then left at 70 ° C. to change to a discotic liquid crystal phase in a supercooled state.

Here, an ultraviolet irradiation device (ULTRA-VIOLET PRO)
DUCTS UVSL-588 (16W)) and light source from film to 1
At a distance of 4 cm, 254 nm light was irradiated 5 times in an argon atmosphere. In this state, no change was observed in the morphology of the discotic liquid crystal phase. Further, even when the temperature is raised to 120 ° C., there is no transition to an isotropic phase, and even when the temperature is cooled to 25 ° C., there is no transition to a crystalline phase. It shows what was done. Note that this film has sufficient strength to form an element. The thickness of the hole transport layer was 2.0 μm. A hole transport layer made of D-62 was formed on the color-sensitized TiO ₂ electrode substrate as described above.

D-64 was used in place of D-62, and after heating to 60 ° C., the same procedure was repeated except that the polymerization temperature was set to 30 ° C. by supercooling. A hole transport layer was created. The thickness of the hole transport layer was 2.0 μm.

Further, D-100 was used in place of D-62,
A hole transport layer made of D-100 was formed on the electrode substrate in exactly the same manner except that methylene chloride was used in place of ethyl acetate and heating was performed at 110 ° C, and then the polymerization temperature during supercooling was changed to 90 ° C. did. The thickness of the hole transport layer was 2.0 μm.

Example 6 (Formation of hole transport layer (Method B)) In Example 5, the compounds D-62, D-64 and D-10 of the present invention were prepared.
3% by weight, based on 0, of a polymerization initiator 2,2'-azobis-
(2,4-Dimethylvaleronitrile), D-62, D-64, D-64, D-64,
A hole transport layer made of D-100 was formed on the electrode substrate.
The thickness of each of the hole transport layers was 2.0 μm.

Example 7 (Formation of Counter Electrode) The color sensitizing electrode on which the hole transport layer was formed was fixed to a substrate holder of a vacuum evaporation apparatus (manufactured by Nippon Vacuum Engineering Co., Ltd.). Then, after putting 0.5 g of gold wire into a molybdenum boat, the pressure in the vacuum chamber was reduced to 1 × 10 ⁻⁴ Pa,
Gold was deposited at a deposition rate of 0.1 nm / second to form a counter electrode having a thickness of 50 nm, thereby obtaining a target photoelectric conversion element.

Example 8 (Preparation of a photo-regenerating solar cell) The above-mentioned photoelectric conversion element was superimposed on a platinum-deposited glass of the same size (see FIG. 1; So that it does not come into contact with). Examples 1 to 7 were carried out by changing the combination of the dye and the discotic compound of the present invention as described in Table A.

[0134]

[Table 1]

[0135]

[Table 2]

Example 9 (Measurement of Photoelectric Conversion Efficiency) The light of a 500 W xenon lamp (made by Ushio) was applied to AM1.
Simulated sunlight containing no ultraviolet rays was generated by passing through a 0G filter (manufactured by Oriel) and a sharp cut filter (Kenko L-42). The intensity of this light is 86 mW / cm
^{Was 2} . An alligator clip was connected to each of the conductive glass and the platinum-deposited glass of the photoelectric conversion element of the present invention, simulated sunlight was irradiated, and the generated electricity was measured with a current-voltage measuring device (Keisley SMU238 type). The open-circuit voltage, short-circuit current density, form factor,
Table B shows the conversion efficiency, the short-circuit current density after continuous irradiation for 120 hours, and the reduction rate of the short-circuit current density. [Comparative Example 1] Comparative solar cell A The color-sensitized TiO ₂ electrode substrate (2 cm ×
2 cm) was overlaid with platinum-evaporated glass of the same size (see FIG. 1). Next, an electrolytic solution (acetonitrile and N-methyl-2-
A solar cell for comparison was manufactured by infiltrating a solution of 0.05 mol / l of iodine and 0.5 mol / l of lithium iodide using a mixture of oxazolidinone at a volume ratio of 90:10 as a solvent. [Comparative Example 2] Comparative solar cell B A color-sensitized TiO ₂ electrode substrate (2 cm
1 g of hexaethylene glycol methacrylate (Blenmer PE350 manufactured by NOF CORPORATION)
, 1 g of ethylene glycol, and 2
-Hydroxy-2-methyl-1-phenyl-propane-
1-one (Darocure 1173, manufactured by Nippon Ciba Geigy) 2
In a mixed solution containing 0 mg, 500 mg of lithium iodide was dissolved, degassed under vacuum for 10 minutes, and applied. Next, by placing the porous material coated with the mixed solution under reduced pressure,
After removing bubbles in the porous material and promoting the penetration of the monomer,
Polymerization was performed by irradiation with ultraviolet light, and a uniform gel of the polymer compound was present in the pores of the porous material. The substance thus obtained was exposed to an iodine atmosphere for 30 minutes to diffuse iodine into the polymer compound, thereby obtaining a comparative solar cell B.

