TW201534603A - Novel compound, and photoelectric conversion element comprising the same - Google Patents

Abstract

A compound having a specific structure; a photoelectric conversion element that uses the compound and has a high conversion efficiency at a low cost; and a solar cell that uses the photoelectric conversion element. The compound is represented by formula (1) (in formula (1): m represents an integer from 1 to 5; l and n each independently represent an integer from 0 to 6; j represents an integer from 0 to 3; X1 and X2 represent a hydrogen atom, a carboxyl group, a hydroxyl group, a phosphate group, or the like; Q1 and Q2 represent an oxygen atom, a sulfur atom, or the like; A1 to A8 represent a hydrogen atom, an aliphatic hydrocarbon residue, a cyano group, a halogen group, or the like; R1 represents the residue resulting from removing one hydrogen atom from an aromatic ring (Ar1) of the compound represented in formula (2) (in formula (2): M represents a metalloid atom; Y1 to Y3 represent a hydrogen atom or an aromatic residue; Z1 and Z2 each independently represent a halogen atom; and Ar1 and Ar2 represent an aromatic ring); and R2 represents an aminophenyl group).

Description

Novel compound and photoelectric conversion element containing the same

The present invention relates to a novel organic compound having a specific structure, a photoelectric conversion element including the compound as a sensitizing dye, and a solar cell including the photoelectric conversion element.

Solar cells that use sunlight as an energy resource to replace fossil fuels such as petroleum and charcoal are attracting attention. At present, research and development are being actively carried out for tantalum solar cells using crystalline or amorphous germanium or compound semiconductor solar cells using gallium or arsenic. However, since such manufacturing requires a large amount of energy, as a result, the manufacturing cost is still expensive. On the other hand, a photoelectric conversion element produced using semiconductor fine particles sensitized by a dye or a solar cell including the photoelectric conversion element is known, and materials such as sensitizing dyes and semiconductor fine particles, and manufacturing techniques of components and batteries are known. Various types have been disclosed (see Patent Document 1, Non-Patent Document 1, Non-Patent Document 2). In the dye-sensitized photoelectric conversion element, a relatively inexpensive oxide semiconductor such as titanium oxide has been used, and In comparison with solar cells such as the conventional ones, there is a possibility that a photoelectric conversion element can be obtained at a low cost, and attention is paid from obtaining a colorful solar battery. However, in order to obtain an element having high conversion efficiency, the cost of the ruthenium complex itself used as a sensitizing dye is high, and there is a problem in stable supply thereof. Therefore, an organic dye has been tried as a sensitizing dye. However, since the problems of conversion efficiency, stability, and low durability have not been solved, it has not yet been put into practical use, and it is desired to further improve the characteristics such as conversion efficiency (refer to the patent literature). 2).

In view of the above, the present inventors have revealed organic dyes which can improve conversion efficiency and the like of photoelectric conversion elements (Patent Documents 3 and 4)

[Previous Technical Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 01-220380

[Patent Document 2] International Publication No. WO2002/011213

[Patent Document 3] International Publication No. WO2007/100033

[Patent Document 4] International Publication No. WO2013/147145

[Non-patent literature]

[Non-Patent Document 1] B. O'Regan and M. Graetzel Nature, Vol. 353, 737 (1991)

[Non-Patent Document 2] MK Nazeeruddin, A. Kay, I. Rodicio, R. Humphry-Baker, E. Muller, P. Liska, N. Vlachopoulos, M. Graetzel, J. Am. Chem. Soc., No. 115 Volume, 6382 pages (1993) year)

[Non-Patent Document 3] Yuji Kubo, Kazuki Watanabe, Ryuhei Nishiyabu, Reiko Hata, Akinori Murakami, Takayuki Shoda, and Hitoshi Ota, Org. -Lett., Vol. 13, No.17, 2011. 4574

[Non-Patent Document 4] W. Kubo, K. Murakoshi, T. Kitamura, K. Hanabusa, H. Shirai, and S. Yanagida, Chem. Lett., p. 1241 (1998)

However, the development of photoelectric conversion elements having higher conversion efficiency and high practicability by using oxide semiconductor fine particles sensitized by dyes has been sought.

As a result of the active efforts of the inventors of the present invention, it has been found that a thin film of semiconductor fine particles is sensitized by using a novel compound having a specific structure to form a photoelectric conversion element, thereby obtaining a photoelectric conversion element having a higher conversion efficiency. To complete the present invention.

That is, the present invention relates to (1) a compound represented by the following formula (1);

(In the formula (1), m represents an integer of 1 to 5, l and n each independently represent an integer of 0 to 6, and j represents an integer of 0 to 3; and X ₁ and X ₂ independently represent a hydrogen atom, a carboxyl group, a hydroxyl group, a phosphate group, a sulfonic acid group, a cyano group, a decyl group, a decylamino group, an alkoxycarbonyl group or a sulfonylphenyl group, and X ₁ and X ₂ may be bonded to each other to form a ring; and Q ₁ and Q ₂ each independently represent an oxygen atom or a sulfur atom. a selenium atom or NR ₁₁ ; R ₁₁ represents a hydrogen atom, an aromatic residue or an aliphatic hydrocarbon residue. When m is 2 or more and Q ₁ is a plural, individual Q ₁ may be the same or different from each other. When j is 2 or more and Q ₂ is a plural, individual Q ₂ may be the same or different from each other; A ₁ , A ₂ , A ₃ , A ₅ and A ₆ each independently represent a hydrogen atom or an aromatic residue. , an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carboxy oxime amino group, a decylamino group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group or a fluorenyl group; 1 is 2 or more and A ₂ and A ₃ In the case where the plural is present, the individual A ₂ and A ₃ may be the same or different from each other, and when n is 2 or more and A ₅ and A ₆ are plural, the individual A ₅ and A ₆ may be the same as each other. Or different; the case where l is other than 0, A _1, A ₂ and A ₃ are any one of a plurality of a can form a ring; A ₄ represents a hydrogen atom, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carboxylic acyl group, an alkoxy An oxy group, a decylamino group, an alkoxycarbonyl group or a fluorenyl group; when m is 2 or more and A ₄ is a plural number, the individual A ₄ groups may be the same or different from each other; and A ₇ and A ₈ each independently represent a hydrogen atom. , an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carboxylammonium group, an alkoxy group, an alkoxycarbonyl group or a fluorenyl group; wherein j is 2 or more and A ₇ and A ₈ are plural, individual A ₇ And A ₈ may be the same or different from each other; R ₁ represents from the following formula (2)

(In the formula (2), M represents a metalloid atom; Y ₁ , Y ₂ and Y ₃ each independently represent a hydrogen atom or an aromatic residue; Z ₁ and Z ₂ each independently represent a halogen atom; and Ar ₁ and Ar ₂ are each independently When a residue of one hydrogen atom is removed from the aromatic ring Ar ₁ of the compound represented by the aromatic ring); when m is 2 or more and R ₁ is a plural, the individual R ₁ may be the same or different from each other. R ₂ is the following formula (3003)

(In the formula (3003), 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 each independently represent a hydrogen atom or an aromatic residue. A group represented by an aliphatic hydrocarbon residue, a cyano group, a decyl group, a decylamino group, an alkoxy group, an alkoxycarbonyl group or a sulfonylphenyl group. Further, when n is other than 0, any one of A ₅ , A ₆ and R ₂ may form a plurality of rings, and (2) the compound of the above item (1), wherein m in the formula (1) is (3) The compound of the above item (2), wherein, in the formula (1), m is 1, (4) the compound of the above item (1), wherein, in the formula (1), Q ₁ and Q ₂ A compound of the above formula (1), wherein, in the formula (1), l and n are 0, (6) the compound of the above item (1), wherein, in the formula (1), X ₁ And one of X ₂ is a carboxyl group, and the other is a carboxyl group, a cyano group or a fluorenyl group, and (7) a compound according to the above item (6), wherein one of X ₁ and X ₂ in the formula (1) is a carboxyl group. (8) A compound according to the above item (1), wherein X ₁ and X ₂ in the formula (1) are bonded to form a ring structure, and (9) a compound according to the above item (1), Wherein, A ₁ to A ₈ in the formula (1) are a hydrogen atom, and (10) a compound according to the above item (1), wherein the R ₁ in the formula (1) is from the following formula (3)

(In the formula (3), Z ₃ and Z ₄ each independently represent a halogen atom; and A ₂₃ and A ₂₄ each independently represent a benzene ring of a compound represented by a hydrogen atom, a halogen atom, an aliphatic hydrocarbon residue or an alkoxy group) removing ₁ residue a hydrogen atom, the (11) the compound of the preceding paragraph (10) of which, Z in formula (3) of ₃ and Z ₄ is a fluorine atom, and A ₂₃ and A ₂₄ is methoxy, (12) A compound according to the above item (1), wherein R ₁₄ and R ₁₅ in the formula (3003) are the following formula (3001)

(In the formula (3001), R ₁₂ and R ₁₃ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), and R ₁₆ to R ₁₉ are each independently a hydrogen atom or a carbon number of 1 to 4. (13) A compound according to the above item (12), wherein R ₂ in the formula (1) is a formula (3109) to (3114)

(14) A compound according to the above item (13), wherein the R ₂ formula (1) is represented by the formula (3110), (3111), (3113) or (3114) (15) The compound according to the above item (14), wherein R ₂ is a group represented by the formula (1111), and (16) is a compound of the above item (1), which is the following formula ( 812)

(17) A photoelectric conversion element which carries one or more thin films of oxide semiconductor fine particles provided on a substrate, and (18) a photoelectric compound, which is a compound represented by the formula (1) of the above (1) A conversion element that carries one or more of the compounds represented by the formula (1) of the above (1) and a sensitized dye compound having a structure other than the formula (1), and a thin film of the oxide semiconductor fine particles provided on the substrate The photoelectric conversion element according to the above item (17) or (18), wherein the oxide semiconductor fine particles contain titanium oxide, zinc oxide or tin oxide, and (20) a solar cell having the following (17)~ (19) A photoelectric conversion element of any one of them.

By using the compound of the present invention having a specific structure represented by the formula (1) (also referred to as "the compound of the present invention" in the present specification) as a sensitizing dye, it is possible to provide a conversion efficiency and practicability. High pigment-sensitized solar cells.

[Fig. 1] The IPCE spectra of the solar cells obtained in Example 2 and Comparative Example 1.

The invention is described in detail below.

The compound of the present invention has a structure represented by the following formula (1).

The m in the formula (1) represents an integer of 1 to 5, preferably 1 to 3, more preferably 1 to 2, still more preferably 1.

The l in the formula (1) represents an integer of 0 to 6, preferably 0.

The n in the formula (1) represents an integer of 0 to 6, preferably 0.

The j in the formula (1) represents an integer of 0 to 3, preferably 1 to 3, more preferably 1 to 2, still more preferably 2.

X ₁ and X ₂ in the formula (1) each independently represent a hydrogen atom, a carboxyl group, a hydroxyl group, a phosphoric acid group, a sulfonic acid group, a cyano group, a decyl group, a decylamino group, an alkoxycarbonyl group, or a sulfonylphenyl group. A family residue, or X ₁ and X _{2 ,} may be bonded to each other to form a ring.

Examples of the fluorenyl group represented by X ₁ and X _{2 in} the formula (1) include an alkylcarbonyl group having 1 to 10 carbon atoms and an arylcarbonyl group (generally having a monocyclic, bicyclic or tricyclic aryl group). And the like, preferably an alkylcarbonyl group having 1 to 4 carbon atoms and a monocyclic or bicyclic aromatic carbonyl group. Examples of the alkylcarbonyl group having 1 to 4 carbon atoms include an ethyl fluorenyl group, a propyl fluorenyl group, a trifluoromethylcarbonyl group, and a pentafluoroethylcarbonyl group. Examples of the monocyclic or bicyclic arylcarbonyl group include benzoic acid. Sulfhydryl, naphthylmethyl group, and the like.

The mercapto group represented by X ₁ and X _{2 of} the formula (1) may have a substituent as the substituent which may be possessed, for example, in addition to a sulfonic acid group, an amine sulfonyl group, a cyano group, an isocyano group, a thiocyanyl group, Isocyanato, nitro, nitroso, halogen atom, hydroxyl group, phosphate group, phosphate group, substituted or unsubstituted amine group, substituted or unsubstituted fluorenyl group, decylamino group, alkoxy group, aryloxy group, carboxyl group Examples of the substituted carbonyl group such as an aminomethyl group, a fluorenyl group, an aldehyde group, and an alkoxycarbonyl group or an arylcarbonyl group include an aromatic residue and an aliphatic hydrocarbon residue.

Examples of the halogen atom which may have a substituent of the fluorenyl group represented by X ₁ and X _{2 in} the formula (1) include an atom such as fluorine, chlorine, bromine or iodine, and a bromine atom and a chlorine atom are preferred.

Examples of the phosphate group which may have a substituent of the fluorenyl group represented by X ₁ and X _{2 in} the formula (1) include a phosphoric acid (carbon number 1 to 4) alkyl ester group, etc., and a preferred specific example is a phosphoric acid group. Methyl ester, ethyl phosphate, (n-propyl) phosphate and (n-butyl) phosphate.

As the substituted or unsubstituted amino group which may have a substituent of the fluorenyl group represented by X ₁ and X _{2 of} the formula (1), an unsubstituted amino group, a mono or dimethylamino group, a mono or diethylamine may be mentioned. a monocyclic or bicyclic ring such as an alkyl group-substituted amine group having a carbon number of 1 to 4, a mono- or diphenylamino group, a mono- or di-naphthylamino group, or the like, a mono- or di-(n-propyl)amino group or the like. An alkyl group having a tricyclic aromatic substituted amine group, an alkyl group having a single carbon number of 1 to 4, and a monocyclic, bicyclic or tricyclic aromatic residue one by one Substituted amine group, and benzylamino group, etidinyl group, phenylethylamino group and the like.

Examples of the substituted or unsubstituted fluorenyl group which may have a substituent of the fluorenyl group represented by X ₁ and X _{2 of} the formula (1) include an unsubstituted fluorenyl group, an alkyl fluorenyl group, specifically a methyl fluorenyl group, an ethyl fluorenyl group, and n. a fluorenyl group having 1 to 4 carbon atoms, such as a propyl fluorenyl group, an isopropyl fluorenyl group, an n-butyl fluorenyl group, an isobutyl fluorenyl group, a sec-butyl fluorenyl group, a t-butyl fluorenyl group, or a monocyclic group or a second group A cyclic or tricyclic aromatic substituted fluorenyl group, specifically a phenyl fluorenyl group or the like.

Examples of the guanamine group which may have a substituent of the fluorenyl group represented by X ₁ and X _{2 of} the formula (1) include a guanamine group (NH ₂ (CO)H) in a narrow sense; an acetamino group; An amine group, an alkyl acetamino group, an aryl decylamino group, an aryl acetamidine group, and preferred examples thereof include a guanamine group (NH ₂ (CO)H), an acetamino group, and an N-methyl group. Amino group, N-ethyl decylamino group, N-(n-propyl) decylamino group, N-(n-butyl) decylamino group, N-isobutyl decylamino group, N-(sec - butyl decyl), N-(t-butyl) decylamino, N,N-dimethyl decylamino, N,N-diethyl decylamino, N,N-di(n- Propyl) guanamine, N,N-bis(n-butyl)decylamine, N,N-diisobutylammonium, etc. N-methylacetamido, N-ethylethylammonium, N-(n-propyl)acetamido, N-(n-butyl)ethylammonium, N-isobutyl Ethylamino, N-(sec-butyl)acetamido, N-(t-butyl)acetamido, N,N-dimethylacetamido, N,N-diethyl Ethylamino, N,N-di(n-propyl)acetamidamine, N,N-bis(n-butyl)acetamido, N,N-diisobutylethylamino, etc. a single number of carbons of 1 to 4 or a dialkylacetamidamine group; a monocyclic, bicyclic or tricyclic aryl guanamine group such as a phenylguanidino group or a naphthylamino group; or a monocyclic ring such as a phenylethylamino group or a naphthylamino group; An aryl acetamino group of the formula, a bicyclic ring or a tricyclic ring.

Examples of the alkoxy group which may have a substituent of the fluorenyl group represented by X ₁ and X _{2 of} the formula (1) include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and an n-butyl group. An alkoxy group having 1 to 4 carbon atoms such as an oxy group, an isobutoxy group, a sec-butoxy group or a t-butoxy group.

Examples of the aryloxy group which may have a substituent of the fluorenyl group represented by X ₁ and X _{2 in} the formula (1) include a monocyclic, bicyclic or tricyclic ring such as a phenoxy group or a naphthyloxy group. Aryloxy.

The fluorenyl group which may have a substituent of the fluorenyl group represented by X ₁ and X _{2 of} the formula (1) is the same as those described in the item of the fluorenyl group represented by X ₁ and X _{2 of} the formula (1) .

Examples of the alkoxycarbonyl group which may have a substituent of the fluorenyl group represented by X ₁ and X _{2 in} the formula (1) include an alkoxycarbonyl group having 1 to 10 carbon atoms, and specific examples thereof are a methoxycarbonyl group and a Oxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, t-butoxycarbonyl, n-pentyloxycarbonyl , n-hexyloxycarbonyl, n-heptyloxycarbonyl, n-decyloxycarbonyl, n-decyloxycarbonyl.

The arylcarbonyl group which may have a substituent of the fluorenyl group represented by X ₁ and X _{2 of} the formula (1), for example, represents a monocyclic or bicyclic ring which bonds a benzophenone, a naphthophenone or the like. a tricyclic aryl group and a carbonyl group.

The aromatic residue which is a substituent which may have a mercapto group represented by X ₁ and X _{2 of} the formula (1) means that one hydrogen atom is removed from the aromatic ring (containing a condensed ring of an aromatic ring and an aromatic ring) The aromatic residue may have a substituent. Specific examples of the aromatic ring include a monocyclic, bicyclic or tricyclic aromatic such as a benzene ring, a naphthalene ring, an onion ring, a phenanthrene ring, an anthracene ring, an anthracene ring, and a terrylene ring. Aromatic hydrocarbon ring; anthracene ring, anthracene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrazole ring, pyrazolidine ring, Thiazolidine ring, oxazolidine ring, piper ring, pyran (Chromene) a ring, a pyrrole ring, a pyrrolidine ring, a benzimidazole ring, an imidazoline ring, an imidazolidinium ring, an imidazole ring, a triazole ring, a triazine ring, a diazole ring, a porphyrin ring, a furan ring, an oxazole ring, Oxadiazole ring, thiazine ring, thiazole ring, anthracene ring, benzothiazole ring, benzothiadiazole ring, naphthylthiazole ring, benzoxazole ring, naphthoazole ring, ruthenium ring, benzo a heterocyclic element such as an anthracene ring, a quinoline ring or a quinazoline ring, or a heterocyclic ring of a monocyclic or bicyclic condensed type of 4 to 7 members; and an anthracene ring and an indazole ring The hetero-elements such as N, O and S, and the tricyclic condensation type condensed heteroaromatic ring of 4 to 7 members are preferably aromatic rings having 4 to 20 carbon atoms.

Examples of the aliphatic hydrocarbon residue which may have a substituent of the fluorenyl group represented by X ₁ and X _{2 of} the formula (1) include a saturated or unsaturated linear or branched alkyl group or a cyclic alkyl group. The aliphatic hydrocarbon residue may have a substituent. As the aliphatic hydrocarbon residue, a saturated alkyl group is preferred, and a saturated linear alkyl group is more preferred. Further, the aliphatic hydrocarbon residue preferably has a carbon number of from 1 to 36, more preferably from 1 to 18, still more preferably from 1 to 8. Specific examples of such 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, and n. -pentyl, n-hexyl, n-heptyl, n-octyl, n-fluorenyl, n-fluorenyl, n-undecyl, n-dodecyl, n-tridecyl, n -tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, cyclohexyl, vinyl, propenyl, pentynyl, butenyl ,hexenyl, hexadienyl, isopropenyl, isohexenyl, cyclohexenyl, cyclopentadienyl, ethynyl, propynyl, pentynyl, hexynyl, isohexynyl, cyclohexyl Alkynyl and the like. Further, examples of the cyclic alkyl group include a cycloalkyl group having 3 to 8 carbon atoms.

It is a linear alkyl group having a carbon number of 1 to 8.

Formula (1) of X ₁ and X ₂ acyl represented by the group, the acyl group include substituted acyl of items ₁ and X ₂ are represented as X may have the formula (1) as described by the group The same. The mercapto group represented by X ₁ and X _{2 in} the formula (1) may have a substituent, and as the substituent which may be contained, a mercapto group represented by X ₁ and X ₂ which may have the formula (1) may be mentioned. The substituents described in the project are the same.

Alkoxycarbonyl formula (1) of X represented by the ₁ and X _2, include the same alkoxycarbonyl item of acyl of substituent group of X may have the formula (1) of the indicated ₁ and X ₂ are described by The same. Alkoxycarbonyl group X of formula (1) represented the ₁ and X ₂ may have a substituent group, as the may have the substituent include the same as a having the formula (1) of X ₁ and X ₂ are represented by the acyl The substituents are the same as described in the project.

An aromatic residue, an aliphatic hydrocarbon residue, a mercaptoamine group, a mercapto group or an alkoxy group which may have a substituent of a mercapto group, a mercaptoamine group and an alkoxycarbonyl group represented by X ₁ and X _{2 of} the formula (1) The group, the aryloxy group, the arylcarbonyl group and the alkoxycarbonyl group may have a substituent, and as the substituent which may be present, a substituent which may be a fluorenyl group represented by X ₁ and X _{2 of} the formula (1) may be mentioned. The items described in the project are the same.

Specific examples of the aromatic residue represented by X ₁ and X _{2 in} the formula (1) include aromatic residues which are substituents which may have a mercapto group represented by X ₁ and X _{2 of} the formula (1). The same as described in the base project. The aromatic residue may have a substituent, and examples of the substituent include the same as those described for the item which may have a substituent of the fluorenyl group represented by X ₁ and X _{2 of} the formula (1).

The aromatic residue represented by X ₁ and X ₂ is preferably 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 selected from the acidic group. The aromatic residue of the above substituent is more preferably a group represented by any one of the following formulas (1001) to (1033).

Examples of the ring formed by bonding X ₁ and X _{2 to} each other include an aromatic ring, a hetero ring, and the like, and the rings may have a substituent.

Specific examples of the aromatic ring formed by bonding X ₁ and X _{2 to} each other are exemplified as the aromatic residue which is a substituent which may have a mercapto group represented by X ₁ and X _{2 of} the formula (1). It is the same as the aromatic ring described as a specific example. Further, examples of the substituent which may have a ring in which X ₁ and X ₂ are bonded to each other include those described as an item which may have a substituent of a fluorenyl group represented by X ₁ and X _{2 of} the formula (1). The same.

The heterocyclic ring formed by bonding X ₁ and X _{2 to} each other is, for example, a heterocyclic ring containing a hetero atom such as S, O or N of a 4 to 7 member ring, preferably in the following formula (2001) to (2017). The ring represented by any one of them is more preferably a ring represented by the formula (2007) or the formula (2012), and even more preferably a ring represented by the formula (2007).

Further, the imprint of the above formula (2001) to (2017) indicates that carbon atoms of both of X ₁ and X ₂ are bonded in the formula (1).

Preferably, X ₁ and X ₂ in the formula (1) are each independently a carboxyl group, a phosphoric acid group, a cyano group or a fluorenyl group, and more preferably each independently a carboxyl group, a cyano group or a fluorenyl group, and more preferably one of them. It is a carboxyl group and the other is a carboxyl group, a cyano group or a fluorenyl group, and one of them is preferably a carboxyl group and the other is a cyano group.

Q ₁ and Q ₂ in the 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.

The aromatic residue represented by R ₁₁ may be the same as those described for the aromatic residue item which is a substituent which may have a mercapto group represented by X ₁ and X _{2 of} the formula (1).

The aliphatic hydrocarbon residue represented by R ₁₁ may be the same as those described for the aliphatic hydrocarbon residue item which is a substituent which may have a mercapto group represented by X ₁ and X _{2 of} the formula (1).

The aromatic residue and the aliphatic hydrocarbon residue represented by R ₁₁ may have a substituent, and examples of the substituent which may be contained include a thiol group which may be represented by X ₁ and X _{2 of} the formula (1). Substituted items are the same as described in the project.

When m of the formula (1) is 2 or more and Q ₁ is a complex number, the individual Q ₁ may be the same or different from each other, and if j is 2 or more and Q ₂ is a complex number, the individual Q _{2 may be present.} Can be the same or different from each other.

Preferably, Q ₁ and Q ₂ in the formula (1) are each independently an oxygen atom, a sulfur atom or a selenium atom, more preferably a sulfur atom.

A ₁ , A ₂ , A ₃ , A ₅ and A ₆ in the formula (1) each independently represent a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carboxy oxime group, and a guanamine. Alkyl, alkoxy, aryloxy, alkoxycarbonyl, arylcarbonyl or fluorenyl.

As the aromatic residue represented by A ₁ , A ₂ , A ₃ , A ₅ and A ₆ , an aliphatic hydrocarbon residue, a halogen atom, a decylamino group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group and an arylcarbonyl group Examples thereof include an aromatic residue, an aliphatic hydrocarbon residue, a halogen atom, a decylamino group, an alkoxy group, and an aryloxy group which may have a substituent of the fluorenyl group represented by X ₁ and X _{2 of} the formula (1). The same as described for the alkoxycarbonyl and arylcarbonyl projects.

The thiol group represented by A ₁ , A ₂ , A ₃ , A ₅ and A ₆ may be the same as those described in the item of the thiol group represented by X ₁ and X _{2 of} the formula (1).

The aromatic residue, aliphatic hydrocarbon residue, decylamino group, alkoxy group, aryloxy group, alkoxycarbonyl group, arylcarbonyl group and fluorenyl group represented by A ₁ , A ₂ , A ₃ , A ₅ and A ₆ may be having a substituent group, which may have as the substituent group, and may include having the formula (1) of X ₁ and X ₂ are the same as those represented by the substituent of acyl group as described items.

When l of the formula (1) is 2 or more and A ₂ and A ₃ are plural, the individual A ₂ and A ₃ may be the same or different from each other, n is 2 or more, and A ₅ and A ₆ are plural. In the case where they exist, the individual A ₅ and A ₆ may be the same or different from each other. Further, when l is other than 0, any one of A ₁ , A ₂ and A ₃ may form a plurality of rings.

Examples of the ring formed by any of A ₁ , A ₂ and A ₃ include an unsaturated hydrocarbon ring or a hetero ring.

Examples of the unsaturated hydrocarbon ring which may be formed by any of A ₁ , A ₂ and A ₃ include a benzene ring, a naphthalene ring, an onion ring, a phenanthrene ring, an anthracene ring, an anthracene ring, an anthracene ring, and an anthracene ring. And a cyclobutene ring, a cyclohexene ring, a cyclopentene ring, a cyclohexadiene ring, a cyclopentadiene ring, etc., and examples of the hetero ring include a piper ring, a pyridine ring, a pyrazine ring, and a piperidine. Ring, porphyrin ring, oxazole ring, thiazole ring, thiadiazole ring, oxadiazole ring, anthracene ring, benzothiazole ring, benzoxazole ring, quinoline ring, indazole ring, benzopyrazine Ring and so on. Among these, a benzene ring, a cyclobutene ring, a cyclopentene ring, and a cyclohexene ring are preferable.

These unsaturated hydrocarbon rings, heterocyclic rings and the like may have a substituent, and examples of the substituent which may be included are as described in the item which may have a substituent of the fluorenyl group represented by X ₁ and X _{2 of} the formula (1). The same person.

Any one of A ₁ , A ₂ and A ₃ may be a plurality of heterocyclic rings formed, and when it has a substituent such as a carbonyl group or a thiocarbonyl group, a cyclic ketone or a cyclic thioketone may be formed. Further having a substituent. The substituent which may be contained may be the same as those described for the item which may have a substituent of the fluorenyl group represented by X ₁ and X _{2 of} the formula (1).

Preferably, A ₁ , A ₂ , A ₃ , A ₅ and A ₆ in the formula (1) are each independently a hydrogen atom or an aliphatic hydrocarbon residue, and more preferably each independently represents a hydrogen atom or a carbon number of 1~. A linear alkyl group of 8 is more preferably a hydrogen atom.

A ₄ in the formula (1) represents a hydrogen atom, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carboxy oxime group, an alkoxy group, a decylamino group, an alkoxycarbonyl group or a fluorenyl group.

Examples of the aliphatic hydrocarbon residue, halogen atom, alkoxy group, decylamino group and alkoxycarbonyl group represented by A ₄ include a substituent which may have a mercapto group represented by X ₁ and X _{2 of} the formula (1). The same is true for the aliphatic hydrocarbon residue, halogen atom, alkoxy group, decylamino group and alkoxycarbonyl group.

The thiol group represented by A ₄ may be the same as those described in the item of the thiol group represented by X ₁ and X _{2 of} the formula (1).

The aliphatic hydrocarbon residue, alkoxy group, decylamino group, alkoxycarbonyl group and fluorenyl group represented by A ₄ may have a substituent, and as the substituent which may be present, an X ₁ group having the formula (1) may be mentioned And the same as described in the item of the substituent of the thiol group represented by X ₂ .

When m is 2 or more and A ₄ is a plural, the individual A ₄ may be the same or different from each other.

The A ₄ in the formula (1) is preferably a hydrogen atom or an aliphatic hydrocarbon residue, more preferably a hydrogen atom or a linear alkyl group having 1 to 8 carbon atoms, still more preferably a hydrogen atom.

A ₇ and A ₈ in the formula (1) each independently represent a hydrogen atom, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carboguanamine group, an alkoxy group, an alkoxycarbonyl group or a fluorenyl group.

Examples of the aliphatic hydrocarbon residue, the halogen atom, the alkoxy group and the alkoxycarbonyl group represented by A ₇ and A ₈ include a substituent which may be a fluorenyl group represented by X ₁ and X _{2 of} the formula (1). The aliphatic hydrocarbon residue, halogen atom, alkoxy group and alkoxycarbonyl group are the same as described in the item.

The thiol group represented by A ₇ and A ₈ may be the same as those described in the item of the thiol group represented by X ₁ and X _{2 of} the formula (1).

The aliphatic hydrocarbon residue, the alkoxy group, the alkoxycarbonyl group and the fluorenyl group represented by A ₇ and A ₈ may have a substituent, and as the substituent which may be present, may be exemplified by X _{1 which} may have the formula (1) The items described in the item of the substituent of the fluorenyl group represented by X ₂ are the same.

When j is 2 or more and A ₇ and A ₈ are plural, the individual A ₇ and A ₈ may be the same or different from each other.

Preferably, each of A ₇ and A ₈ in the formula (1) is independently a hydrogen atom or an aliphatic hydrocarbon residue, and more preferably each independently represents a hydrogen atom or a linear alkyl group having 1 to 8 carbon atoms, and further Good is a hydrogen atom. Accordingly, in a preferred embodiment of the invention, all of A ₁ to A ₈ are hydrogen.

R ₁ in the formula (1) represents a residue obtained by removing one hydrogen atom from the aromatic ring Ar ₁ of the compound represented by the following formula (2). Further, the position at which one hydrogen atom on the aromatic ring Ar ₁ is removed is not particularly limited.

In the formula (2), M represents a metalloid atom. The term "metalloid" as used in the present invention means a substance which exhibits an intermediate property between a metal and a nonmetal. Specifically, a boron atom, a germanium atom, a germanium atom and a germanium atom are preferable, and a boron atom is preferred.

In the formula (2), Y ₁ , Y ₂ and Y ₃ each independently represent a hydrogen atom or an aromatic residue, and examples of the aromatic residue represented by Y ₁ , Y ₂ and Y ₃ include the formula ( 1) The same as described for the aromatic residue item of the substituent of the fluorenyl group represented by X ₁ and X ₂ .

The aromatic residue represented by Y ₁ , Y ₂ and Y ₃ may have a substituent, and examples of the substituent which may be contained include a substituent which may have a mercapto group represented by X ₁ and X _{2 of} the formula (1) The base item is the same as described by the project.

The substituent which may have an aromatic residue represented by Y ₁ , Y ₂ and Y ₃ is preferably an alkoxy group.

Preferably, Y ₁ and Y ₂ in the formula (2) are each independently an aromatic residue, and more preferably each independently a phenyl group or a naphthyl group, and more preferably a phenyl group. Further, as Y ₃ in the formula (1), a hydrogen atom is preferred.

In the formula (2), Z ₁ and Z ₂ each independently represent a halogen atom. The halogen atom represented by Z ₁ and Z ₂ may be the same as those described for the item which may have a substituent of the fluorenyl group represented by X ₁ and X _{2 of} the formula (1), and is preferably a fluorine atom.

In the formula (2), Ar ₁ and Ar ₂ each independently represent an aromatic ring. Specific examples of the aromatic ring represented by Z ₁ and Z ₂ include the description of the aromatic residue which is a substituent which may have a mercapto group represented by X ₁ and X _{2 of} the formula (1), and The aromatic rings described in the specific examples are preferably the same as the benzene ring or the naphthalene ring, and more preferably the benzene ring.

In other words, as R ₁ in the formula (1), a residue of one hydrogen atom is preferably removed from the benzene ring b ₁ of the compound represented by the following formula (3). Further, the position at which one hydrogen atom on the benzene ring b ₁ is removed is not particularly limited, but is preferably the 6-position of the anthracene ring including the benzene ring b ₁ in the formula (3).

In the formula (3), Z ₃ and Z ₄ each independently represent a halogen atom. The halogen atom represented by Z ₃ and Z ₄ may be the same as those described for the halogen atom which is a substituent which may have a mercapto group represented by X ₁ and X _{2 of} the formula (1), and is preferably fluorine. atom.

In the formula (3), A ₂₃ and A ₂₄ each independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon residue or an alkoxy group.

Examples of the halogen atom, the aliphatic hydrocarbon residue, and the alkoxy group represented by A ₂₃ and A _{24 include} a halogen atom which is a substituent which may have a mercapto group represented by X ₁ and X _{2 of} the formula (1). The aliphatic hydrocarbon residue and the alkoxy item are the same as described in the item.

When m is 2 or more and R ₁ is a plural, the individual R ₁ may be the same or different from each other.

The A ₂₃ and A ₂₄ in the formula (1) are preferably an alkoxy group, more preferably an alkoxy group having 1 to 4 carbon atoms, still more preferably a methoxy group.

R ₂ in the formula (1) is a group represented by the following formula (3003).

In the formula (3003), R ₁₄ and R ₁₅ each independently represent a hydrogen atom, an aromatic residue or an aliphatic hydrocarbon residue.

Examples of the aromatic residue and the aliphatic hydrocarbon residue represented by R ₁₄ and R ₁₅ include an aromatic residue which is a substituent which may have a mercapto group represented by X ₁ and X _{2 of} the formula (1). The same as described in the Aliphatic Hydrocarbon Residues Project.

The aromatic residue and the aliphatic hydrocarbon residue represented by R ₁₄ and R ₁₅ may have a substituent, and examples of the substituent which may be included may be represented by X ₁ and X _{2 of} the formula (1). The base of the substituents described in the project is the same.

R ₁₄ and R ₁₅ in the formula (3003) are preferably each independently an aromatic residue, and more preferably each independently represents a group represented by the following formula (3001), and more preferably both are the same. The base represented by the formula (3001).

