JP2016193954A - Methine dye and dye-sensitized photoelectric conversion element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To develop a dye having a specific structure, a photoelectric conversion element using the dye and having high conversion efficiency, and a solar cell using the photoelectric conversion element.SOLUTION: The methine dye is represented by formula (1) (m is an integer of 1-5; l and n are each an integer of 0-6; j is an integer of 0-3; Xand Yare each a carboxyl group, a cyano group, or the like; Zand Zare each an oxygen atom, a sulfur atom, or the like; A-A, A, and Aare each a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, or the like; Ais a hydrogen atom, an aliphatic hydrocarbon residue, a cyano group, or the like; Aand Aare each a hydrogen atom, an aliphatic hydrocarbon residue, a cyano group, or the like; and Rand Rare each a specific aromatic residue, a heterocyclic residue, or the like).SELECTED DRAWING: None

Description

  The present invention relates to a novel methine dye having a specific structure, a photoelectric conversion element having a thin film of semiconductor fine particles sensitized with the dye, and a solar cell using the same, and more specifically, to a thin film of oxide semiconductor fine particles. The present invention relates to a photoelectric conversion element carrying a methine compound (pigment) having a structure and a solar cell using the photoelectric conversion element.

  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, there is a problem that they are difficult to use for general purposes because of the high energy and cost required for production. A photoelectric conversion element using semiconductor fine particles sensitized with a dye or a solar cell using the same is also known, and a material and a manufacturing technique for producing the photoelectric conversion element are disclosed (Patent Document 1, Non-Patent Document). 1, see non-patent document 2). This photoelectric conversion element is manufactured using a relatively inexpensive oxide semiconductor such as titanium oxide, and there is a possibility that a photoelectric conversion element having a lower cost than a conventional solar cell using silicon or the like can be obtained. It has attracted more attention than solar cells. However, the ruthenium complex itself used as a sensitizing dye for obtaining an element with high conversion efficiency is expensive, and a problem remains in its stable supply. On the other hand, attempts have been made to use organic dyes as sensitizing dyes, but problems such as low conversion efficiency, stability, and durability of photoelectric conversion elements using the dyes have been sufficiently solved. Therefore, the present situation is that it has not been put into practical use, and further improvement in conversion efficiency is desired (see Patent Document 2).

Japanese Patent No. 2664194 WO2002 / 011213

B.O'Regan and M.Graetzel Nature, 353, 737 (1991) MKNazeeruddin, A. Kay, I. Rodicio, R. Humphry-Baker, E. Muller, P. Liska, N. Vlachopoulos, M. Graetzel, J. Am. Chem. Soc., 115, 6382 (1993) Year)

  In photoelectric conversion elements using oxide semiconductor fine particles sensitized with an organic dye, development of photoelectric conversion elements that are inexpensive and have high durability and high conversion efficiency is required.

As a result of diligent efforts to solve the above problems, the present inventors have sensitized a thin film of semiconductor fine particles using a methine dye having a specific structure and created a photoelectric conversion element, thereby improving durability and conversion. The inventors have found that a photoelectric conversion element with high efficiency can be obtained, and have completed the present invention.
That is, the present invention
(1) Methine dye represented by the following formula (1)

(In the formula (1), m represents an integer of 1 to 5, l and n each independently represents an integer of 0 to 6, and j represents an integer of 0 to 3, respectively.
X ₁ and Y ₁ are each independently a hydrogen atom, aromatic residue, aliphatic hydrocarbon residue, carboxyl group, phosphoric acid group, sulfonic acid group, cyano group, acyl group, amide group, alkoxycarbonyl group or sulfonylbenzene. Represents a group. X ₁ and Y ₁ may be bonded to form a ring.
Z ₁ and Z ₂ each independently represents an oxygen atom, a sulfur atom, a selenium atom or NR ₁₁ . R ₁₁ represents a hydrogen atom, an aromatic residue or an aliphatic hydrocarbon residue. at least one of m or j is 2 or more, if Z ₁ and / or Z ₂ there are a plurality, each of Z ₁ and / or Z ₂ may be the same or different from each other.
A ₁ , A ₂ , A ₃ , A ₅ and A ₆ are each independently a hydrogen atom, aromatic residue, aliphatic hydrocarbon residue, cyano group, halogen atom, carbonamido group, amide group, alkoxy group, aryl An oxy group, an alkoxycarbonyl group, an arylcarbonyl group or an acyl group is represented. Further, when at least one of l or n is 2 or more and any one of A ₂ , A ₃ , A ₅ and A ₆ is present, each of A ₂ , A ₃ , A ₅ and A ₆ is They may be the same or different from each other. When l is other than 0, any one of A ₁ , A ₂ and A ₃ may form a ring.
A ₄ represents a hydrogen atom, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carbonamido group, an alkoxy group, an amide group, an alkoxycarbonyl group or an acyl group. When m is 2 or more and a plurality of A ₄ are present, each A ₄ may be the same as or different from each other.
A ₇ and A ₈ each independently represents a hydrogen atom, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carbonamido group, an alkoxy group, an alkoxycarbonyl group or an acyl group. When j is 2 or more and a plurality of A ₇ and A ₈ exist, each A ₇ and A ₈ may be the same as or different from each other.
R ₁ is represented by the following formula (3002)

(In the formula (3002), p represents an integer of 1 to 3, and q represents an integer of 0 to 6, respectively.
X ₂ and Y ₂ are each independently a hydrogen atom, aromatic residue, aliphatic hydrocarbon residue, carboxyl group, phosphate group, sulfonate group, cyano group, acyl group, amide group, alkoxycarbonyl group or sulfonylbenzene. Represents a group. X ₂ and Y ₂ may combine to form a ring.
Z ₄ represents an oxygen atom, a sulfur atom, a selenium atom or NR ₁₂ . R ₁₂ represents a hydrogen atom, an aromatic residue or an aliphatic hydrocarbon residue. When p is 2 or more and a plurality of Z ₄ are present, each Z ₄ may be the same as or different from each other.
A ₁₁ and A ₁₂ each independently represent a hydrogen atom, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carbonamido group, an alkoxy group, an alkoxycarbonyl group or an acyl group. When p is 2 or more and a plurality of A ₁₁ and A ₁₂ are present, each A ₁₁ and A ₁₂ may be the same as or different from each other.
A ₁₃ , A ₁₄ and A ₁₅ are each independently a hydrogen atom, aromatic residue, aliphatic hydrocarbon residue, cyano group, halogen atom, carbonamido group, amide group, alkoxy group, aryloxy group, alkoxycarbonyl group Represents an arylcarbonyl group or an acyl group. In the case where q is A ₁₃ and A ₁₄ there are a plurality of two or more, each of A ₁₃ and A ₁₄ may be the same or different from each other. In addition, when q is other than 0, any one of A ₁₃ , A ₁₄ , and A ₁₅ may form a ring. )
Represents a group represented by When m is 2 or more and a plurality of R ₁ are present, each R ₁ may be the same as or different from each other.
R ₂ represents the following formula (3001) or (3003)

(In the formula (3001) or (3003), R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ each independently represent a hydrogen atom, an aromatic residue or an aliphatic hydrocarbon residue.
R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ are each independently a hydrogen atom, aromatic residue, aliphatic hydrocarbon residue, cyano group, acyl group, amide group, alkoxy group, alkoxycarbonyl group or sulfonylbenzene group. Represents. )
Represents a hydrogen atom or an aliphatic hydrocarbon residue. When n is other than 0, any one of A ₅ , A ₆ and R ₂ may form a ring. ),
(2) The methine dye according to (1), wherein l, n, and q in formula (1) are 0,
(3) The methine dye according to item (1), wherein m in formula (1) is 1 to 3,
(4) The methine dye according to item (1), wherein j in formula (1) is 1 to 3,
(5) The methine dye according to the above item (1), wherein Z _{1 to} Z ₄ in formula (1) are sulfur atoms,
(6) In formula (1), one of X ₁ and Y ₁ is a carboxyl group and the other is a carboxyl group, a cyano group or an acyl group, and / or one of X ₂ and Y ₂ is a carboxyl group and the other is a carboxyl group. , A methine dye according to item (1), which is a cyano group or an acyl group,
(7) In Formula (1), one of X ₁ and Y ₁ is a carboxyl group and the other is a cyano group, and / or one of X ₂ and Y ₂ is a carboxyl group and the other is a cyano group (6) A methine dye described in
(8) At least one of X ₁ and Y ₁ in Formula (1) is at least one group selected from the group consisting of a carboxyl group, a hydroxyl group, a phosphate group, a sulfonate group, and a salt of these acidic groups. An aromatic residue as a substituent and / or at least one of X ₂ and Y ₂ is selected from the group consisting of a carboxyl group, a hydroxyl group, a phosphate group, a sulfonate group, and a salt of these acidic groups The methine dye according to item (1), which is an aromatic residue having at least one group as a substituent,
(9) at least one of X ₁ and Y ₁ in the formula (1), and / or at least one of the following formula X ₂ and Y ₂ (1001) ~ (1033)

The methine dye according to item (8), which is any of the groups represented by:
(10) The methine dye according to the above item (1), wherein X ₁ and Y ₁ in Formula (1) are bonded and / or X ₂ and Y ₂ are bonded to form a ring structure,
(11) A ring structure formed by combining X ₁ and Y ₁ in Formula (1) and / or combining X ₂ and Y ₂ is represented by the following formulas (2001) to (2044).

(In formulas (2001) to (2044), * represents a carbon atom to which X ₁ and Y ₁ are bonded and / or a carbon atom to which X ₂ and Y ₂ are bonded in formula (1).)
The methine dye according to item (10), which is any of the ring structures represented by:
(12) The methine according to item (11), wherein the ring structure formed by combining X ₁ and Y ₁ in formula (1) and / or combining X ₂ and Y ₂ has a carboxyl group as a substituent. Pigments,
(13) (1) X ₁ and Y ₁ are bonded in, and / or X ring _{structure 2} and Y ₂ is formed by bonding is a ring structure represented by Formula (2007) or (2012) The methine dye described in (12) above,
(14) The methine dye according to the above item (1), wherein A _{1 to} A ₁₅ in formula (1) are hydrogen atoms,
(15) R ₂ in the formula (1) is
(I) is a group represented by the formula (3001), and R ₁₂ and R ₁₃ in the formula (3001) are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
Or (II) a group represented by the formula (3003), wherein R ₁₄ and R ₁₅ in the formula (3003) are each independently a phenyl group or a group represented by the formula (3001), and R _{16 to} R ₁₉ are In the above item (1), each independently a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms, and R ₁₂ and R ₁₃ in the formula (3001) are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. The methine dyes described,
(16) R ₂ in the formula (1) is represented by the following formulas (3101) to (3114)

The methine dye according to the above item (15), which is any of the groups represented by:
(17) The methine according to item (16), wherein R ₂ in formula (1) is a group represented by formula (3107), (3108), (3110), (3111), (3113) or (3114) Pigments,
(18) The methine dye according to item (17), wherein R ₂ in formula (1) is a group represented by formula (3107) or (3111),
(19) The following formula (705), (710) or (712)

The methine dye according to the preceding item (1) represented by:
(20) A photoelectric conversion element in which a methine dye represented by the formula (1) described in (1) above is supported on a thin film of oxide semiconductor fine particles provided on a substrate,
(21) A solar cell using the photoelectric conversion element according to (20) above,
About.

  By using a methine dye having a specific structure, it was possible to provide a solar cell having high durability and capable of maintaining high conversion efficiency even after a light durability test.

The present invention is described in detail below.
The methine dye of the present invention has a structure represented by the following formula (1). One of the characteristics of the methine dye represented by the formula (1) is that R ₁ in a specific site is a specific structure represented by the formula (3002), and the methine dye is supported on the methine dye. The photoelectric conversion element provided with a thin film of oxide semiconductor fine particles has a higher conversion efficiency than a photoelectric conversion element using a methine dye or other dye that does not have a specific structure in which R ₁ is represented by the formula (3002). And has excellent durability. Hereinafter, the methine dye represented by the formula (1) will be described.

M in Formula (1) represents an integer of 1 to 5, preferably 1 to 3, more preferably 1 to 2, and still more preferably 1.
L in Formula (1) represents an integer of 0 to 6, and is preferably 0.
N in Formula (1) represents an integer of 0 to 6, and is preferably 0.
J in Formula (1) represents an integer of 0 to 3, preferably 1 to 3, and more preferably 1 to 2.

X ₁ and Y ₁ in formula (1) are each independently a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a carboxyl group, a phosphoric acid group, a sulfonic acid group, a cyano group, an acyl group, an amide group, An alkoxycarbonyl group or a sulfonylbenzene group is represented.

The aromatic residue represented by X ₁ and Y _{1 in} formula (1) means an aromatic ring or a group obtained by removing one hydrogen atom from a condensed ring including an aromatic ring, and the aromatic residue has a substituent. You may have. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, pyrene, perylene and terylene, indene, azulene, pyridine, pyrazine, pyrimidine, pyrazole, pyrazolidine, thiazolidine, oxazolidine, pyran, and chromene. , Pyrrole, pyrrolidine, benzimidazole, imidazoline, imidazolidine, imidazole, triazole, triazine, diazole, indoline, thiophene, thienothiophene, furan, oxazole, oxadiazole, thiazine, thiazole, indole, benzothiazole, benzothiadiazole, naphthothiazole , Heteroaromatic rings such as benzoxazole, naphthoxazole, indolenine, benzoindolenine, quinoline and quinazoline, Condensed aromatic ring such as Ren and carbazole, and the like, is preferably a group obtained by removing one hydrogen atom from a condensed ring containing an aromatic ring or aromatic ring having 4 to 20 carbon atoms.

There are no particular limitations on the substituent that the aromatic residue represented by X ₁ and Y ₁ may have, for example, sulfonic acid group, sulfamoyl group, cyano group, isocyano group, thiocyanato group, isothiocyanato group, nitro group , Nitrosyl group, halogen atom, hydroxyl group, phosphate group, phosphate ester group, substituted or unsubstituted amino group, mercapto group, amide group, alkoxy group, aryloxy group, carboxyl group, carbamoyl group, acyl group, aldehyde group And substituted carbonyl groups such as an alkoxycarbonyl group and an arylcarbonyl group, and aromatic residues and aliphatic hydrocarbon residues.
Examples of the halogen atom as a substituent that the aromatic residue may have include fluorine, chlorine, bromine, iodine and the like, and a bromine atom and a chlorine atom are preferable.
Examples of the phosphoric acid ester group as a substituent that the aromatic residue may have include a phosphoric acid (having 1 to 4 carbon atoms) alkyl ester group, and a preferred specific example is a methyl phosphate group. , Ethyl phosphate group, phosphoric acid (n-propyl) group, and phosphoric acid (n-butyl) group.
Examples of the substituted or unsubstituted amino group as a substituent that the aromatic residue may have include an amino group, a mono- or dimethylamino group, a mono- or diethylamino group, a mono- or di (n-propyl) amino group, and the like. Alkyl-substituted amino group, mono- or diphenylamino group, aromatic group-substituted amino group such as mono- or dinaphthylamino group, amino group such as monoalkylmonophenylamino group and amino group substituted with one aromatic residue or benzyl An amino group, an acetylamino group, a phenylacetylamino group, etc. are mentioned.

Examples of the mercapto group as a substituent that the aromatic residue may have include a mercapto group, an alkyl mercapto group, and the like. Specifically, a methyl mercapto group, an ethyl mercapto group, an n-propyl mercapto group, and isopropyl Examples include a mercapto group, an n-butyl mercapto group, an isobutyl mercapto group, a sec-butyl mercapto group and a t-butyl mercapto group, and an alkyl mercapto group having 1 to 4 carbon atoms or a phenyl mercapto group.
Examples of the amide group as a substituent that the aromatic residue may have include an amide group, an acetamide group, and an alkylamide group, and specifically preferred examples include an amide group, an acetamido group, an N-methylamide group, N-ethylamide group, N- (n-propyl) amide group, N- (n-butyl) amide group, N-isobutyramide group, N- (sec-butylamide) 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 -Methylacetamide group, N-ethylacetamide group, N- (n-propyl) acetamide group, N- (n-butyl) acetamide group, N-isobutylacetamide group, N- (sec-butyl) ) Acetamide group, N- (t-butyl) 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-diisobutylacetamide group, and arylamide group, specifically preferably phenylamide group, naphthylamide group, phenylacetamide group, naphthylacetamide group and the like.

Examples of the alkoxy group as a substituent that the aromatic residue may have include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and t- And a butoxy group.
Examples of the aryloxy group as a substituent that the aromatic residue may have include a phenoxy group and a naphthoxy group.
Examples of the acyl group as a substituent that the aromatic residue may have include an alkylcarbonyl group having 1 to 10 carbon atoms and an arylcarbonyl group, and preferably an alkylcarbonyl group having 1 to 4 carbon atoms. Specific examples include an acetyl group, a propionyl group, a trifluoromethylcarbonyl group, a pentafluoroethylcarbonyl group, a benzoyl group, and a naphthoyl group.
Examples of the alkoxycarbonyl group as a substituent that the aromatic residue may have include an alkoxycarbonyl group having 1 to 10 carbon atoms. Specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a t-butoxycarbonyl group, and an n-pen. A tooxycarbonyl group, an n-hexyloxycarbonyl group, an n-heptyloxycarbonyl group, an n-nonyloxycarbonyl group, and an n-decyloxycarbonyl group.

The arylcarbonyl group as a substituent that the aromatic residue may have represents, for example, a group in which an aryl group such as benzophenone or naphthophenone and carbonyl are linked.
Examples of the aromatic residue as a substituent that the aromatic residue may have include the same as those described in the section of the aromatic residue represented by X ₁ and Y _{1 in} the formula (1). .
Examples of the aliphatic hydrocarbon residue as a substituent that the aromatic residue may have include a saturated or unsaturated, linear, branched or cyclic alkyl group, and the aliphatic hydrocarbon residue. The group may have a substituent. The aliphatic hydrocarbon residue is preferably a saturated alkyl group, and more preferably a saturated linear alkyl group. Moreover, it is preferable that carbon number which an aliphatic hydrocarbon residue has is 1-36, It is more preferable that it is 1-18, It is still more preferable that it is 1-8. Specific examples of these aliphatic hydrocarbon residues include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group, n-pentyl. Group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group Group, n-hexadecyl group, n-heptadecyl group, n-octadecyl 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, pentynyl group, hexynyl group, isohexynyl group, cyclohexyl group Group, and the like. Moreover, as a cyclic | annular alkyl group, a C3-C8 cycloalkyl group etc. are mentioned, for example. Particularly preferably, it is a linear alkyl group having 1 to 8 carbon atoms.

The aromatic residue, aliphatic hydrocarbon residue, amide group, acyl group, alkoxy group, aryloxy group, arylcarbonyl group and alkoxycarbonyl group as substituents that the aromatic residue may have are substituents. Examples of the substituent include the same as those described in the section of the substituent that the aromatic residue represented by X ₁ and Y _{1 in} Formula (1) may have. .

The aromatic residue represented by X ₁ and Y _{1 in} the formula (1) is at least one group selected from the group consisting of a carboxyl group, a hydroxyl group, a phosphate group, a sulfonate group, and a salt of these acidic groups. It is preferably an aromatic residue having one or more substituents, and more preferably any one of groups represented by the following formulas (1001) to (1033).

The aliphatic hydrocarbon residue represented by X ₁ and Y ₁ in the formula (1) is described in the section of the substituent that the aromatic residue represented by X ₁ and Y _{1 in} the formula (1) may have. And the same aliphatic hydrocarbon residues. The aliphatic hydrocarbon residue may have a substituent, and examples of the substituent include substituents that the aromatic residue represented by X ₁ and Y _{1 in} the formula (1) may have. The same as mentioned in the section.
As the acyl group represented by X ₁ and Y ₁ in the formula (1), the acyl group described in the section of the substituent that the aromatic residue represented by X ₁ and Y _{1 in} the formula (1) may have and The same can be mentioned. The acyl group may have a substituent, and the substituent is described in the section of the substituent that the aromatic residue represented by X ₁ and Y _{1 in} the formula (1) may have. The same thing is mentioned.
The amide group represented by X ₁ and Y ₁ in the formula (1) is the same as that described in the section of the substituent that the aromatic residue represented by X ₁ and Y _{1 in} the formula (1) may have. Things. The amide group may have a substituent, and the substituent is described in the section of the substituent that the aromatic residue represented by X ₁ and Y _{1 in} the formula (1) may have. The same thing as an amide group is mentioned.
The alkoxycarbonyl group represented by X ₁ and Y ₁ in the formula (1) is an alkoxycarbonyl described in the section of the substituent that the aromatic residue represented by X ₁ and Y _{1 in} the formula (1) may have. The same thing as a group is mentioned. The alkoxycarbonyl group may have a substituent, and the substituent is described in the section of the substituent that the aromatic residue represented by X ₁ and Y _{1 in} the formula (1) may have. The same thing is mentioned.

X ₁ and Y ₁ in formula (1) may be bonded to form a ring. The ring may have a substituent, and examples of the substituent include those described in the section of the substituent that the aromatic residue represented by X ₁ and Y ₁ in formula (1) may have. The same thing is mentioned. Specific examples of the ring structure formed by combining X ₁ and Y ₁ include ring structures represented by the following formulas (2001) to (2044), among which the ring structure has a carboxyl group as a substituent. It is particularly preferable that the ring structure is (2007) or (2012), and (2007) is very preferable.

The * mark in the above formulas (2001) to (2044) represents the carbon atom to which X ₁ and Y ₁ are bonded in formula (1).

X ₁ and Y ₁ in Formula (1) are preferably any of the following (i) to (iii).
(I) X ₁ and Y ₁ are preferably each independently a carboxyl group, a phosphate group, a cyano group or an acyl group, more preferably each independently a carboxyl group, a cyano group or an acyl group, Is more preferably a carboxyl group and the other is a carboxyl group, a cyano group or an acyl group, and it is particularly preferable that one is a carboxyl group and the other is a cyano group.
(Ii) At least one of X ₁ and Y ₁ is at least one group selected from the group consisting of a carboxyl group, a hydroxyl group, a phosphoric acid group, a sulfonic acid group, and a salt of these acidic groups. An aromatic residue as a substituent is preferable, and the aromatic residue is more preferably represented by the above formulas (1001) to (1033).
(Iii) X ₁ and Y ₁ are preferably bonded to form a ring structure, and the ring structure is more preferably the above formulas (2001) to (2044), and the ring structure substitutes a carboxyl group as a substituent. The ring structure is more preferably the formula (2007) or (2012), and the formula (2007) is very particularly preferable.

Z ₁ and Z ₂ in formula (1) each independently represent an oxygen atom, a sulfur atom, a selenium atom or NR ₁₁ , and R ₁₁ represents a hydrogen atom, an aromatic residue or an aliphatic hydrocarbon residue.
Examples of the aromatic residue represented by R ₁₁ include the same as those described in the section of the aromatic residue represented by X ₁ and Y _{1 in} the formula (1).
Examples of the aliphatic hydrocarbon residue represented by R ₁₁ include the aliphatic hydrocarbon residues described in the section of the substituent that the aromatic residue represented by X ₁ and Y ₁ in Formula (1) may have; The same can be mentioned.
The aromatic residue and aliphatic hydrocarbon residue represented by R ₁₁ may have a substituent, and specific examples of the substituent include sulfamoyl group, cyano group, isocyano group, thiocyanato group, isothiocyanato group, Nitro group, nitrosyl group, halogen atom, phosphate ester group, substituted or unsubstituted amino group, amide group, alkoxy group, aryloxy group, carbamoyl group, acyl group, aldehyde group, alkoxycarbonyl group and arylcarbonyl group, etc. An aromatic residue, an aliphatic hydrocarbon residue, etc. other than a substituted carbonyl group are mentioned.
Halogen atom, phosphate group, substituted or unsubstituted amino group, amide group, alkoxy group, aryloxy group as a substituent which the aromatic residue and aliphatic hydrocarbon residue represented by R ₁₁ may have , Acyl group, alkoxycarbonyl group, arylcarbonyl group, and aliphatic hydrocarbon residue are described in the section of the substituent that the aromatic residue represented by X ₁ and Y ₁ in formula (1) may have. The same thing is mentioned.
Examples of the aromatic residue as the substituent that the aromatic residue and the aliphatic hydrocarbon residue represented by R ₁₁ may have include the aromatic residues represented by X ₁ and Y _{1 in} the formula (1). The same as mentioned in the section.

In at least one of m or j in the formula (1) is 2 or more, if Z ₁ and / or Z ₂ there are a plurality, each of Z ₁ and / or Z ₂ may be the same or different from each other .
Z ₁ and Z ₂ in formula (1) are each independently preferably an oxygen atom, a sulfur atom or a selenium atom, and more preferably a sulfur atom.

A ₁ , A ₂ , A ₃ , A ₅ and A ₆ are each independently a hydrogen atom, aromatic residue, aliphatic hydrocarbon residue, cyano group, halogen atom, carbonamido group, amide group, alkoxy group, Represents an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group or an acyl group;
Examples of the aromatic residue represented by A ₁ , A ₂ , A ₃ , A ₅ and A ₆ include the same aromatic residues as those represented by X ₁ and Y _{1 in} the formula (1).
As the aliphatic hydrocarbon residue, halogen atom, amide group, alkoxy group, aryloxy group, alkoxycarbonyl group, arylcarbonyl group and acyl group represented by A ₁ , A ₂ , A ₃ , A ₅ and A ₆ , (1) X ₁ and Y aromatic _{residues 1} represents of may be the same as those described in the section of the substituent which may have.
The aromatic residue, aliphatic hydrocarbon residue, amide group, alkoxy group, aryloxy group, alkoxycarbonyl group, arylcarbonyl group and acyl group represented by A ₁ , A ₂ , A ₃ , A ₅ and A ₆ are substituted. The substituent may have a group, and as the substituent, those described in the section of the substituent that the aromatic residue and the aliphatic hydrocarbon residue represented by R _{11 in} the formula (1) may have The same thing is mentioned.

When at least one of l and n in formula (1) is 2 or more and a plurality of any of A ₂ , A ₃ , A ₅ and A ₆ are present, each of A ₂ , A ₃ , A ₅ and A ₆ may be the same or different from each other.
When l is other than 0, at least two selected from A ₁ , A ₂ and A ₃ may be bonded to form a ring.
Examples of the ring formed by A ₁ , A ₂ and A ₃ include an unsaturated hydrocarbon ring or a heterocyclic ring.
Examples of the unsaturated hydrocarbon ring include benzene, naphthalene, anthracene, phenanthrene, pyrene, indene, azulene, fluorene, cyclobutene, cyclohexene, cyclopentene, cyclohexadiene, cyclopentadiene, etc. Examples include pyran, pyridine, pyrazine, piperidine, indoline, oxazole, thiazole, thiadiazole, oxadiazole, indole, benzothiazole, benzoxazole, quinoline, carbazole, benzopyran and the like. Of these, benzene, cyclobutene, cyclopentene, and cyclohexene are preferable.
These unsaturated hydrocarbon rings and heterocyclic rings may have a substituent, and the substituent has an aromatic residue and an aliphatic hydrocarbon residue represented by R _{11 in the} formula (1). And the same as those described in the section of the substituent which may be used.

When the heterocyclic ring formed by at least two selected from A ₁ , A ₂ and A ₃ has a substituent such as a carbonyl group or a thiocarbonyl group, these substituents are cyclic ketones or cyclic thioketones, etc. These rings may further have a substituent. Examples of the substituent in that case include the same substituents as those described in the section of the substituent that the aromatic residue and the aliphatic hydrocarbon residue represented by R ₁₁ in the formula (1) may have.
Among them, A ₁ , A ₂ , A ₃ , A ₅ and A ₆ in the formula (1) are each independently preferably a hydrogen atom or an aliphatic hydrocarbon residue, and more preferably a hydrogen atom.

A ₄ in Formula (1) represents a hydrogen atom, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carbonamido group, an alkoxy group, an amide group, an alkoxycarbonyl group, or an acyl group.
As the aliphatic hydrocarbon residue, halogen atom, alkoxy group, amide group, alkoxycarbonyl group and acyl group represented by A _{4, the} aromatic residue represented by X ₁ and Y ₁ in formula (1) has And the same as those described in the section of the good substituent.
The aliphatic hydrocarbon residue, alkoxy group, amide group, alkoxycarbonyl group acyl group represented by A ₄ may have a substituent, and the substituent is an aromatic represented by R _{11 in} formula (1). The same thing as what was mentioned in the term of the substituent which the residue and an aliphatic hydrocarbon residue may have is mentioned.
When m is 2 or more and a plurality of A ₄ are present, each A ₄ may be the same as or different from each other.
A ₄ in Formula (1) is preferably a hydrogen atom or an aliphatic hydrocarbon residue, and more preferably a hydrogen atom.

A ₇ and A ₈ in Formula (1) each independently represent a hydrogen atom, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carbonamido group, an alkoxy group, an alkoxycarbonyl group, or an acyl group.
As the aliphatic hydrocarbon residue, halogen atom, alkoxy group, alkoxycarbonyl group and acyl group represented by A ₇ and A _{8, the} aromatic residue represented by X ₁ and Y ₁ in formula (1) has And the same as those described in the section of the good substituent.
The aliphatic hydrocarbon residue, alkoxy group, alkoxycarbonyl group and acyl group represented by A ₇ and A ₈ may have a substituent, and examples of the substituent include an aromatic group represented by R _{11 in} formula (1). The same thing as what was mentioned in the term of the substituent which a group residue and an aliphatic hydrocarbon residue may have is mentioned.
When j in formula (1) is A ₇ and A ₈ there are multiple with 2 or more, each A ₇ and A ₈ may be the same or different from each other.
A ₇ and A ₈ in Formula (1) are each independently preferably a hydrogen atom or an aliphatic hydrocarbon residue, and more preferably a hydrogen atom.

R ₁ in the formula (1) is the following formula (3002)

Represents a group represented by
P in the formula (3002) represents an integer of 1 to 3, and preferably 1 to 2. Further, it is particularly preferable that p and the aforementioned j are the same integer.
Q in the formula (3002) represents an integer of 0 to 6, and is preferably 0. Moreover, it is particularly preferable that q and the aforementioned l are the same integer.
That is, it is most preferable that p and j are the same integer, and q and l are the same integer.
X ₂ and Y ₂ in formula (3002) each independently represent a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a carboxyl group, a phosphate group, a sulfonic acid group, a cyano group, an acyl group, an amide group, It represents an alkoxycarbonyl group or a sulfonylbenzene group, and these definitions and preferred ones are the same as those for X ₁ and Y ₁ in the above formula (1).
When X ₂ and Y ₂ are bonded to form a ring structure represented by the above formulas (2001) to (2044), the * mark in the formulas (2001) to (2044) is the same as that in the formula (3002). A carbon atom to which X ₂ and Y ₂ are bonded is shown.

Z ₄ in the formula (3002) represents an oxygen atom, a sulfur atom, a selenium atom or NR ₁₂ , and R ₁₂ represents a hydrogen atom, an aromatic residue or an aliphatic hydrocarbon residue. The definitions and preferred examples of the aromatic residue and aliphatic hydrocarbon residue represented by R ₁₂ are the same as those described in the section of R _{11 in} formula (1), and the definition and preferred examples of Z ₄ are those of the formula This is the same as described in the Z ₁ and Z ₂ terms of (1).
A ₁₁ and A ₁₂ in formula (3002) each independently represent a hydrogen atom, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carbonamido group, an alkoxy group, an alkoxycarbonyl group, or an acyl group, and these definitions The preferable ones are the same as those described in the paragraphs A ₇ and A _{8 in} the formula (1).
A ₁₃ , A ₁₄ and A ₁₅ in formula (3002) are each independently a hydrogen atom, aromatic residue, aliphatic hydrocarbon residue, cyano group, halogen atom, carbonamido group, amide group, alkoxy group, aryl Represents an oxy group, an alkoxycarbonyl group, an arylcarbonyl group or an acyl group, and these definitions and preferred ones are those described in the paragraphs A ₁ , A ₂ , A ₃ , A ₅ and A ₆ of the formula (1). It is the same.
When m is 2 or more and a plurality of R ₁ are present, each R ₁ may be the same as or different from each other.
R ₂ in the formula (1) is the following formula (3001) or (3003)

Represents a hydrogen atom or an aliphatic hydrocarbon group.
In formula (3001) or (3003), R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ each independently represent a hydrogen atom, an aromatic residue or an aliphatic hydrocarbon residue. R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ are each independently a hydrogen atom, aromatic residue, aliphatic hydrocarbon residue, cyano group, acyl group, amide group, alkoxy group, alkoxycarbonyl group or sulfonylbenzene group. Represent.
Examples of the aromatic residue represented by R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ are the same as those described in the section of the aromatic residue represented by X ₁ and Y _{1 in} the formula (1).
As the aliphatic hydrocarbon residue represented by R ₁₂ , R ₁₃ , R ₁₄ and R _15, an aromatic residue represented by X ₁ and Y _{1 in} the formula (1) may be substituted. The same thing as the aliphatic hydrocarbon residue mentioned is mentioned.

The aromatic residue and aliphatic hydrocarbon residue represented by R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ may have a substituent, and the substituent is represented by R _{11 in the} formula (1). The same thing as what was mentioned in the term of the substituent which an aromatic residue and an aliphatic hydrocarbon residue may have is mentioned.
R ₁₂ and R ₁₃ in the formula (3001) are preferably each independently a hydrogen atom or an aliphatic hydrocarbon residue, more preferably each independently a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. Preferably, it is a C1-C8 alkyl group, and it is especially preferable that it is a C1-C8 linear alkyl group.
R ₁₄ and R ₁₅ in formula (3003) are preferably each independently an aromatic residue, more preferably each independently a phenyl group or a group represented by formula (3001). More preferably, they are the same phenyl group or the same group represented by the same formula (3001). R ₁₂ and R ₁₃ in the group represented by the formula (3001) represented by R ₁₄ and R ₁₅ are the same as those described above, and preferable ones are also the same as described above.

Examples of the aromatic residue represented by R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ are the same as those described in the section of the aromatic residue represented by X ₁ and Y _{1 in} the formula (1).
Examples of the aliphatic hydrocarbon residue, acyl group, amide group, alkoxy group and alkoxycarbonyl group represented by R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ include aromatic residues represented by X ₁ and Y _{1 in} the formula (1). The same thing as what was mentioned in the term of the substituent which group may have is mentioned.
The aromatic residue, aliphatic hydrocarbon residue, acyl group, amide group, alkoxy group, alkoxycarbonyl group and sulfonylbenzene group represented by R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ may have a substituent. Well, examples of the substituent include the same as those described in the section of the substituent that the aromatic residue and the aliphatic hydrocarbon residue represented by R ₁₁ in the formula (1) may have.
R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ in formula (3003) are each independently preferably a hydrogen atom or an alkoxy group, more preferably a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms. And more preferably a hydrogen atom.

As the group represented by the formula (3001), R ₁₂ and R ₁₃ are preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ₁₂ and R ₁₃ are an alkyl group having 1 to 8 carbon atoms. It is more preferable.
As the group represented by the formula (3003), R ₁₄ and R ₁₅ are a phenyl group or a group represented by the formula (3001), and R ₁₂ and R ₁₃ in the formula (3001) are a hydrogen atom or a carbon number. It is preferably an alkyl group having 1 to 8 and R _{16 to} R ₁₉ are each independently a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms, R ₁₄ and R ₁₅ are phenyl groups, and More preferably, R _{16 to} R ₁₉ are hydrogen atoms.
More specifically, the group represented by the formula (3001) or (3003) is preferably a group represented by any of the following formulas (3101) to (3114). ), (3103), (3107), (3108), (3110), (3111), (3113) or (3114), more preferably a group represented by the following formulas (3103), (3107) Or it is more preferable that it is group represented by (3111), and it is especially preferable that it is group represented by following formula (3103) or (3107).

Examples of the aliphatic hydrocarbon residue represented by R ₂ include the aliphatic hydrocarbon residues described in the section of the substituent that the aromatic residue represented by X ₁ and Y ₁ in Formula (1) may have, The same can be mentioned.
When n is other than 0, at least two selected from A ₅ , A ₆ and R ₂ may be bonded to form a ring.
The ring formed by A ₅ , A ₆ and R ₂ may have a substituent, and examples of the substituent include an aromatic residue and an aliphatic hydrocarbon residue represented by R _{11 in} formula (1). Examples thereof are the same as those described in the section of the substituent which may be included.

R ₂ in Formula (1) is a group represented by Formula (3001), and R ₁₂ and R ₁₃ are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, or Formula (3003) R ₁₄ and R ₁₅ are a phenyl group or a group represented by the formula (3001), and R ₁₂ and R ₁₃ are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R _{16 to} R ₁₉ are more preferably each independently a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms.
Further, a group represented by the formula (3003), an R ₁₄ and R ₁₅ is a phenyl group, and R ₁₆ to R ₁₉ is each independently a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms Or a group represented by formula (3003), wherein R ₁₄ and R ₁₅ are groups represented by formula (3001), and R ₁₂ and R ₁₃ are a hydrogen atom or a group having 1 to 8 carbon atoms. More preferably, it is an alkyl group, and R _{16 to} R ₁₉ are each independently a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms.
More specifically, it is preferably a group represented by any one of the above formulas (3101) to (3114), and the above formulas (3102), (3103), (3107), (3108), (3110) , (3111), (3113) or (3114) is more preferable, and a group represented by the formula (3103), (3107) or (3111) is more preferable. A group represented by formula (3107) or (3111) is particularly preferable.

  When the methine 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 may form a salt. A salt with an alkali metal such as lithium, sodium or potassium, or an alkaline earth metal such as magnesium or calcium, or an organic base such as tetramethylammonium, tetrabutylammonium, pyridinium, imidazolium, piperazinium or piperidinium Mention may be made of salts such as ammonium salts.

  The methine dye represented by the formula (1) can take a structural isomer such as a cis isomer, a trans isomer, a racemate and the like, but is not particularly limited, and any isomer is used as a photosensitizing dye in the present invention. It can be used satisfactorily.

Preferred combinations of m, l, n, j, p, q, X _{1 to} X ₂ , Y _{1 to} Y ₂ , Z _{1 to} Z ₄ , A _{1 to} A ₁₅ and R _{1 to} R ₂ in formula (1) are , M, l, n, j, p, q, X _{1 to} X ₂ , Y _{1 to} Y ₂ , Z _{1 to} Z ₄ , A _{1 to} A ₁₅ and R _{1 to} R _2. It is a combination of those, and a more preferable combination is as follows.
That is, as a preferable combination, m is 1 to 3, l, n, and q are 0, j is 1 to 3, p is 1 to 3, and Z _{1 to} Z ₄ are each independently An oxygen atom, a sulfur atom, a selenium atom, an amino group, an N-methylamino group, or an N-phenylamino group, and R ₂ is a group represented by any one of the above formulas (3101) to (3114); ₁ and Y ₁ are each independently a carboxyl group, a phosphate group, a cyano group, or an acyl group, or one of X ₁ and Y ₁ is a group represented by the above formulas (1001) to (1033), and the other is is a hydrogen atom or a cyano group, or forms a ring with X ₁ and Y _1, the ring is a group selected from the group consisting of groups represented by the formula (2001) ~ (2044), X 2 and Y ₂ are each independently a carboxyl group, a phosphoric acid Or a cyano group or an acyl group, or one of X ₁ and Y ₁ is a group represented by the formula (1001) - (1033), and the other is hydrogen atom or a cyano group, or X ₂ and Y ₂ forms a ring, and the ring is a group selected from the group consisting of the above formulas (2001) to (2044), and A _{1 to} A ₁₅ are each independently a hydrogen atom, chlorine atom, cyano. Group or an alkyl group having 1 to 36 carbon atoms.

As a particularly preferred combination, m is 1 to 3, l, n and q are 0, j is 1 to 3, p is 1 to 3, and Z _{1 to} Z ₄ are each independently oxygen. An atom, a sulfur atom or a selenium atom; R ₂ is a group represented by any one of the above formulas (3103), (3107) or (3111); one of X ₁ and Y ₁ is a carboxyl group and the other Is a carboxyl group, a cyano group or an acyl group, or the ring formed by combining X ₁ and Y ₁ is a group represented by the above formula (2007), and one of X ₂ and Y ₂ is a carboxyl group And the other is a carboxyl group, a cyano group or an acyl group, or the ring formed by combining X ₂ and Y ₂ is a group represented by the above formula (2007), and A _{1 to} A ₁₅ are each Independently hydrogen atom, chlorine atom, cyano group or carbon number 1 8 or an alkyl group.
The most preferable combination is that m is 1 to 2, l, n, and q are 0, j is 1 to 2, p is 1 to 2, and Z _{1 to} Z ₄ are sulfur atoms. R ₂ is a group represented by the above formula (3107) or (3111), _one of X ₁ and Y ₁ is a carboxyl group and the other is a cyano group, or X ₁ and Y ₁ are bonded. The ring formed is a group represented by the above formula (2007), and one of X ₂ and Y ₂ is a carboxyl group and the other is a cyano group, or X ₂ and Y ₂ are combined to form. The ring is a group represented by the above formula (2007), and A _{1 to} A ₁₅ are hydrogen atoms.

  As shown in the above formulas (1001) to (1017), (1019) and (1020), the counter ion for neutralizing the positive charge of the nitrogen atom may be formed either intermolecularly or intramolecularly. . Preferable counter ions between molecules include anions such as iodine, perchloric acid, bistrifluoromethylsulfonimide, tristrifluoromethylsulfonylmethane, hexafluoroantimonic acid, and tetrafluoroboric acid. Preferred counter ions in the molecule include anions such as 2-yl acetate, 3-yl propionate and sulfoethane-2-yl bonded to a positively charged nitrogen atom.

  The methine dye represented by the formula (1) can be produced by, for example, the following reaction formula, but the present invention is not limited to these synthesis methods. Compound (5) is obtained by reaction of compound (3) and boronic acids (4). Compound (5) is treated with N-iodosuccinimide to obtain compound (6). Then, the compound (6) and the boronic acid (7) are reacted to derive the compound (8), and further, the carbonyl compound (10) is obtained by the reaction with the boronic acid (9). If necessary, a base such as caustic soda, sodium methylate, sodium acetate, diethylamine, triethylamine, piperidine, piperazine, diazabicycloundecene, etc., if this compound (10) and the compound having active methylene represented by formula (11) are required 20 ° C to 180 ° C in an aprotic polar solvent such as alcohols such as methanol, ethanol, isopropanol and butanol, dimethylformamide and N-methylpyrrolidone, and solvents such as toluene, acetic anhydride and acetonitrile. Is condensed at 50 ° C. to 150 ° C. to obtain a methine compound (dye) represented by the formula (1). In the above reaction, when the compound (11) having active methylene has an ester group, it is also possible to obtain a carboxylic acid form by hydrolysis or the like after the condensation reaction.

  In particular, in the case of a methine dye having l = 0 in the formula (1), the reaction between the compound (3) and the boronic acids (4) is not performed, and the following compound (5) is used instead of the compound (5). It can be synthesized in the same way using ').

In particular, in the formula (1), when n = 0 and R ₂ is a methine dye having a hydrogen atom or an aliphatic hydrocarbon residue, the following compound (3 ′) is used instead of the compound (3): ) Can be used to synthesize the compound (5 ″), and the corresponding compound (1) can be synthesized by using the compound (5 ″) instead of the compound (8). it can.

Specific examples of methine dyes represented by formula (1-1) (methine dyes in which l, n, and q in formula (1) are 0) are shown in Tables 1 to 7. In each table, Ph means a phenyl group. Those described as (1001) to (1033) correspond to the above formulas (1001) to (1033). Those expressed as (2001) to (2044) represent a ring formed by combining X ₁ and Y ₁ and / or X ₂ and Y ₂ , and in the above formulas (2001) to (2044), Correspond. Also, the notations (3101) to (3114) correspond to the above formulas (3101) to (3114).

In formula (1-1), R ₁ represents the following formula (3002-1).

Methine dye represented by the following formula (1-2) (methine in which A ₁ , A ₂ , A ₃ , A ₁₃ and A ₁₄ in formula (1) are hydrogen atoms, and l and q are 1 Specific examples of the pigments are shown in Tables 8 to 20. In each table, Ph means a phenyl group. The substituents expressed as (1001) to (1033) correspond to the above formulas (1001) to (1033). The substituents represented by (2001) to (2044) represent a ring formed by combining X ₁ and Y ₁ and / or X ₂ and Y _2, and correspond to the above formulas (2001) to (2044). Also, the notations (3101) to (3114) correspond to the above formulas (3101) to (3114).

In formula (1-2), R ₁ represents the following formula (3002-2).

In the photoelectric conversion element of the present invention, for example, a thin film of oxide semiconductor fine particles is provided on a substrate using oxide semiconductor fine particles, and then the dye represented by the formula (1) is supported on the thin film.
As a substrate on which a thin film of oxide semiconductor fine particles is provided, a substrate having a conductive surface is preferable, but such a substrate is easily available in the market. For example, conductive metal oxides such as tin oxide doped with indium, fluorine and antimony on the surface of transparent polymer materials such as glass or polyethylene terephthalate or polyether sulfone, and metals such as copper, silver and gold A substrate provided with a thin film can be used as the substrate. The conductivity is usually 1000Ω or less, and particularly preferably 100Ω or less.
The oxide semiconductor fine particles are preferably metal oxides, and specific examples thereof include oxides of titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum, vanadium, and the like. Of these, oxides such as titanium, tin, zinc, niobium or indium are preferred, and titanium oxide, zinc oxide and tin oxide are most preferred. These oxide semiconductors can be used alone, but can also be used by mixing or coating the surface of the semiconductor. The average particle size of the oxide semiconductor fine particles is usually 1 to 500 nm, preferably 1 to 100 nm. The oxide semiconductor fine particles may be mixed with a large particle size and a small particle size, or may be used in multiple layers.

  The thin film of oxide semiconductor fine particles is a method of directly forming oxide semiconductor fine particles as a thin film of semiconductor fine particles on the substrate by spray spraying, a method of electrically depositing semiconductor fine particles into a thin film using the substrate as an electrode, It can be produced by applying a paste containing fine particles obtained by hydrolyzing a precursor of semiconductor fine particles such as slurry or semiconductor alkoxide on a substrate, followed by drying, curing or baking. In view of the performance of the electrode using an oxide semiconductor, a method using a slurry is preferable. In the case of this method, the slurry is obtained by dispersing the 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 may be anything as long as it can disperse the semiconductor fine particles. Water, alcohols such as ethanol, ketones such as acetone and acetylacetone, hydrocarbons such as hexane, and the like are used. In addition, the use of water is preferable in that the viscosity change of the slurry is reduced. A dispersion stabilizer can be used 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, and nitric acid, and organic solvents such as acetylacetone, acrylic acid, polyethylene glycol, and polyvinyl alcohol.

  The substrate coated with the slurry may be fired, and the firing temperature is usually 100 ° C. or higher, preferably 200 ° C. or higher, and the upper limit is generally lower than the melting point (softening point) of the substrate material. Yes, preferably 600 ° C. or lower. The firing time is not particularly limited but is preferably within 4 hours. The thickness of the thin film on a board | substrate is 1-200 micrometers normally, Preferably it is 1-50 micrometers.

  A secondary treatment may be applied to the thin film of oxide semiconductor fine particles. That is, improving the performance of the thin film of semiconductor fine particles by, for example, immersing the thin film together with the substrate directly in a solution of the same metal alkoxide, chloride, nitride, sulfide, etc. as the semiconductor and drying or refiring. You can also. Examples of the metal alkoxide include titanium ethoxide, titanium isopropoxide, titanium t-butoxide, n-dibutyl-diacetyltin, and alcohol solutions thereof are used. Examples of the chloride include titanium tetrachloride, tin tetrachloride, zinc chloride and the like, and an aqueous solution thereof is used. The oxide semiconductor thin film thus obtained is composed of fine particles of an oxide semiconductor.

Next, a method for supporting a methine 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 methine dye represented by the formula (1), a solution obtained by dissolving the dye in a solvent capable of dissolving the dye or a dye having low solubility is dispersed. A method of immersing the substrate provided with the thin film of oxide semiconductor fine particles in the dispersion obtained by caking is exemplified. The concentration in the solution or dispersion is appropriately determined depending on the dye. A thin film of semiconductor fine particles formed on the substrate is immersed in the solution or dispersion. The immersion temperature is generally from room temperature to the boiling point of the solvent, and the immersion time is about 1 minute to 48 hours. Specific examples of solvents that can be used to dissolve the dye include, for example, methanol, ethanol, isopropanol, tetrahydrofuran (THF), acetonitrile, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), acetone, n-butanol, t- Examples include butanol, water, n-hexane, chloroform, dichloromethane, toluene, and the like, and can be used alone or in combination according to the solubility of the dye. The dye concentration of the solution is usually 1 × 10 ⁻⁶ M to 1M, and preferably 1 × 10 ⁻⁵ M to ¹ × 10 ⁻¹ M.
After the immersion, the solvent is removed by air drying or heating if necessary. Thus, the photoelectric conversion element of the present invention having a thin film of oxide semiconductor fine particles sensitized with the methine dye represented by the formula (1) is obtained.

  The methine dye represented by the formula (1) to be carried may be one kind or a mixture of several kinds. Moreover, when mixing, the methine pigment | dye represented by Formula (1) of this invention may be sufficient, and another pigment | dye and a metal complex pigment | dye may be mixed. In particular, by mixing dyes having different absorption wavelengths, a wide absorption wavelength can be used, and a solar cell with high conversion efficiency can be obtained. Examples of metal complex dyes that can be mixed are not particularly limited, but ruthenium complexes and their quaternary ammonium salt compounds, phthalocyanines, porphyrins, and the like shown in Non-Patent Document 2 are preferable, and there are no organic dyes that are mixed and used. Metallic phthalocyanine, porphyrin, cyanine, merocyanine, oxonol, triphenylmethane, methine dyes such as acrylic acid dyes shown in Patent Document 2, dyes such as xanthene, azo, anthraquinone, and perylene Can be mentioned. Preferably, a ruthenium complex, a merocyanine, an acrylic acid-based methine dye, or the like is used. When two or more dyes are used, the dyes may be adsorbed sequentially on the thin film of semiconductor fine particles, or may be admixed and dissolved.

  The ratio of the dye to be mixed is not particularly limited, and the optimization condition is appropriately selected for each dye. Generally, it is preferable to use about 10% mol or more per one dye from the mixing of equimolar amounts. . When a dye is adsorbed to a thin film of oxide semiconductor fine particles using a solution in which two or more kinds of dyes are dissolved or dispersed, the total concentration of the dye in the solution may be the same as when only one kind is supported. As the solvent in the case of using a mixture of dyes, the above-mentioned solvents can be used, and the solvents for the respective dyes to be used may be the same or different.

  When the dye is supported on the thin film of oxide semiconductor fine particles, it is advantageous to support the dye in the presence of an inclusion compound in order to prevent association between the dyes. Examples of inclusion compounds include steroidal compounds such as cholic acid, crown ethers, cyclodextrins, calixarene, polyethylene oxide, and the like. Specific examples of preferable compounds include deoxycholic acid, dehydrodeoxycholic acid, chenodeoxycholic acid, and cholic acid. And cholic acids such as acid methyl ester and sodium cholate, and polyethylene oxide. Further, after the dye is supported, the semiconductor fine particle thin film 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 semiconductor fine particles carrying a dye in an ethanol solution of amine is employed.

  The solar cell of the present invention comprises a photoelectric conversion element in which a dye is supported on a thin film of oxide semiconductor fine particles as one electrode, and is composed of a counter electrode, a redox electrolyte, a hole transport material, a p-type semiconductor, or the like. As the form of the redox electrolyte, the hole transport material, the p-type semiconductor, etc., those known per se such as liquid, solidified body (gel and gel) and solid can be used. Liquids such as redox electrolytes, molten salts, hole transport materials, p-type semiconductors, etc., dissolved in solvents and room temperature molten salts are solidified (gels and gels). Examples include a matrix and a low molecular gelling agent. As a solid material, a redox electrolyte, a molten salt, a hole transport material, a p-type semiconductor, or the like can be used. Examples of the hole transport material include amine derivatives, conductive polymers such as polyacetylene, polyaniline, and polythiophene, and triphenylene compounds. Examples of the p-type semiconductor include CuI and CuSCN. The counter electrode is preferably conductive and has a catalytic action on the reduction reaction of the redox electrolyte. For example, a glass or polymer film deposited with platinum, carbon, rhodium, ruthenium or the like, or a film coated with conductive fine particles can be used.

The redox electrolyte used in the solar cell of the present invention is a halogen redox electrolyte composed of a halogen compound and a halogen molecule as a counter ion, ferrocyanate-ferricyanate, ferrocene-ferricinium ion, cobalt complex, etc. Metal redox electrolytes such as metal complexes, and 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 iodine molecule and bromine molecule, and iodine molecule is preferable. The above, as the halogen compound to halide ions 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 Examples include halogen organic quaternary ammonium salts such as imidazolium iodide and pyridinium iodide, and salts having iodine ions as counter ions are preferred. Moreover, it is also preferable to use the electrolyte which uses imide ions, such as a bis (trifluoromethanesulfonyl) imide ion and a dicyano imide ion, as a counter ion other than the said iodine ion.

  When the redox electrolyte is constituted in the form of a solution containing the redox electrolyte, an electrochemically inert solvent is used as the solvent. For example, acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxypropionitrile, methoxyacetonitrile, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, γ-butyrolactone, dimethoxyethane, diethyl carbonate, diethyl ether, diethyl carbonate, dimethyl carbonate, 1,2-dimethoxyethane, dimethylformamide, dimethyl sulfoxide, 1,3-dioxolane, methyl formate, 2-methyltetrahydrofuran, 3-methyl-oxazolidin-2-one, sulfolane, tetrahydrofuran, water and the like. Among these, in particular, acetonitrile, propylene carbonate, ethylene carbonate, 3-methoxypropylene Nitrile, 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 of a gel electrolyte, examples include those in which an electrolyte or an electrolyte solution is contained in a matrix such as an oligomer and a polymer, and those in which a low-molecular gelling agent or the like is similarly contained in an electrolyte or an electrolyte solution. The density | concentration of a redox electrolyte is 0.01-99 mass% normally, Preferably it is about 0.1-90 mass%.

  In the solar cell of the present invention, the counter electrode is disposed so as to sandwich the electrode of the photoelectric conversion element carrying the methine dye represented by the formula (1) of the present invention on the thin film of oxide semiconductor fine particles on the substrate. To do. In the meantime, it is obtained by filling a solution containing a redox electrolyte.

  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. M representing the concentration of the solution represents mol / L. Moreover, a compound number is a compound number in the said specific example. The maximum absorption wavelength was measured with an ultraviolet-visible spectrophotometer (UV-3100PC, manufactured by Shimadzu Corporation). Nuclear magnetic resonance was measured by JNM-ECS400 (manufactured by JEOL Ltd.).

Synthesis example 1
20 parts 2,3-dibromothiophene, 31 parts 5-formyl-2-thiopheneboronic acid, 1.7 parts bis (tri-tert-butylphosphine) palladium (0), 50 parts cesium fluoride, 112 parts water , 4-Dioxane was added to 516 parts and reacted at 80 ° C. for 3 hours. The reaction mixture was extracted with chloroform-water, the chloroform phase was concentrated, separated and purified by column chromatography (chloroform-hexane), and 21 parts of a compound represented by the following formula (700) was obtained as a yellow solid.

Synthesis example 2
To a solution obtained by dissolving 10 parts of the compound represented by the formula (700) obtained in Synthesis Example 1 in a mixed solution of 210 parts of acetic acid and 296 parts of chloroform, 9 parts of N-iodosuccinimide is added, and light-shielded at 100 ° C. For 5 hours. The reaction mixture was extracted with chloroform-water, the chloroform phase was concentrated, separated and purified by column chromatography (chloroform-hexane), and 13 parts of a compound represented by the following formula (701) were obtained as a dark yellow solid.

Synthesis example 3
1.6 parts of [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II) · dichloromethane adduct, 2 parts of potassium acetate and 2 parts of bis (pinacolato) diboron are added to 22 parts of dimethyl sulfoxide and a nitrogen atmosphere. Stirred under. A solution prepared by dissolving 5 parts of 9,9-dibutyl-N- (9,9-dibutylfluoren-2-yl) -N- (4-iodophenyl) fluoren-2-amine in 66 parts of dimethyl sulfoxide was added. Stir at 5 ° C. for 5 hours. The reaction mixture was extracted with toluene-water, and the toluene phase was concentrated and then separated and purified by column chromatography (chloroform-hexane) to obtain 3.5 parts of a compound represented by the following formula (702) as a white solid.

Synthesis example 4
5.9 parts of the compound represented by the formula (701) obtained in Synthesis Example 2, 13 parts of the compound represented by the formula (702) obtained in Synthesis Example 3, tetrakis (triphenylphosphine) palladium (0) 0.47 parts and 49 parts of a 20% aqueous sodium carbonate solution were added to 373 parts of 1,2-dimethoxyethane and reacted for 7 hours under reflux. The reaction mixture was extracted with chloroform-water, the chloroform phase was concentrated, separated and purified by column chromatography (chloroform-hexane), and 9.3 parts of a compound represented by the following formula (703) was obtained as a red solid.

Example 1
In a solution obtained by dissolving 9.3 parts of the compound represented by the formula (703) obtained in Synthesis Example 4 and 5.0 parts of cyanoacetic acid in a mixed solution of 526 parts of ethanol and 289 parts of toluene, 0.02 part of anhydrous piperazine And reacted under reflux for 6 hours. 5.0 parts of cyanoacetic acid and 0.02 part of anhydrous piperazine were added, and the mixture was further reacted for 7 hours under reflux. The reaction mixture was extracted with chloroform-water, the chloroform phase was concentrated, and then separated and purified by column chromatography (chloroform-methanol). The reddish brown solid obtained after concentration was recrystallized from chloroform-hexane to obtain 3.1 parts of a compound represented by the following formula (705) (compound 1 in Table 1) as a reddish brown solid.
The maximum absorption wavelength of the compound represented by the formula (705) and the measured values of the nuclear magnetic resonance apparatus were as follows.
Maximum absorption wavelength; λmax = 368 nm (1.6 × 10 ⁻⁵ M, tetrahydrofuran solution)
Measurement value of nuclear magnetic resonance: ¹ H-NMR (PPM: DMSO-d6): 0.53 (m.8H), 0.60 (t.12H), 0.96 (m.8H),
1.84 (m.8H), 7.00 (d.2H), 7.02 (dd.2H), 7.16 (d.2H), 7.25 (m.4H), 7.33 (d.1H), 7.37 (dd.2H), 7.42 (d.1H), 7.62 (d.2H), 7.68 (s.1H), 7.69 (d.2H), 7.72 (d.2H), 7.78 (d.1H), 7.82 (d.1H), 8.22 ( s, 1H), 8.23 (s, 1H)

Synthesis Example 6
2,3-dibromothiophene 5 parts, 5'-formyl-2,2'-bithiophene-5-boronic acid 5.5 parts, bis (tri-tert-butylphosphine) palladium (0) 0.22 parts, fluoride Cesium (6.4 parts) and water (28 parts) were added to 1,4-dioxane (126 parts) and reacted at 80 ° C. for 3 hours. The reaction mixture was extracted with chloroform-water, the chloroform phase was concentrated, separated and purified by column chromatography (chloroform-hexane), and 2.8 parts of a compound represented by the following formula (706) was obtained as a yellow solid.

Synthesis example 7
To a solution obtained by dissolving 2.5 parts of the compound represented by the formula (706) obtained in Synthesis Example 6 in a mixed solution of 250 parts of acetic acid and 375 parts of chloroform, 1.6 parts of N-iodosuccinimide is added, The mixture was stirred for 5 hours at room temperature under light shielding. 0.8 part of N-iodosuccinimide was added, and the mixture was further stirred at room temperature for 19 hours under light shielding. After the reaction, the precipitate was filtered and washed with hexane to obtain 2.9 parts of a compound represented by the following formula (707) as a pale orange solid.

Synthesis Example 8
2.1 parts of the compound represented by the formula (707) obtained in Synthesis Example 7, 4.1 parts of the compound represented by the formula (702) obtained in Synthesis Example 3, tetrakis (triphenylphosphine) palladium ( 0) 0.15 part and 16 parts of a 20% aqueous sodium carbonate solution were added to 300 parts of 1,2-dimethoxyethane and reacted for 4 hours under reflux. 2.0 parts of the compound represented by the formula (702) and 0.08 part of tetrakis (triphenylphosphine) palladium (0) were added, and the mixture was further reacted for 3 hours under reflux. The reaction mixture was extracted with chloroform-water, the chloroform phase was concentrated, separated and purified by column chromatography (chloroform-hexane and toluene-hexane), and 1.2 parts of the compound represented by the following formula (708) was concentrated. Obtained as an orange solid.

Synthesis Example 9
0.43 part of the compound represented by the formula (708) obtained in Synthesis Example 8 and 0.16 part of 5′-formyl-2,2′-bithiophene-5-boronic acid, bis (tri-tert-butylphosphine) ) 0.004 part of palladium (0), 0.13 part of cesium fluoride and 0.6 part of water were added to 8 parts of 1,4-dioxane and reacted at 80 ° C. for 3 hours. The reaction mixture was extracted with chloroform-water, the chloroform phase was concentrated, separated and purified by column chromatography (chloroform-hexane), and 0.36 parts of a compound represented by the following formula (709) was obtained as a vermilion solid.

Example 2
0.36 parts of the compound represented by the formula (709) obtained in Synthesis Example 9 and 162 parts of cyanoacetic acid are dissolved in 67 parts of an ethanol-toluene (2: 1) mixed solution, and 0.01 part of anhydrous piperazine is added. And reacted for 5 hours under reflux. The reaction mixture was extracted with toluene-water, the toluene phase was concentrated, and then separated and purified by column chromatography (chloroform-acetic acid). The dark red solid obtained after the concentration was recrystallized from chloroform-hexane to obtain 0.12 part of a compound represented by the following formula (710) (compound 249 of Table 5) as a dark red solid.
The maximum absorption wavelength of the compound represented by the formula (710) and the measured values of the nuclear magnetic resonance apparatus were as follows.
Maximum absorption wavelength; λmax = 368 nm (1.6 × 10 ⁻⁵ M, tetrahydrofuran solution)
Measurement value of nuclear magnetic resonance: ¹ H-NMR (PPM: DMSO-d6): 0.56 (m.8H), 0.66 (t.12H), 1.02 (m.8H),
1.89 (m.8H), 7.05 (d.2H), 7.07 (dd.2H), 7.21 (d.2H), 7.31 (m.6H), 7.42 (m.4H), 7.46 (m.2H), 7.64 (m.4H), 7.69 (s.1H), 7.74 (d.2H), 7.76 (d.2H), 8.01 (s.2H)

Synthesis Example 10
0.87 part of the compound represented by the formula (708) obtained in Synthesis Example 8, 0.34 part of 5-formyl-2-thiopheneboronic acid, bis (tri-tert-butylphosphine) palladium (0) 0. 017 parts, 0.53 parts of cesium fluoride and 0.07 parts of water were added to 13 parts of 1,4-dioxane and reacted at 80 ° C. for 4 hours. 0.34 part of 5-formyl-2-thiopheneboronic acid and 0.017 part of bis (tri-tert-butylphosphine) palladium (0) were added and reacted at 80 ° C. for 2 hours. Further, 0.34 part of 5-formyl-2-thiopheneboronic acid and 0.017 part of bis (tri-tert-butylphosphine) palladium (0) were added and reacted at 80 ° C. for 5 hours. The reaction mixture was extracted with chloroform-water, the chloroform phase was concentrated, separated and purified by column chromatography (chloroform-hexane), and 0.70 part of a compound represented by the following formula (711) was obtained as a red-orange solid. .

Example 3
0.36 parts of the compound represented by the formula (711) obtained in Synthesis Example 10 and 162 parts of cyanoacetic acid are dissolved in 67 parts of an ethanol-toluene (2: 1) mixed solution, and 0.01 part of anhydrous piperazine is added. And reacted for 5 hours under reflux. The reaction mixture was extracted with toluene-water, the toluene phase was concentrated, and then separated and purified by column chromatography (chloroform-methanol). The dark red solid obtained after the concentration was recrystallized from chloroform-hexane to obtain 0.12 part of a compound represented by the following formula (712) (compound 125 of Table 3) as a dark red solid.
The maximum absorption wavelength of the compound represented by the formula (712) and the measured values of the nuclear magnetic resonance apparatus were as follows.
Maximum absorption wavelength; λmax = 369 nm (1.6 × 10 ⁻⁵ M, THF solution)
Measurement value of nuclear magnetic resonance: ¹ H-NMR (PPM: DMSO-d6): 0.57 (m.8H), 0.67 (t.12H), 1.01 (m.8H),
1.89 (m.8H), 7.04 (d.2H), 7.06 (dd.2H), 7.20 (d.2H), 7.29 (m.5H), 7.41 (m.4H), 7.45 (d.1H), 7.65 (m.4H), 7.71 (d.1H), 7.74 (dd.2H), 7.76 (d.2H), 8.06 (s.1H), 8.07 (s.1H)

Examples 4-5 and Comparative Examples 1-2
1.6 × 10 ⁻⁴ M (3.2 × 10 ⁻⁴ M in Comparative Example 1) and the following cholic acid (formula (d)) of the methine dyes and comparative dyes having the compound numbers shown in Table 21 It was dissolved in acetone (tetrahydrofuran (THF) in Example 5) to 1 × 10 ⁻² M (4 × 10 ⁻² M in Example 5). In this solution, a porous substrate (a semiconductor thin film electrode obtained by sintering porous titanium oxide on a transparent conductive glass electrode for 30 minutes at 450 ° C. for 30 minutes) was immersed at 40 ° C. for 3 days to carry a dye, washed with a solvent, It was dried to obtain a dye sensitized semiconductor thin film treated with cholic acid. A conductive glass whose surface was sputtered with platinum was fixed so as to sandwich it, and a solution containing an electrolyte was injected into the gap. The electrolyte was 3-methoxypropionitrile, iodine / lithium iodide / 1-methyl-3-n-propylimidazolium iodide / guanidine thiocyanate, 0.1M / 0.2M / 1.2M / 0.05M, respectively. Or dissolved in 3-methoxypropionitrile with 0.1M / iodine of iodine / lithium iodide / 1-methyl-3-n-propylimidazolium iodide / butylthiocholine iodide, respectively. What (B) melt | dissolved so that it might become 0.2M / 1.2M / 0.2M was used.
The size of the battery to be measured was 12 cm ² at the effective part. The light durability test was performed at 1 SUN and 40 ° C. for 500 hours using a light resistance tester (ESC0405-F70, manufactured by Iwasaki Electric Co., Ltd.) with UV cut filters (UV400, manufactured by Bisou Co., Ltd.) on both surfaces of the battery. The photoelectric conversion characteristic was set to 100 mW / cm ² through an AM (atmosphere passing air amount) 1.5 filter using a 500 W xenon lamp as a light source. Short-circuit current, release voltage, and conversion efficiency were measured using a potentio galvanostat.

  The compound (160) described in International Patent Publication No. WO2007 / 100033 was defined as Compound No. C and evaluated as a comparative dye.

  From Table 21, it is clear that a solar cell excellent in light resistance can be obtained by using the photoelectric conversion element sensitized by the methine dye represented by the general formula (1).

In the dye-sensitized photoelectric conversion element of the present invention, a solar cell having high conversion efficiency and stability can be provided by using a dye having a specific partial structure.

Claims (21)

Methine dye represented by the following formula (1)

(In the formula (1), m represents an integer of 1 to 5, l and n each independently represents an integer of 0 to 6, and j represents an integer of 0 to 3, respectively.
X ₁ and Y ₁ are each independently a hydrogen atom, aromatic residue, aliphatic hydrocarbon residue, carboxyl group, phosphoric acid group, sulfonic acid group, cyano group, acyl group, amide group, alkoxycarbonyl group or sulfonylbenzene. Represents a group. X ₁ and Y ₁ may be bonded to form a ring.
Z ₁ and Z ₂ each independently represents an oxygen atom, a sulfur atom, a selenium atom or NR ₁₁ . R ₁₁ represents a hydrogen atom, an aromatic residue or an aliphatic hydrocarbon residue. at least one of m or j is 2 or more, if Z ₁ and / or Z ₂ there are a plurality, each of Z ₁ and / or Z ₂ may be the same or different from each other.
A ₁ , A ₂ , A ₃ , A ₅ and A ₆ are each independently a hydrogen atom, aromatic residue, aliphatic hydrocarbon residue, cyano group, halogen atom, carbonamido group, amide group, alkoxy group, aryl An oxy group, an alkoxycarbonyl group, an arylcarbonyl group or an acyl group is represented. Further, when at least one of l or n is 2 or more and any one of A ₂ , A ₃ , A ₅ and A ₆ is present, each of A ₂ , A ₃ , A ₅ and A ₆ is They may be the same or different from each other. When l is other than 0, any one of A ₁ , A ₂ and A ₃ may form a ring.
A ₄ represents a hydrogen atom, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carbonamido group, an alkoxy group, an amide group, an alkoxycarbonyl group or an acyl group. When m is 2 or more and a plurality of A ₄ are present, each A ₄ may be the same as or different from each other.
A ₇ and A ₈ each independently represents a hydrogen atom, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carbonamido group, an alkoxy group, an alkoxycarbonyl group or an acyl group. When j is 2 or more and a plurality of A ₇ and A ₈ exist, each A ₇ and A ₈ may be the same as or different from each other.
R ₁ is represented by the following formula (3002)

(In the formula (3002), p represents an integer of 1 to 3, and q represents an integer of 0 to 6, respectively.
X ₂ and Y ₂ are each independently a hydrogen atom, aromatic residue, aliphatic hydrocarbon residue, carboxyl group, phosphate group, sulfonate group, cyano group, acyl group, amide group, alkoxycarbonyl group or sulfonylbenzene. Represents a group. X ₂ and Y ₂ may combine to form a ring.
Z ₄ represents an oxygen atom, a sulfur atom, a selenium atom or NR ₁₂ . R ₁₂ represents a hydrogen atom, an aromatic residue or an aliphatic hydrocarbon residue. When p is 2 or more and a plurality of Z ₄ are present, each Z ₄ may be the same as or different from each other.
A ₁₁ and A ₁₂ each independently represent a hydrogen atom, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carbonamido group, an alkoxy group, an alkoxycarbonyl group or an acyl group. When p is 2 or more and a plurality of A ₁₁ and A ₁₂ are present, each A ₁₁ and A ₁₂ may be the same as or different from each other.
A ₁₃ , A ₁₄ and A ₁₅ are each independently a hydrogen atom, aromatic residue, aliphatic hydrocarbon residue, cyano group, halogen atom, carbonamido group, amide group, alkoxy group, aryloxy group, alkoxycarbonyl group Represents an arylcarbonyl group or an acyl group. In the case where q is A ₁₃ and A ₁₄ there are a plurality of two or more, each of A ₁₃ and A ₁₄ may be the same or different from each other. In addition, when q is other than 0, any one of A ₁₃ , A ₁₄ , and A ₁₅ may form a ring. )
Represents a group represented by When m is 2 or more and a plurality of R ₁ are present, each R ₁ may be the same as or different from each other.
R ₂ represents the following formula (3001) or (3003)

(In the formula (3001) or (3003), R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ each independently represent a hydrogen atom, an aromatic residue or an aliphatic hydrocarbon residue.
R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ are each independently a hydrogen atom, aromatic residue, aliphatic hydrocarbon residue, cyano group, acyl group, amide group, alkoxy group, alkoxycarbonyl group or sulfonylbenzene group. Represents. )
Represents a hydrogen atom or an aliphatic hydrocarbon residue. When n is other than 0, any one of A ₅ , A ₆ and R ₂ may form a ring. ). The methine dye according to claim 1, wherein l, n and q in formula (1) are 0. The methine dye according to claim 1, wherein m in the formula (1) is 1 to 3. The methine dye according to claim 1, wherein j in Formula (1) is 1 to 3. The methine dye according to claim 1, wherein Z _{1 to} Z ₄ in formula (1) are sulfur atoms. In formula (1), one of X ₁ and Y ₁ is a carboxyl group and the other is a carboxyl group, a cyano group or an acyl group, and / or one of X ₂ and Y ₂ is a carboxyl group and the other is a carboxyl group, a cyano group Or a methine dye according to claim 1, which is an acyl group. The methine according to claim 6, wherein one of X ₁ and Y ₁ in formula (1) is a carboxyl group and the other is a cyano group, and / or one of X ₂ and Y ₂ is a carboxyl group and the other is a cyano group. Pigments. In the formula (1), at least one of X ₁ and Y _{1 is} a substituent selected from the group consisting of a carboxyl group, a hydroxyl group, a phosphate group, a sulfonate group, and a salt of these acidic groups. And / or at least one group selected from the group consisting of a carboxyl group, a hydroxyl group, a phosphate group, a sulfonic acid group, and a salt of these acidic groups is at least one of X ₂ and Y ₂ The methine dye according to claim 1, which is an aromatic residue having one or more substituents. At least one of X ₁ and Y ₁ in the formula (1), and / or X ₂ and at least one of the following formula Y ₂ (1001) ~ (1033)

The methine dye according to claim 8, which is any one of groups represented by The methine dye according to claim 1, wherein X ₁ and Y ₁ in formula (1) are bonded and / or X ₂ and Y ₂ are bonded to form a ring structure. The ring structure formed by combining X ₁ and Y ₁ in formula (1) and / or combining X ₂ and Y ₂ is represented by the following formulas (2001) to (2044).

(In formulas (2001) to (2044), * represents a carbon atom to which X ₁ and Y ₁ are bonded and / or a carbon atom to which X ₂ and Y ₂ are bonded in formula (1).)
The methine dye according to claim 10, which is any one of the ring structures represented by the formula: The methine dye according to claim 11, wherein the ring structure formed by combining X ₁ and Y ₁ in Formula (1) and / or combining X ₂ and Y ₂ has a carboxyl group as a substituent. By bonding X ₁ and Y ₁ in the formula (1), and / or claim 12 ring structure X ₂ and Y ₂ is formed by bonding is a ring structure represented by Formula (2007) or (2012) The methine dye described in 1. The methine dye according to claim 1, wherein A _{1 to} A ₁₅ in formula (1) are hydrogen atoms. R ₂ in formula (1) is
(I) is a group represented by the formula (3001), and R ₁₂ and R ₁₃ in the formula (3001) are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms,
Or (II) a group represented by the formula (3003), wherein R ₁₄ and R ₁₅ in the formula (3003) are each independently a phenyl group or a group represented by the formula (3001), and R _{16 to} R ₁₉ are 2. The hydrogen atom or the alkoxy group having 1 to 4 carbon atoms each independently, and R ₁₂ and R ₁₃ in the formula (3001) are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Methine dyes. R ₂ in the formula (1) is represented by the following formulas (3101) to (3114)

The methine dye according to claim 15, which is any one of groups represented by: The methine dye according to claim 16, wherein R ₂ in the formula (1) is a group represented by the formula (3107), (3108), (3110), (3111), (3113) or (3114). The methine dye according to claim 17, wherein R ₂ in the formula (1) is a group represented by the formula (3107) or (3111). The following formula (705), (710) or (712)

The methine dye according to claim 1 represented by: The photoelectric conversion element which carry | supported the methine dye represented by Formula (1) of Claim 1 in the thin film of the oxide semiconductor fine particle provided on the board | substrate. A solar cell using the photoelectric conversion element according to claim 20.