[0137]

[Table 3]

[0138]

[Table 4]

Compared with the comparative examples, at the level of the present invention, the photopolymerization method
It is clear that deterioration of the photoelectric conversion characteristics with time is small regardless of which of the thermal polymerization methods is used to form the hole transport layer, the metal complex dye, and the organic dye.

[0140]

According to the present invention, there is no fear of electrolyte leakage,
A photoelectric conversion element with less deterioration in characteristics over time was obtained.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a layer configuration of a photoelectrochemical cell prepared in an example.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 conductive glass 2 conductive layer 3 TiO electrode 4 dye layer 5 hole transport layer 6 counter electrode 7 platinum-deposited glass

Claims (6)

[Claims] 1. A photoelectric conversion element comprising a semiconductor and a charge transporting material containing a discotic compound having a substituent capable of forming a chemical bond by reacting with light or heat energy or a reactant thereof. 2. The photoelectric conversion device according to claim 1, wherein the discotic compound contained in the charge transporting material is represented by the following general formula (I). Embedded image In the formula, P represents a reactive substituent, D represents an n-functional group located at the center of the molecule and radially distributing a total of n substituents A and substituents (PL). (Nk) A each independently represents a substituent that does not contribute to the formation of the reaction composition, L each independently represents a group or a chemical bond connecting P and D, and n represents 3 to 8 Represents an integer, and k represents an integer from 1 to n. k Ps are each independently an isocyanate group, a thiocyanate group, an amino group, an alkylamino group, an arylamino group, a mercapto group, a formyl group, an acyl group, a hydroxyl group, a carboxyl group, a sulfo group, a phosphoryl group, a halocarbonyl group. , A halosulfonyl group, a halophosphoryl group, an acryloyl group, a methacryloyl group, a crotonyl group, a vinyloxy group, an epoxy group, an acetylene group, a propargyl group, an allenyl group, and a diacetylene group. 3. A compound of the formula (I) wherein a reactive substituent P
Is independently represented by any _one of the following polymerizable substituents M _{1 to} M ₄ . Embedded image R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R _{21 of} the substituents M ₁ , M ₂ , M _3
22 , R ₂₃ , R ₃₁ , R ₃₂ and R ₃₃ each independently represent a hydrogen atom or an alkyl group. In the substituent M ₄ , R ₄₁ represents a hydrogen atom, an alkyl group, or an aryl group. In the substituent M _1, m represents 0 or 1. 4. A compound represented by the following general formulas (II) to (V):
A compound comprising a compound or a polymer thereof.
2. The photoelectric conversion element according to 1. Embedded imageIn the general formulas (II) to (V), M₁ ~ M_Four Is represented by the general formula (I)
It is synonymous. X₁~ X _FourAre independently oxygen or sulfur
Represents yellow. In general formula (II), the compound binds to a triphenylene ring
6 R₁ Is an alkyl group which may be the same or different, or
Represents an aryl group, at least one of which is substituted
Substitution M₁ Having. In the general formula (III), a triphenylene ring
6 Rs that bind to_Two Is the same or different
Represents an aryl group or an aryl group, at least
And the substituent M_Two Having. In general formula (IV),
Six Rs attached to the Nylene ring_Three May be the same or different
Represents an alkyl group or an aryl group.
At least one is a substituent M_Three Having. In the general formula (V),
6 Rs attached to the triphenylene ring_Four Are the same but different
Represents an alkyl group or an aryl group which may be
At least one of which is a substituent M_Four Having. 5. The photoelectric conversion device according to claim 1, wherein the semiconductor is a fine particle semiconductor sensitized by a dye. 6. A photoregenerative photoelectrochemical cell using the photoelectric conversion element according to claim 1. Description: