JP5300454B2 - Dye-sensitized photoelectric conversion element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photoelectric conversion element in which dye-sensitized semiconductor particulates are used, and which is inexpensive and superior in conversion efficiency, and to provide a solar cell using them. <P>SOLUTION: A metal complex dye represented by specified formula [1], or a salt thereof is carried by a thin film of oxide semiconductor particulates formed on a substrate. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a dye-sensitized photoelectric conversion element having a thin film of semiconductor fine particles sensitized with a metal complex dye and a solar cell using the same, and more specifically, a metal complex dye having a specific structure in a thin film of oxide semiconductor fine particles. The present invention relates to a dye-sensitized photoelectric conversion element carrying (metal complex compound) or a salt thereof and a solar cell using the same.

Solar cells that use sunlight as an energy resource to replace fossil fuels such as oil and coal are drawing attention. Currently, active studies are being made on silicon solar cells using crystalline or amorphous silicon, or compound semiconductor solar cells using gallium, arsenic, or the like. However, a great deal of energy is required for the production of these solar cells, and as a result, the production cost of the solar cells is still high, which is one factor preventing the solar cells from being used for general purposes.
On the other hand, a photoelectric conversion element using a semiconductor layer composed of semiconductor fine particles sensitized with a dye (hereinafter also simply referred to as a dye-sensitized photoelectric conversion element) and a solar cell using the element are also known. The constituent materials and manufacturing techniques have been reported. (See Patent Document 1, Non-Patent Document 1, and Non-Patent Document 2)
Since the semiconductor layer of the dye-sensitized photoelectric conversion element uses relatively inexpensive oxide semiconductor fine particles such as titanium oxide, the photoelectric conversion element is cheaper than the conventional photoelectric conversion element using a semiconductor layer made of silicon or the like. A conversion element may be obtained. In addition, solar cells using a dye-sensitized photoelectric conversion element are attracting attention because a colorful solar cell can be obtained.
Patent Document 2 describes a dye-sensitized photoelectric conversion element using a certain metal complex dye as a sensitizing dye. However, the solar cell using the dye-sensitized photoelectric conversion element described herein has a lower conversion efficiency than a solar cell using silicon as a semiconductor layer, and further improvement in conversion efficiency is desired.

Japanese Patent No. 2664194 Japanese Patent No. 3731552 B. O '' Regan et al., Nature; 353, 737 (1991). M.M. K. Nazeeruddin et al., J. MoI. Am. Chem. Soc. 115, 6382 (1993)

  It is an object of the present invention to provide a dye-sensitized photoelectric conversion element that is sensitized with a metal complex dye, is stable, has high conversion efficiency, and is highly practical, and a solar cell using the dye-sensitized photoelectric conversion element.

  As a result of diligent efforts to solve the above-mentioned problems, the present inventors have sensitized a thin film of semiconductor fine particles using a metal complex dye having a specific structure, and have produced the dye-sensitized photoelectric conversion element. The present invention has been found to be solved, and the present invention has been completed.

That is, the present invention
(1) A dye-sensitized photoelectric conversion element obtained by supporting a metal complex dye represented by the following formula (1) or a salt thereof on a thin film of oxide semiconductor fine particles provided on a substrate,

(In formula (1), Y ₁ and Y ₂ each independently represent a thiocyanate group (—SCN), a halogen atom or an isothiocyanate group (—NCS), or Y ₁ and Y ₂ are bonded to form one M ₁ and M ₂ each independently represents a hydrogen atom or an ammonium ion, and Q _{1 to} Q ₁₄ each independently represent a hydrogen atom or an aromatic residue optionally having a substituent. Group, optionally substituted aliphatic hydrocarbon residue, hydroxyl group, phosphate group, cyano group, nitro group, halogen atom, carboxyl group, carbonamido group, alkoxycarbonyl group, arylcarbonyl group, alkoxyl group, an aryloxy group, a substituted amide group, an acetamide group, an acyl group or a substituted or unsubstituted amino group (provided that one or two following formulas selected from Q ₇ to Q ₁₄ ( )

(In formula (2), n ₁ represents an integer of 0 to 3. R ₁ and R ₂ are each independently an aliphatic hydrocarbon optionally having a hydrogen atom, a cyano group, a halogen atom, or a substituent. Represents an alkoxyl group which may have a residue or a substituent, or an aromatic ring which may have a substituent by bonding a plurality of R ₁ and / or R ₂ ; An aliphatic hydrocarbon ring which may optionally be substituted or a heterocyclic ring which may have a substituent, wherein n ₁ is 2 or more and / or two selected from Q _{7 to} Q ₁₄ are represented by formula (2) In the case where a plurality of R ₁ and R ₂ are present, each R ₁ and R ₂ may be the same or different, and R ₃ and R ₄ each independently have a hydrogen atom or a substituent. or to represent an aromatic residue which may also have an aliphatic hydrocarbon residue or substituent have, or the R _{3 4} to form a heterocyclic ring which may have a bond to an aliphatic substituted hydrocarbon ring or a substituent. Also, 2 Exemplary ethynylphenylbiadamantane derivatives selected from Q ₇ to Q ₁₄ (2 And a plurality of R ₃ and R ₄ are present, each R ₃ and R ₄ may be the same or different. )
(2) The dye-sensitized photoelectric conversion element according to the above item (1), wherein at least one of Q ₉ and Q ₁₂ in the formula (1) is a metal complex dye represented by the formula (2) or a salt thereof,
(3) The dye-sensitized photoelectric conversion element according to the above item (2), wherein Q ₉ and Q ₁₂ in the formula (1) are a metal complex dye represented by the formula (2) or a salt thereof,
(4) The dye-sensitized photoelectric conversion element according to any one of (1) to (3), wherein Y ₁ and Y ₂ in Formula (1) are NCS groups,
(5) The dye-sensitized photoelectric conversion element according to the above item (4), wherein R ₃ and R ₄ in formula (2) are each independently an aliphatic hydrocarbon residue which may have a substituent,
(6) R ₃ and R ₄ in Formula (2) are each independently a saturated aliphatic hydrocarbon residue having 1 to 18 carbon atoms that may have a substituent, Dye-sensitized photoelectric conversion element,
(7) The dye-sensitized photoelectric conversion device according to the above item (6), wherein R ₃ and R ₄ in the formula (2) are n-butyl groups,
(8) The dye-sensitized photoelectric conversion element according to any one of (1) to (7), wherein R ₁ and R ₂ in Formula (2) are hydrogen atoms,
(9) The foregoing (1) to (1), wherein a thin film of oxide semiconductor fine particles provided on a substrate is further supported with a methine dye and / or a metal complex dye having a structure other than the formula (1) or a salt thereof. 8) The dye-sensitized photoelectric conversion element according to any one of
(10) The dye-sensitized photoelectric conversion element according to any one of (1) to (9) above, which uses a thin film of oxide semiconductor fine particles containing titanium dioxide, zinc oxide, or tin oxide.
(11) The dye-sensitized photoelectric conversion according to any one of (1) to (10) above, wherein the metal complex dye represented by formula (1) or a salt thereof is supported in the presence of an inclusion compound. element,
(12) A solar cell using the dye-sensitized photoelectric conversion element according to any one of (1) to (11) above,
(13) The metal complex dye represented by the formula (1) described in the preceding item (1) or a salt thereof,
About.

  By using a specific metal complex dye or a salt thereof of the present invention as a sensitizing dye, a dye-sensitized photoelectric conversion element having high conversion efficiency and high stability and a solar cell using the dye-sensitized photoelectric conversion element are provided. I was able to do it.

The present invention is described in detail below.
The dye-sensitized photoelectric conversion element of the present invention is obtained by supporting a metal complex dye represented by the following formula (1) or a salt thereof on a thin film of oxide semiconductor fine particles provided on a substrate. In the following text, “metal complex dye” represents “metal complex dye or salt thereof” and “compound” represents “compound or salt thereof” unless otherwise specified.

In formula (1), Y ₁ and Y ₂ each independently represent a thiocyanate group (—SCN), a halogen atom or an isothiocyanate group (—NCS), or Y ₁ and Y ₂ are bonded to form one coordination. Form a child.
Examples of the “halogen atom” in Y ₁ and Y ₂ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., preferably a fluorine atom or a chlorine atom, and more preferably a chlorine atom.
The “ligand” formed by combining Y ₁ and Y ₂ is not particularly limited, and examples thereof include the following formulas (3) to (8).

In formulas (3) to (8), each R independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, a perfluoroalkyl group having 1 to 7 carbon atoms, or an alkoxyalkyl having 1 to 30 carbon atoms. Group, an aminoalkyl group having 1 to 30 carbon atoms, an aryl group having 1 to 30 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms, an amino group having 1 to 4 carbon atoms, or a carboxyl group.
Of these, Y ₁ and Y ₂ are particularly preferably an isothiocyanate group (—NCS).

In formula (1), M ₁ and M ₂ may be the same or different and each represents a hydrogen atom or an ammonium ion. Examples of the “ammonium ion” include alkylammonium ions such as tetramethylammonium ion, tetrabutylammonium ion and tetrahexylammonium ion, and cyclic aromatic ammonium ions such as 1,3-dimethylimidazolium ion.

In formula (1), Q _{1 to} Q ₁₄ are each independently a hydrogen atom, an aromatic residue optionally having substituent (s), an aliphatic hydrocarbon residue optionally having substituent (s), Hydroxyl group, phosphate group, cyano group, nitro group, halogen atom, carboxyl group, carbonamido group, alkoxycarbonyl group, arylcarbonyl group, alkoxyl group, aryloxy group, substituted amide group, acyl group or substituted or unsubstituted amino Represents a group (however, one or two selected from Q _{7 to} Q ₁₄ represents the following formula (2)).

The “aromatic residue” in the “aromatic residue optionally having substituent (s)” represented by Q _{1 to} Q ₁₄ means a group in which one hydrogen atom has been removed from an aromatic ring. Specific examples of the aromatic ring include, for example, aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, pyrene, perylene, and terylene, indene, azulene, pyridine, pyrazine, pyrimidine, pyrazole, pyrazolidine, thiazolidine, oxazolidine, pyran, Chromene, pyrrole, pyrrolidine, benzimidazole, imidazoline, imidazolidine, imidazole, pyrazole, triazole, triazine, diazole, indoline, thiophene, thienothiophene, furan, oxazole, oxadiazole, thiazine, thiazole, indole, benzothiazole, benzothia Heteroaromatic rings such as azole, naphthothiazole, benzoxazole, naphthoxazole, indolenine, benzoindolenine, pyrazine, quinoline and quinazoline, condensed aromatic rings such as fluorene and carbazole, etc., and aromatics having 5 to 16 carbon atoms An aromatic residue having a ring (an aromatic ring and a condensed ring including an aromatic ring) is preferable.
Examples of the “substituent” in the “aromatic residue optionally having a substituent” represented by Q _{1 to} Q ₁₄ include an aromatic residue, an aliphatic hydrocarbon residue, a hydroxyl group, and a phosphate group. Cyano group, nitro group, halogen atom, carboxyl group, carbonamido group, alkoxycarbonyl group, arylcarbonyl group, alkoxyl group, aryloxy group, substituted amide group, acyl group or substituted or unsubstituted amino group.

As the “aromatic residue” as the substituent that the “aromatic residue” represented by Q _{1 to} Q ₁₄ may have, the “aromatic residue” represented by Q _{1 to} Q ₁₄ may have the “substituent”. The same substituents as the “aromatic residue” in “good aromatic residue” can be mentioned.
The “aliphatic hydrocarbon residue” as a substituent that the “aromatic residue” represented by Q _{1 to} Q ₁₄ may have is a saturated or unsaturated linear or branched group having 1 to 36 carbon atoms. And a chain alkyl group and a cycloalkyl group having 3 to 8 carbon atoms, preferably a saturated or unsaturated linear or branched alkyl group having 1 to 18 carbon atoms or a cycloalkyl group having 4 to 6 carbon atoms. And more preferably a saturated linear alkyl group having 1 to 10 carbon atoms. Specific examples of these aliphatic hydrocarbon residues include, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, t-butyl group, octyl joy, octadecyl group. , Isopropyl group, cyclohexyl group, vinyl group, propenyl group, pentynyl group, butenyl group, hexenyl group, hexadienyl group, isopropenyl group, isohexenyl group, cyclohexenyl group, cyclopentadienyl group, ethynyl group, propynyl group , A pentynyl group, a hexynyl group, an isohexynyl group, a cyclohexynyl group, and the like.
Examples of the “halogen atom” as a substituent that the “aromatic residue” represented by Q _{1 to} Q ₁₄ may have include the same halogen atoms as those described above for Y ₁ and Y ₂ , and a fluorine atom Or it is preferable that it is a chlorine atom, and it is still more preferable that it is a chlorine atom.

The “alkoxycarbonyl group” as a substituent that the “aromatic residue” represented by Q _{1 to} Q ₁₄ may have is an alkoxycarbonyl group having 1 to 10 carbon atoms, and specific examples thereof include For example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, t-butoxycarbonyl, n-pentoxycarbonyl, n-hexyloxycarbonyl, n- Examples include heptyloxycarbonyl, n-nonyloxycarbonyl, and n-decyloxycarbonyl.
Specific examples of the “arylcarbonyl group” as a substituent that the “aromatic residue” represented by Q _{1 to} Q ₁₄ may have include, for example, a group in which an aryl group such as benzophenone and naphthophenone and carbonyl are linked, etc. Is mentioned.
Q ₁ to Q ₁₄ represents an "aromatic residue" is a substituent which may have "alkoxyl group" have the "aromatic residue" the Q ₁ to Q ₁₄ represents A group obtained by ether-bonding an “aliphatic hydrocarbon residue” as a good substituent and an oxygen atom, and specific examples thereof include, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, n -Butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group and the like can be mentioned.
Specific examples of the “aryloxy group” as a substituent that the “aromatic residue” represented by Q _{1 to} Q ₁₄ may have include a phenoxy group and a naphthoxy group.

Specific examples of the “substituted amide group” as a substituent that the “aromatic residue” represented by Q _{1 to} Q ₁₄ may have include, for example, an amide group, an acetamide group, an N-methylamide group, and an N-ethylamide. Group, N- (n-propyl) amide group, N- (n-butyl) amide group, N-isobutylamide group, N- (sec-butyl) amide group, N- (t-butyl) amide group, N, N-dimethylamide group, N, N-diethylamide group, N, N-di (n-propyl) amide group, N, N-di (n-butyl) amide group, N, N-diisobutyramide group, N-methyl Acetamide group, N-ethylacetamide group, N- (n-propyl) acetamide group, N- (n-butyl) acetamide group, N-isobutylacetamide group, N- (sec-butyl) acetamide group, N- (t- Spotted ) Acetamide group, N, N-dimethylacetamide group, N, N-diethylacetamide group, N, N-di (n-propyl) acetamide group, N, N-di (n-butyl) acetamide group, N, N- An amide group such as a diisobutylacetamide group, an acetamide group and an alkylamide group, or an arylamide group such as a phenylamide group, a naphthylamide group, a phenylacetamide group, and a naphthylacetamide group.

Examples of the “acyl group” as a substituent that the “aromatic residue” represented by Q _{1 to} Q ₁₄ may have include an alkylcarbonyl group having 1 to 10 carbon atoms and an arylcarbonyl group. Preferred is an alkylcarbonyl group having 1 to 4 carbon atoms, specifically, an acetyl group, a propionyl group, a trifluoromethylcarbonyl group, a pentafluoroethylcarbonyl group, a benzoyl group, a naphthoyl group, or the like.
Specific examples of the “substituted or unsubstituted amino group” as the substituent that the “aromatic residue” represented by Q _{1 to} Q ₁₄ may have include, for example, an amino group, a mono- or dimethylamino group, a mono- or Alkyl-substituted amino groups such as diethylamino group, mono or di (n-propyl) amino group, mono or di (n-butyl) amino group, mono or di (n-hexyl) amino group, mono or diphenylamino group, mono or Aromatic substituted amino groups such as dinaphthylamino group, alkyl groups such as monoalkylmonophenylamino group and amino groups substituted with aromatic residues one by one or benzylamino group, acetylamino group, phenylacetylamino group, etc. Can be mentioned.
The above-mentioned “substituent” in the “aromatic residue optionally having substituent (s)” represented by Q _{1 to} Q ₁₄ may further have a substituent. Are the same as the “substituent” in the “aromatic residue optionally having substituent (s)” represented by Q _{1 to} Q ₁₄ .

Q ₁ to Q ₁₄ are represented as the "aliphatic hydrocarbon residue" in the "aliphatic hydrocarbon residue which may be substituted", the Q ₁ to Q ₁₄ represents "aromatic residue" The same thing as the "aliphatic hydrocarbon residue" as a substituent which may have is mentioned.
As the "substituent" of the "aliphatic hydrocarbon residue which may have a substituent" represented by Q ₁ to Q _14, it has a "substituent the Q ₁ to Q ₁₄ represents And the same as the “substituent” in “good aromatic residue”.
Examples of the “halogen atom” represented by Q _{1 to} Q ₁₄ include the same halogen atoms as those described above for Y ₁ and Y _2, preferably a fluorine atom or a chlorine atom, and more preferably a chlorine atom. .
Q ₁ to Q ₁₄ as "alkoxycarbonyl group" represented by the aforementioned Q ₁ to Q ₁₄ that represents "aromatic residue" is a substituent which may have "alkoxycarbonyl group" and similar is Can be mentioned.
Q ₁ to Q ₁₄ as the "arylcarbonyl group" represented by the aforementioned Q ₁ to Q ₁₄ represents "aromatic residue" is a substituent which may have the same as the "arylcarbonyl group" ones Can be mentioned.

As the "alkoxyl group" represented by Q ₁ to Q _14, include those similar to the "alkoxyl group" as the Q ₁ to Q ₁₄ represents "aromatic residue" substituents which may be possessed by .
Q ₁ to Q ₁₄ as the "aryloxy group" represented by the aforementioned Q ₁ to Q ₁₄ represents "aromatic residue" is a substituent which may have the same "aryloxy group" ones Can be mentioned.
The “substituted amide group” represented by Q _{1 to} Q ₁₄ is the same as the “substituted amide group” as the substituent that the “aromatic residue” represented by Q _{1 to} Q ₁₄ may have. Can be mentioned.
As the "acyl group" represented by Q ₁ to Q _14, include those similar to the "acyl group" as the Q ₁ to Q ₁₄ represents "aromatic residue" substituents which may be possessed by .
The “substituted or unsubstituted amino group” represented by Q _{1 to} Q ₁₄ is a “substituted or unsubstituted amino group” as a substituent that the “aromatic residue” represented by Q _{1 to} Q ₁₄ may have. And the like.
However, one or two selected from Q _{7 to} Q ₁₄ in the formula (1) represents the above formula (2).

In formula (2), n ₁ represents an integer of 0 to 3.
In formula (2), R ₁ and R ₂ may each independently have a hydrogen atom, a cyano group, a halogen atom, an aliphatic hydrocarbon residue which may have a substituent or a substituent. An aromatic ring which may represent a good alkoxyl group, or a plurality of R ₁ and / or R ₂ may be bonded to each other to have a substituent, an aliphatic hydrocarbon ring which may have a substituent, or A heterocyclic ring which may have a substituent is formed. Further, n ₁ is represented by 2 Exemplary ethynylphenylbiadamantane derivatives (2) is selected from 2 or more and / or Q ₇ to Q _14, if R ₁ and R ₂ are present in plural, or each of R ₁ and R ₂ identical Or they may be different.
Examples of the “halogen atom” represented by R ₁ and R ₂ include the same halogen atoms as those described above for Y ₁ and Y _2, preferably a fluorine atom or a chlorine atom, and more preferably a chlorine atom. .
The “aliphatic hydrocarbon residue” in the “aliphatic hydrocarbon residue optionally having substituents” represented by R ₁ and R ₂ is the “aromatic residue” represented by Q _{1 to} Q ₁₄ above. The same thing as the "aliphatic hydrocarbon residue" as a substituent which may have is mentioned.

In addition, the “substituent” in the “aliphatic hydrocarbon residue optionally having substituent (s)” represented by R ₁ and R ₂ is “having a substituent (s)” represented by Q _{1 to} Q ₁₄ above. And the same as the “substituent” in “good aromatic residue”.
The “alkoxyl group” in the “alkoxyl group optionally having substituent (s)” represented by R ₁ and R ₂ is a substituent that the “aromatic residue” represented by Q _{1 to} Q ₁₄ may have. Examples thereof include the same “alkoxyl group” as the group.
The “substituent” in the “alkoxyl group optionally having substituent (s)” represented by R ₁ and R ₂ is “the aromatic optionally having substituent (s)” represented by Q _{1 to} Q ₁₄ above. Examples thereof include the same as the “substituent” in the “residue”.
The “aromatic ring” in the “aromatic ring optionally having substituent (s)” formed by combining a plurality of R ₁ and / or R ₂ is the “substituent” represented by Q _{1 to} Q ₁₄ above. Specific examples of the aromatic ring described in the explanation section of “Aromatic residue” in “Aromatic residue optionally having benzene” may be mentioned.
Further, the “substituent” in the “aromatic ring optionally having substituent (s)” formed by combining a plurality of R ₁ and / or R ₂ is the “substitution” represented by Q _{1 to} Q ₁₄ above. Examples thereof include the same as the “substituent” in the “aromatic residue optionally having a group”.

Specific examples of the “aliphatic hydrocarbon ring” in the “aliphatic hydrocarbon ring optionally having substituents” formed by combining a plurality of R ₁ and / or R ₂ include, for example, a cyclobutane ring And saturated hydrocarbon rings such as cyclopentane ring, cyclohexane ring and cycloheptane ring, and unsaturated hydrocarbon rings such as cyclobutene ring, cyclopentene ring and cyclohexene ring.
In addition, the “substituent” in the “aliphatic hydrocarbon ring optionally having substituent (s)” formed by combining a plurality of R ₁ and / or R ₂ represents Q _{1 to} Q ₁₄ above. Examples thereof include the same as the “substituent” in the “aromatic residue optionally having substituent (s)”.
Specific examples of the “heterocycle” in the “heterocycle optionally having substituent (s)” formed by combining a plurality of R ₁ and / or R ₂ include, for example, a 1,3-dioxane ring, 1, 3-dithiane ring, 1,3-dioxolane ring, 2,3,4,5-tetrahydropyridine ring, 3,4,5,6-tetrahydropyridazine ring, 5,5-dimethyl-1,3-dioxane ring, etc. Can be mentioned.
The “substituent” in the “heterocycle optionally having substituent (s)” formed by combining a plurality of R ₁ and / or R ₂ is the “substituent” represented by Q _{1 to} Q ₁₄ above. The same as the “substituent” in the “aromatic residue optionally having”.
Of these, R ₁ and R _{2 in} the formula (2) are preferably a hydrogen atom or an aliphatic hydrocarbon residue which may have a substituent, and particularly preferably a hydrogen atom.

In formula (2), R ₃ and R ₄ each independently represent a hydrogen atom, an aliphatic hydrocarbon residue that may have a substituent, or an aromatic residue that may have a substituent. R ₃ and R ₄ are bonded to each other to form an aliphatic hydrocarbon ring which may have a substituent or a heterocyclic ring which may have a substituent. Further, when two selected from Q _{7 to} Q ₁₄ are represented by the formula (2) and a plurality of R ₃ and R ₄ are present, each R ₃ and R ₄ may be the same or different.

The “aliphatic hydrocarbon residue” in the “aliphatic hydrocarbon residue optionally having substituents” represented by R ₃ and R ₄ is the “aromatic residue” represented by Q _{1 to} Q ₁₄ above. The same thing as the "aliphatic hydrocarbon residue" as a substituent which may have is mentioned.
In addition, as the “substituent” in the “aliphatic hydrocarbon residue optionally having substituent (s)” represented by R ₃ and R ₄ , “having a substituent (s)” represented by Q _{1 to} Q ₁₄ above. And the same as the “substituent” in “good aromatic residue”.
The “aromatic residue” in the “aromatic residue optionally having substituent (s)” represented by R ₃ and R ₄ may have “substituent (s) represented by Q _{1 to} Q ₁₄ above”. Examples thereof include those similar to the “aromatic residue” in the “aromatic residue”.
The “substituent” in the “aromatic residue optionally having substituent” represented by R ₃ and R ₄ may have “substituent” represented by the above Q _{1 to} Q _14. Examples thereof include the same as the “substituent” in the “aromatic residue”.

The “aliphatic hydrocarbon ring” in the “aliphatic hydrocarbon ring optionally having a substituent” formed by combining R ₃ and R ₄ includes a plurality of R ₁ and / or R ₂ . Examples thereof include those similar to the “aliphatic hydrocarbon ring” in the “aliphatic hydrocarbon ring optionally having substituents” formed by bonding.
Further, the “substituent” in the “aliphatic hydrocarbon ring optionally having substituent (s)” formed by combining R ₃ and R ₄ is the “having substituent (s)” represented by Q _{1 to} Q ₁₄ above. And the same as the “substituent” in the “aromatic residue optionally”.
The “heterocycle” in the “heterocycle optionally having substituent (s)” formed by combining R ₃ and R ₄ is formed by combining a plurality of R ₁ and / or R ₂ above. Examples thereof include those similar to the “heterocycle” in the “heterocycle optionally having substituent (s)”.
In addition, the “substituent” in the “heterocycle optionally having substituents” formed by combining R ₃ and R ₄ is “having substituents” represented by Q _{1 to} Q ₁₄ above. And the same as the “substituent” in “good aromatic residue”.

Of the metal complex dyes represented by the formula (1), at least one of Q ₉ and Q _{12 in} the formula (1) is preferably a metal complex dye represented by the formula (2), and the Q ₉ in the formula (1) is preferred. And a metal complex dye in which both of Q ₁₂ are represented by the formula (2) are particularly preferred.
Moreover, as R < ₃ > and R < ₄ > in Formula (2), it is preferable that they are the aliphatic hydrocarbon residues which may have a substituent, and are saturated which may have a substituent. The aliphatic hydrocarbon residue is more preferably, a saturated aliphatic hydrocarbon residue having 1 to 18 carbon atoms is particularly preferable, and an n-butyl group is particularly preferable.

  When the metal complex dye represented by the formula (1) has an acidic group such as a carboxyl group, a phosphoric acid group, a hydroxyl group, and a sulfonic acid group as a substituent, each of them may form a salt thereof, Examples of salts include salts with alkali metals or alkaline earth metals such as lithium, sodium, potassium, magnesium and calcium, or organic bases such as tetramethylammonium, tetrabutylammonium, pyridinium, imidazolium, piperazinium, piperidinium And salts with quaternary ammonium and the like. Preference is given to tetrabutylammonium salts and piperidinium salts.

  The metal complex dye represented by the formula (1) may take a structural isomer such as a cis isomer, a trans isomer and a mixture thereof, an optically active isomer, a racemate, and the like, but is not particularly limited, and any isomer may be used in the present invention. Can be satisfactorily used as a photosensitizing dye.

The metal complex dye represented by the formula (1) can be produced by, for example, the reaction formula shown below. In the following reaction formula, n ₁ , Y ₁ , Y ₂ , M ₁ , M ₂ , R ₁ , R ₂ , R ₃ , R ₄ and Q _{1 to} Q ₁₄ are the same as those in the above formula (1). The meaning of

  That is, a bromofluorene compound represented by the following formula (10) is substituted with an alkylating agent or the like to obtain a substitution formula (11), this formula (11) is changed to an olefin substitution product of the formula (12), and 2-chloro-4- Formula (13) and formula (14) are obtained by a coupling reaction with iodopyridine. A bipyridine compound of the formula (15) can be obtained by further coupling the formula (13) and the formula (14). Reacting ruthenium-p-cymene dimer with formula (15) to formula (16), and further reacting with the bipyridine compound represented by formula (17) and ammonium thiocyanate of formula (18) Thus, the metal complex dye represented by the above formula (1) is obtained.

In the following, Q ₉ and Q ₁₂ in the formula (1) are the formula (2), and M ₁ , M ₂ , Q _{1 to} Q ₈ , Q ₁₀ , Q ₁₁ , Q ₁₃ and Q ₁₄ are all hydrogen atoms. A specific example of the metal complex dye is shown based on the following formula (20).

Other specific examples are shown below.

In the dye-sensitized photoelectric conversion element of the present invention, a metal complex dye represented by the above formula (1) is supported on a thin film of oxide semiconductor fine particles provided on a substrate.
As a substrate on which a thin film of oxide semiconductor fine particles is provided, a substrate whose surface is conductive is preferable. Specifically, for example, tin oxide doped with indium, fluorine, antimony, or the like on the surface of a transparent polymer material such as glass or polyethylene terephthalate or polyether sulfone by vapor deposition or electroless plating. A conductive metal oxide such as copper or a thin film of metal such as copper, silver, or gold can be used. The surface resistance of the substrate is typically 1000 [Omega] / cm ² or less, preferably 100 [Omega / cm ² or less. As the substrate provided with such a conductive thin film, FTO glass, ITO glass, Zn glass, ATO glass, and the like are available as commercial products, and they can be used as they are.
The oxide semiconductor used in the fine particles is preferably a metal oxide, and specific examples thereof include oxides such as titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum, and vanadium. Of these, oxides such as titanium, tin, zinc, niobium and indium are preferable, and oxides of titanium, zinc and tin are most preferable. These oxide semiconductors can be used alone, but can also be mixed or used by coating the surface of the semiconductor. The average particle diameter of these oxide semiconductor fine particles is usually 1 to 500 nm, preferably 1 to 100 nm. The fine particles of the oxide semiconductor may be mixed with a large particle size and a small particle size, or may be used as a multilayer.

  As a method of providing a thin film of oxide semiconductor fine particles on a substrate, a method of directly forming a thin film of oxide semiconductor fine particles on a substrate by spray spraying, etc., a thin film of oxide semiconductor fine particles is electrically formed on a substrate using a substrate as an electrode. After applying a paste containing fine particles obtained by hydrolyzing a precursor of oxide semiconductor fine particles such as a slurry of oxide semiconductor fine particles or semiconductor alkoxide on a substrate, drying, curing or baking And the like. The substrate provided with the oxide semiconductor fine particles serves as one electrode of the solar cell of the present invention, but a method using slurry is preferable in terms of electrode performance. In this method, a slurry is prepared by dispersing secondary agglomerated oxide semiconductor fine particles in a dispersion medium by an ordinary method so that the average primary particle diameter is 1 to 200 nm.

  The dispersion medium for dispersing the slurry is not particularly limited as long as the oxide semiconductor fine particles can be dispersed. Water, alcohols such as ethanol, ketones such as acetone and acetylacetone, hydrocarbons such as hexane, and the like are used. May be used as a mixture. In particular, the use of water is preferable in terms of reducing the change in viscosity of the slurry. Further, a dispersion stabilizer can be used in combination with the slurry for the purpose of stabilizing the dispersion state of the oxide semiconductor fine particles. Examples of the dispersion stabilizer that can be used include acids such as acetic acid, hydrochloric acid, nitric acid and acrylic acid, or organic solvents such as acetylacetone, polyethylene glycol and polyvinyl alcohol.

  The substrate coated with the slurry may be baked, and the baking temperature is usually 100 ° C. or higher, preferably 200 ° C. or higher, and the upper limit is generally 900 ° C. or lower, preferably 600 ° C. or lower, which is generally below the melting point (softening point) of the substrate. It is below ℃. The firing time is not particularly limited, but is preferably within 4 hours. The thickness of the thin film of oxide semiconductor fine particles on the substrate thus obtained is usually 1 to 200 μm, preferably 3 to 50 μm, particularly preferably 5 to 30 μm.

The thin film of oxide semiconductor fine particles may be subjected to secondary treatment. For example, the entire substrate provided with a thin film of oxide semiconductor particles is directly immersed in a solution of the same metal alkoxide, metal acyloxide, chloride, nitride, sulfide or acetylate as the oxide semiconductor, and then dried or dried. By refiring, the performance of the oxide semiconductor fine particle thin film can be improved. Examples of the metal alkoxide that can be used include titanium ethoxide, titanium isopropoxide and titanium t-butoxide, and examples of the metal acyloxide include n-dibutyl-diacetyltin, and alcohol solutions thereof are usually used. Examples of the chloride include titanium tetrachloride, tin tetrachloride and zinc chloride, and their aqueous solutions are usually used.
The oxide semiconductor thin film thus obtained is composed of fine particles of an oxide semiconductor.

Next, a method for supporting the metal complex dye represented by the formula (1) of the present invention on a thin film of oxide semiconductor fine particles will be described.
As a method for supporting the metal complex dye of the formula (1), a solution obtained by dissolving the dye in a solvent capable of dissolving the dye or a dye having low solubility may be obtained by dispersing the dye. A method of immersing a substrate provided with a thin film of the oxide semiconductor fine particles in the dispersion liquid. The immersion temperature is generally from room temperature to the boiling point of the solvent used for dissolving or dispersing the dye, and the immersion time is about 1 minute to 48 hours. Specific examples of the solvent that can be used to dissolve the metal complex dye of the present invention include methanol, ethanol, acetonitrile, dimethyl sulfoxide, dimethylformamide, acetone, and t-butanol. The density | concentration of the pigment | dye in a pigment | dye solution or a pigment | dye dispersion liquid is 1 * 10 < ^-6 > M-1M normally, Preferably it is 1 * 10 < ^-5 > M-1 * 10 < ^-1 > M. In this manner, the dye-sensitized photoelectric conversion element of the present invention having a thin film of oxide semiconductor fine particles sensitized with the metal complex dye of the formula (1) is obtained.

  As the metal complex dye represented by the formula (1) supported on the thin film of oxide semiconductor fine particles, only one type may be used, or a plurality of types may be mixed and used. Moreover, you may mix and use the metal complex pigment | dye represented by Formula (1) of this invention, the metal complex pigment | dye other than Formula (1), and an organic pigment | dye. In particular, by using a mixture of pigments having different absorption wavelengths, light in a wide wavelength region can be used, so that a solar cell with high conversion efficiency can be obtained. Examples of the metal complex dye other than the formula (1) that can be mixed include a ruthenium complex and a quaternary salt thereof, phthalocyanine, porphyrin, and the like. Examples include methine dyes such as merocyanine, oxonol, triphenylmethane, and acrylic acid dyes, and dyes such as xanthene, azo, anthraquinone, and perylene, preferably ruthenium complexes, merocyanine, and acrylic acid dyes. And methine dyes such as When two or more dyes are used, each dye may be sequentially adsorbed on a thin film of semiconductor fine particles, or each dye may be admixed and dissolved in advance.

  Examples of the methine dye include International Publication No. 2002-011213, International Publication No. 2004-082061, International Application JP / 2007/053885, Japanese Unexamined Patent Publication No. 2002-334729, Japanese Unexamined Patent Publication No. 2003-007358, Japanese Unexamined Patent Publication No. 2003-. No. 017146, JP 2003-059547, JP 2003-086257, JP 2003-115333, JP 2003-132965, JP 2003-142172, JP 2003-151649 JP, JP 2003-157915, JP 2003-282165, JP 2004-014175, JP 2004-022222, JP 2004-022387, JP 2004-227825, JP 2005-005026, JP 2005-019130, JP 2005-135656, JP 2006-079898, 2006-134649, JP 11-086916, JP JP-A-11-163378, JP-A-11-167937, JP-A-11-214730, JP-A-11-214731, JP2000-106224, JP2000-223167, JP2000- JP 228233, JP 2000-251958, JP 2000-277180 JP, 2000-285978, 2000-294303, 2000-294305, 2001-006761, 2001-024253, 2001-043906, JP 2001-052766, JP 2001-067931, JP 2001-076773, JP 2001-076775, JP 2001-229984, JP 2002-042907, JP JP 2002-042908, JP 2002-050779, JP 2002-100420, JP 2002-164089, JP 2002-231325, JP 2002-343455, JP 2002- JP 352871, JP 2003-007359, JP 2003-007360, JP 2003-017145, JP 2003-059547, JP 2003-078152, JP 2003-115333 JP, 2003-132965, JP 2003-142172, JP 2003-147329, JP 2003-151649, JP 2003-157915, JP 2003-197281, JP2003-203684, JP2003-234133, JP2003-249274, JP2 003-327948, JP2003-346925, JP2004-139755, JP2003-249275, JP2003-264010, JP2003-282165, JP2004- No. 143355, No. 2004-152854, No. 2004-171969, No. 2004-200068, No. 2004-207224, No. 2004-220974, No. 2004-234953 JP, 2004-235052, JP 2004-247158, JP 2004-253333, JP 2004-269695, JP 2004-292742, JP 2004-292743, JP 2004-292744, JP 2004-296170, JP 2004-319202, JP 2004-319309, JP 2005-005026, JP 2005-011800, JP JP 2005-019124, JP 2005-019249, JP 2005-019250, JP 2005-019251, JP 2005-0192520, JP 2005-019253, JP 2005- 019756, 2005-026030, 2005-026114, 2005-026115 JP, 2005-026116, JP 2005-032475, JP 2005-056650, JP 2005-056697, JP 2005-078887, JP 2005-078888, JP 2005-078995, JP 2005-085643, JP 2005-123013, JP 2005-123033, JP 2005-126586, JP 2005-129329, JP JP 2005-129429, JP 2005-129430, JP 2005-132914, JP 2005-135656, JP 2005-209359, JP 2005-209682, JP 2005- Examples thereof include dyes described in Japanese Patent No. 264025 and Japanese Patent Application Laid-Open No. 2001-052766.

  Examples of the metal complex dye include, for example, JP-A-2000-026487, JP-A-2000-268889, JP-A-2000-268890, JP-A-2001-006760, JP-A-2001-039995, JP 2001-059062, JP 2001-060467, JP 2001-060468, JP 2001-203005, JP 2001-226607, JP 2001-229983, JP 2001 -236999, JP-A-2001-237000, JP-A-2001-247546, JP-A-2001-247546, JP-A-2001-253894, JP-A-2001-291534, JP-A-2002-025636 JP, JP 2002-093473, JP 2002-093474, JP 2002-100417, JP 2002-105346, JP 2002-176188, JP 2002-193935 JP, 2002-241634, JP 2003-003083, JP 2003-051343, JP 2003-051344, JP 2003-212851, JP 2003-261536, JP 2003-272721, JP 2003-288953, JP 2001-253894 JP, 2004-176072, JP 2000-268890, JP 2005-120042, JP 2005-222941, JP 2005-222942, JP 2005-255992, JP 2001-039995, JP 2001-247546, JP 26664194, JP 3717552, JP 3738772, JP 3849005, JP 8-15097, U.S. Patent And complex dyes described in No. 5350644.

  As dyes other than the methine dyes and metal complex dyes, JP-A-9-199744, JP-A-10-051049, JP-A-10-093118, JP-A-10-093121, JP-A-10- 189065, JP-A-10-334954, JP-A-10-340742, JP-A-11-049773, JP-A-11-097725, JP-A-11-204821, JP-A-10-093118 JP, 2000-082506, JP 2000-100482, JP 2000-100483, JP 2000-195570, JP 2000-243463, JP 2000-251956, JP 2000-251957, JP 2000-285976, JP 2001-093589, JP 2001-203006, JP 2002-042909, JP 2002-047290, JP JP 2002-063949, JP 2002-100419, JP 2002-184476, JP 2002-270865, JP 2002-334729, JP 1999-049773, JP 2003- 007358, JP2003-017146, JP2003-03 1273, JP2003-086257, JP2003-123863, JP2003-152208, JP2003-346926, JP1998-340742, JP2002-0639497 JP-A 2004-143463, JP-A 2004-363096, JP-A 2002-047290, JP-A 2005-085659, JP-A 2004-143463, etc. I can do it.

  There are no particular limitations on the mixing ratio of the respective dyes when a plurality of types of dyes are mixed and carried, and the optimum conditions are appropriately selected depending on the respective dyes. It is preferable to mix at least about 10% mol or more per one dye. Even when a plurality of types of dyes are mixed and carried, the total concentration of the dyes in the solution may be the same as when only one kind is carried. In addition, examples of the solvent that can be used at this time include the same solvents as described above. One type of solvent may be used, or a different solvent may be used for each dye and then mixed. In addition, as a method of supporting a plurality of types of dyes, a method of supporting one type at a time may be used.

Supporting the dye on the thin film of oxide semiconductor fine particles in the presence of the inclusion compound is effective for preventing association of the dyes. Examples of the inclusion compound include steroidal compounds such as cholic acid, crown ether, cyclodextrin, calixarene, polyethylene oxide, and the like. Deoxycholic acid, dehydrodeoxycholic acid, chenodeoxycholic acid, cholic acid are preferable. Examples include cholic acids such as methyl ester and sodium cholate, and polyethylene oxide.
Alternatively, after the dye is supported, the thin film of oxide semiconductor fine particles may be treated with an amine compound such as 4-t-butylpyridine. As a treatment method, for example, a method of immersing a substrate provided with a thin film of oxide semiconductor fine particles carrying a dye in an ethanol solution of an amine compound is employed. The immersion temperature is usually room temperature (about 20 ° C.), and the immersion time is usually 1 to 72 hours, preferably 2 to 48 hours.

In the solar cell of the present invention, the dye-sensitized photoelectric conversion element in which the dye represented by the formula (1) is supported on the thin film of the oxide semiconductor fine particles is used as one electrode, and the other is provided opposite to the electrode. And a charge transfer layer filled between the electrodes.
As the counter electrode, a substrate having conductivity on its surface, for example, a substrate obtained by depositing a conductive material on glass or a polymer film, or a substrate coated with fine particles of a conductive material is used. Examples of the conductive material used for the counter electrode include Pt, Ti, W, Rh, Ru, carbon, and metal oxide used as a thin film of oxide semiconductor fine particles of the dye-sensitized photoelectric conversion element. Although it can be used without particular limitation as long as it has conductivity, metals such as Pt, Ti, W, and metal oxides are usually preferably used from the viewpoint of conductivity and corrosion resistance to the electrolyte, and Pt is particularly preferable. . When a material having conductivity other than Pt is used, it is preferable that a thin film such as Pt or carbon that acts catalytically on the reduction reaction of the redox electrolyte (described later) is formed on the surface.

  Examples of the charge transfer layer constituting the solar cell of the present invention include a redox electrolyte, a hole transport material, a p-type semiconductor, and the like, and any of these selected from a liquid, a solidified body (gel and gel), and a solid. It may be a form. Examples of liquids include redox electrolytes, molten salts, hole transport materials or p-type semiconductors dissolved in solvents, room temperature molten salts, and the like as solidified (gel and gel) A liquid in which a liquid matrix is contained in a polymer matrix or a low molecular gelling agent can be used. Further, as a solid material, a redox electrolyte, a molten salt, a hole transport material, a p-type semiconductor, or the like can be used.

Redox electrolytes include halogen redox electrolytes composed of halogen compounds and halogen molecules with halogen ions as counter ions, metals such as ferrocyanate-ferricyanate, ferrocene-ferricinium ions, and metal complexes such as cobalt complexes. Examples include redox electrolytes, organic redox electrolytes such as alkylthiol-alkyldisulfides, viologen dyes, hydroquinone-quinones, and the like, and halogen redox electrolytes are preferred. Examples of the halogen molecule in the halogen redox electrolyte comprising a halogen compound-halogen molecule include an iodine molecule and a bromine molecule, and an iodine molecule is preferable. As the halogen compound having a halogen ion as a counter ion, for example LiBr, NaBr, KBr, LiI, NaI, KI, CsI, CaI 2, MgI 2, CuI and halogenated metal salt or tetraalkylammonium iodide, and imidazolium Examples include halogen organic quaternary ammonium salts such as rhodium iodide and pyridinium iodide, and salts having iodine ions as counter ions are preferred. It is also preferable to use an electrolyte having an imide ion such as bis (trifluoromethanesulfonyl) imide ion or dicyanoimide ion as a counter ion in addition to the iodine ion. The concentration of the redox electrolyte in the charge transfer layer is usually about 0.01 to 99% by mass, preferably about 0.1 to 90% by mass.

Examples of the hole transport material include conductive polymers such as amine derivatives, polyacetylene, polyaniline, polythiophene polyphenylene vinylene, and polyfluorene vinylene, and compounds used for discotic liquid crystal phases such as triphenylene compounds.
Examples of the p-type semiconductor include CuI and CuSCN.

  When the charge transfer layer is formed in the form of a solution containing a redox electrolyte, a hole transport material, or a p-type semiconductor, an electrochemically inert solvent is used. For example, acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitrile, methoxyacetonitrile, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, γ-butyrolactone, dimethoxyethane, diethyl ether, diethyl carbonate, dimethyl carbonate, 1, 2 -Dimethoxyethane, N, N-dimethylformamide, N, N-dimethylsulfoxide, 1,3-dioxolane, methyl formate, 2-methyltetrahydrofuran, 3-methyl-oxazolidine-2-one, sulfolane, tetrahydrofuran, water, etc. Among these, in particular, acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitrile Methoxy acetonitrile, ethylene glycol, 3-methyl - oxazolidin-2-one, .gamma.-butyrolactone and the like are preferable. You may use these individually or in combination of 2 or more types.

  In the case where the charge transfer layer is a solidified electrolyte containing a redox electrolyte, a hole transport material, a p-type semiconductor, or the like, an electrolyte or an electrolyte solution is contained in a matrix such as an oligomer and a polymer, Chem. Lett. , 1241 (1998), and the like, in which the electrolyte or electrolyte solution is contained in the same manner.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the examples, parts represent parts by mass unless otherwise specified.

Synthesis example 1
Under a nitrogen atmosphere, a solution prepared by dissolving 20.8 parts of potassium tert-butoxide in 102 parts of N, N-dimethylsulfoxide (DMSO) and a solution obtained by dissolving 15.4 parts of 2-bromofluorene in 153 parts of DMSO were added dropwise. did. After stirring for 30 minutes, 27.8 parts of butyl iodide was added dropwise while maintaining the reaction solution temperature at 40 to 45 ° C. After stirring at 40 ° C. for 40 minutes, the reaction solution was added to ice water. Extraction was performed with chloroform-water, and the chloroform phase was dried over magnesium sulfate, and then chloroform was distilled off to obtain a brown tar-like solid. This brown tar-like solid was dissolved in a small amount of chloroform, separated and purified by column chromatography (filler; Wakogel C-400HG (trade name, manufactured by Wako Pure Chemical Industries, Ltd.), eluent: hexane), and purified by 2-bromo-9, 12.6 parts of 9-dibutylfluorene were obtained as colorless crystals.

Synthesis example 2
In a nitrogen atmosphere, 0.40 part of potassium vinyl trifluoroborate and 0.89 part of 2-bromo-9,9-dibutylfluorene were dissolved in 32 parts of 1-propanol, and then [1,1′-bis (diphenylphosphino ) Ferrocene] 0.039 part of dichloromethane adduct of dichloropalladium (II) and 0.25 part of triethylamine were added and reacted for 3 hours under reflux. The reaction mixture was extracted with chloroform, and the chloroform phase was dried over magnesium sulfate, and then chloroform was distilled off. The obtained tar-like mixture was separated and purified by column chromatography (filler; Wakogel C-400HG (trade name, manufactured by Wako Pure Chemical Industries, Ltd.), eluent: hexane), and 0.70 part of the following compound (1001) was white solid. Got as.

Synthesis example 3
After dissolving 0.43 part of the above compound (1001) and 0.34 part of 2-chloro-4-iodopyridine in 3.1 parts of triethanolamine, 0.011 part of palladium (II) acetate was added, and The reaction was allowed for 10 hours. The reaction mixture was extracted with chloroform, and the chloroform phase was dried over magnesium sulfate, and then chloroform was distilled off. The mixture was separated and purified by column chromatography (filler; Wakogel C-400HG (trade name, manufactured by Wako Pure Chemical Industries, Ltd., eluent: chloroform)) to obtain 0.15 part of the following compound (1002) as a white solid.

Synthesis example 4
In a nitrogen atmosphere, 0.61 part of the above compound (1002) was dissolved in 8.9 parts of tetrahydrofuran, and then 0.23 part of dibromobis (triphenylphosphine) nickel (II), 0.18 part of zinc powder, 0. 11 parts and 0.39 part of tetraethylammonium iodide were added and reacted under reflux for 20 hours. After the reaction mixture was brought to room temperature, 7.0 parts of 26% aqueous ammonia, 4.8 parts of water, and 27 parts of dichloromethane were added and stirred for 15 minutes. The reaction mixture was extracted with dichloromethane, and the dichloromethane phase was dried over magnesium sulfate, and then dichloromethane was distilled off. The mixture was separated and purified by column chromatography (filler: Wakogel C-400HG (trade name, manufactured by Wako Pure Chemical Industries, Ltd., eluent: chloroform)) to obtain 0.046 part of the following compound (1003) as a white solid.

Synthesis example 5
Under a nitrogen atmosphere, 0.048 part of the compound (1003) and 0.019 part of ruthenium-p-cymene dimer were heated to reflux in 4 parts of chloroform for 4 hours. After completion of the reaction, chloroform was distilled off, and purification was performed by column chromatography (filler; Sephadex-LH-20 (trade name: Amersham Biosciences), eluent: methanol). After purification, it was dried at 60 ° C. for 14 hours to obtain 0.054 part of the following compound (1004) as yellow crystals.

Example 1
Under a light-shielding and nitrogen atmosphere, 0.039 part of the above compound (1004) and 0.0082 part of 2,2′-bipyridine-4,4′-dicarboxylic acid were added to 140 parts of dehydrated N, N-dimethylformamide (DMF). Stir at 4 ° C. for 4 hours. 0.054 parts of ammonium thiocyanate was added, and the mixture was further stirred for 4 hours. After completion of the reaction, the mixture was allowed to cool to room temperature and left for 36 hours. Thereafter, the reaction solution was filtered, the filtrate was poured into 15 parts of water, and the precipitated crystals were collected by filtration. This was washed twice with 2 parts of water and dried at 70 ° C. for 14 hours to obtain 0.033 part of compound (6) (see Table 1) as black-brown crystals.

About this compound (6), the measurement result of the light absorbency implemented with the spectrophotometer (made by UV-3150 Shimadzu Corporation) is as follows.
Maximum absorption wavelength; λmax = 367 nm
Molecular extinction coefficient (ε) = 55063 (solvent: N, N-dimethylformamide)
This compound has a maximum absorption wavelength at 541 nm.

Example 2
A titanium oxide film was formed by applying a titanium oxide dispersion PASOL HPW-18NR (trade name, manufactured by Catalyst Kasei Kogyo Co., Ltd.) as a paste on a transparent conductive glass electrode. The transparent conductive glass electrode having a titanium oxide film was baked at 450 ° C. for 30 minutes to obtain a transparent conductive glass electrode having a 7 μm thick titanium dioxide semiconductor film. The film thickness of the titanium dioxide semiconductor film was measured using a surface roughness shape measuring instrument (Surfcom 570A manufactured by Tokyo Seimitsu Co., Ltd.). Next, about 1 cc of a 0.04M titanium tetrachloride aqueous solution was dropped onto the titanium dioxide semiconductor film on the electrode, and then allowed to stand at 60 ° C. for 30 minutes, further washed with water, and then fired again at 450 ° C. for 30 minutes. A porous substrate for use was obtained.
The compound (6) obtained in Example 1 is dissolved in a 1: 1 mixed solution of tert-butanol and acetonitrile so as to be 3.0 × 10 ⁻⁴ M, and chenodeoxycholic acid is further added to 40 mM. did. The porous substrate for evaluation obtained by the above method is immersed in this solution at room temperature (20 ° C.) for 12 hours to carry the dye, and then the porous substrate is washed with the mixed solvent and further dried. Thus, a dye-sensitized photoelectric conversion element of the present invention comprising a thin film of semiconductor fine particles dye-sensitized by the above was obtained. The dye-sensitized photoelectric conversion element of the present invention thus obtained is opposed to the sputtered surface of the conductive glass sputtered with platinum so that a 20 μm gap is provided and fixed with a clip, and an electrolyte is placed in the gap. A solar cell of the present invention was obtained by injecting a solution (electrolytic solution) containing the solution to fill the voids. As the electrolytic solution, 3-methoxypropionitrile, 1,2-dimethyl-3-propylimidazolium iodide / LiI / I ₂ / tert-butylpyridine was 0.6 M / 0.1 M / 0.00%, respectively. A redox electrolyte dissolved to 1M / 0.5M was used.

The photoelectric conversion ability of the solar cell obtained in Example 2 was evaluated.
The solar cell used for the evaluation had an effective area of 0.25 cm ² . A 500 W xenon lamp was used as the light source, and the irradiation amount to the solar cell through an AM (air passing through the atmosphere) 1.5 filter was 100 mW / cm ² . The open circuit voltage, short circuit current, conversion efficiency, and fill factor measured using a solar simulator YSS-50A (Yamashita Denso Co., Ltd.) were as follows.
Open-circuit voltage (V) 0.69
Short circuit current (mA / cm ² ) 10.09
Conversion efficiency (%) 4.62
Fill factor 0.66

  From the above results, when the compound (6) represented by the formula (1) of the present invention is used as a sensitizing dye of a dye-sensitized photoelectric conversion element, the semiconductor layer of titanium dioxide fine particles is 7 μm thinner than usual. It was confirmed that high conversion efficiency can be obtained even in The dye-sensitized photoelectric conversion element sensitized with this compound is excellent in various performances other than the conversion efficiency, and the metal complex dye represented by the formula (1) of the present invention is used in the purification process or on the titanium dioxide electrode. Since it is highly soluble in an organic solvent when adsorbed on the surface, it has an excellent property that these operations can be performed efficiently.

Claims (13)

A dye-sensitized photoelectric conversion element obtained by supporting a metal complex dye represented by the following formula (1) or a salt thereof on a thin film of oxide semiconductor fine particles provided on a substrate.

(In formula (1), Y ₁ and Y ₂ each independently represent a thiocyanate group (—SCN), a halogen atom or an isothiocyanate group (—NCS), or Y ₁ and Y ₂ are bonded to form one M ₁ and M ₂ each independently represents a hydrogen atom or an ammonium ion, and Q _{1 to} Q ₁₄ each independently represent a hydrogen atom or an aromatic residue optionally having a substituent. Group, optionally substituted aliphatic hydrocarbon residue, hydroxyl group, phosphate group, cyano group, nitro group, halogen atom, carboxyl group, carbonamido group, alkoxycarbonyl group, arylcarbonyl group, alkoxyl group, an aryloxy group, a substituted amide group, an acetamide group, an acyl group or a substituted or unsubstituted amino group (provided that one or two following formulas selected from Q ₇ to Q ₁₄ ( )

(In the formula (2), .R ₁ and R ₂ n ₁ represents 1 are each independently a hydrogen atom, a cyano group, a halogen atom, an aliphatic substituted hydrocarbon residue or a substituted Represents an alkoxyl group which may have a group, or a plurality of R ₁ and / or R ₂ may be bonded to each other to have an aromatic ring or a substituent. have aliphatic hydrocarbon ring or substituent to form a heterocyclic. Further, represented by two Exemplary ethynylphenylbiadamantane derivatives selected from _{Q 7 ~Q 14 (2),} R 1 and R ₂ are each more When present, each R ₁ and R ₂ may be the same or different, and R ₃ and R ₄ each independently represent a hydrogen atom, an aliphatic hydrocarbon residue which may have a substituent, or or it represents an aromatic residue which may have a substituent, or R ₃ and R ₄ are combined to have a substituent There is formed a heterocyclic ring which may have an aliphatic hydrocarbon ring or a substituent. Also, expressed in 2 Exemplary ethynylphenylbiadamantane derivatives selected from _{Q 7 ~Q 14 (2),} R 3 and R ₄ are each more When present, each R ₃ and R ₄ may be the same or different. ) The dye-sensitized photoelectric conversion device according to claim 1, wherein at least one of Q ₉ and Q ₁₂ in the formula (1) is a metal complex dye represented by the formula (2) or a salt thereof. The dye-sensitized photoelectric conversion element according to claim 2, wherein Q ₉ and Q ₁₂ in the formula (1) are a metal complex dye represented by the formula (2) or a salt thereof. The dye-sensitized photoelectric conversion element according to any one of claims 1 to 3, wherein Y ₁ and Y ₂ in Formula (1) are NCS groups. The dye-sensitized photoelectric conversion device according to claim 4, wherein R ₃ and R ₄ in formula (2) are each independently an aliphatic hydrocarbon residue which may have a substituent. 6. The dye-sensitized photoconductor according to claim 5, wherein R ₃ and R ₄ in formula (2) are each independently a saturated aliphatic hydrocarbon residue having 1 to 18 carbon atoms which may have a substituent. Conversion element. The dye-sensitized photoelectric conversion element according to claim 6, wherein R ₃ and R ₄ in the formula (2) are n-butyl groups. The dye-sensitized photoelectric conversion element according to any one of claims 1 to 7, wherein R ₁ and R ₂ in the formula (2) are hydrogen atoms. 9. A thin film of oxide semiconductor fine particles provided on a substrate further supports a methine dye and / or a metal complex dye having a structure other than the formula (1) or a salt thereof. A dye-sensitized photoelectric conversion element according to claim 1. The dye-sensitized photoelectric conversion element according to any one of claims 1 to 9, wherein a thin film of oxide semiconductor fine particles containing titanium dioxide, zinc oxide, or tin oxide is used. The dye-sensitized photoelectric conversion element according to any one of claims 1 to 10, wherein the metal complex dye represented by the formula (1) or a salt thereof is supported in the presence of an inclusion compound. The solar cell which uses the dye-sensitized photoelectric conversion element as described in any one of Claims 1 thru | or 11. The metal complex pigment | dye represented by Formula (1) of Claim 1, or its salt.