In the formula (3001), R ₁₂ and R ₁₃ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

Preferably, R ₁₂ and R ₁₃ in the formula (3001) are each independently an alkyl group having 1 to 8 carbon atoms, more preferably each independently a linear alkyl group having 1 to 8 carbon atoms, and more preferably two. The ones are linear alkyl groups having the same carbon number of 1 to 8, and particularly preferably both are n-butyl groups.

In the formula (3003), R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ each independently represent a hydrogen atom, an aromatic residue, an aliphatic hydrocarbon residue, a cyano group, a decyl group, a decylamino group, an alkoxy group or an alkoxy group. Carbonyl or sulfonylphenyl.

Examples of the aromatic residue, the aliphatic hydrocarbon residue, the decylamino group, the alkoxy group and the alkoxycarbonyl group represented by R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ include X which may have the formula (1). aromatic residue, an aliphatic hydrocarbon residue, acyl group, alkoxy group and alkoxycarbonyl project acyl group of substituents represented by ₁ and X ₂ are the same as those described by.

The fluorenyl group represented by R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ may be the same as those described in the item of the fluorenyl group represented by X ₁ and X _{2 of} the formula (1).

R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ in the formula (3003) are preferably each independently a hydrogen atom or an alkoxy group, and more preferably each independently a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms. More preferably, all of them are hydrogen atoms.

In the case where n of the formula (1) is other than 0, any one of A ₅ , A ₆ and R ₂ may form a plurality of rings.

Any one of A ₅ , A ₆ and R ₂ may have a substituent, and the substituent which may be present may be exemplified by X ₁ and X ₂ which may have the formula (1). The base of the substituents described in the project is the same.

In other words, R ₂ in the formula (1) is particularly preferably a group represented by any one of the following formulas (3109) to (3114).

Among these, as the group represented by R ₂ in the formula (1), preferably any one of the formulas (3110), (3111), (3113) or (3114), the most preferable formula is (3111). ) the basis of the statement.

In the case where the compound represented by the formula (1) has an acidic group such as a carboxyl group, a phosphoric acid group, a hydroxyl group or a sulfonic acid group as a substituent, a salt may be formed, and examples of the salt include an alkali metal such as lithium, sodium or potassium. Or a salt of an alkaline earth metal or the like such as magnesium or calcium, or an organic base, for example, a grade 4 such as tetramethylammonium, tetrabutylammonium, pyridinium, imidazolium, piperazinium or piperidinium. a salt of an ammonium salt.

Although the compound represented by the formula (1) can obtain a structural isomer such as a cis isomer, a trans isomer or a racemate, it is not particularly limited, and any one isomer can be used. It is a good user of the dye for light sensitization of the present invention.

A preferred combination of m, l, n, j, X ₁ to X ₂ , Q ₁ to Q ₂ , A ₁ to A ₈ and R ₁ to R ₂ in the formula (1) is in the above m, l, Individuals of n, j, X ₁ to X ₂ , Q ₁ to Q ₂ , A ₁ to A ₈ and R ₁ to R ₂ are considered to be preferred combinations of each other, and more preferably, the combination is as follows.

That is, it is preferred that l and n are 0, m and j are 1 to 3 (more preferably, m is 1 and j is 1 to 3), and X ₁ and X ₂ are each independently a carboxyl group, a phosphoric acid group, a cyano group or a hydrazine. The bases, Q ₁ and Q ₂ are each independently an oxygen atom, a sulfur atom or a selenium atom, and A ₁ to A ₈ are each independently a hydrogen atom or an aliphatic hydrocarbon residue, and R ₁ is a fragrance derived from the compound represented by the formula (2). Residues of one hydrogen atom are removed from the ring Ar ₁ , Y ₁ and Y ₂ are each independently a phenyl or naphthyl group, Y ₃ is a hydrogen atom, and Ar ₁ and Ar ₂ are each independently a benzene ring or a naphthalene ring, and R _{2 is} independently It is a combination of the groups represented by any one of the above formulas (3109) to (3114).

More preferably, l and n are 0, m and j are 1 to 2 (more preferably, m is 1 and j is 1 to 2), and X ₁ and X ₂ are each independently a carboxyl group, a cyano group or a fluorenyl group, Q ₁ and Q _{2 is} independently an oxygen atom, a sulfur atom or a selenium atom, and A ₁ to A ₈ are each independently a hydrogen atom or a linear alkyl group having 1 to 8 carbon atoms, and R ₁ is a fragrance derived from a compound represented by the formula (3). A residue of one hydrogen atom is removed from the ring Ar ₁ , and R ₂ is a combination of groups represented by any one of the above formulas (3110), (3111), (3113) or (3114).

The preferred series l and n are 0, m and j are 1 to 2 (more preferably, m is 1 and j is 1 to 2), and one of X ₁ and X ₂ is a carboxyl group and the other is a carboxyl group or a cyano group. Or a mercapto group, Q ₁ and Q ₂ are a sulfur atom, A ₁ to A ₈ are a hydrogen atom, and R ₁ is a residue of one hydrogen atom removed from the aromatic ring Ar ₁ of the compound represented by the formula (3), Z ₃ and Z ₄ are a fluorine atom, and A ₂₃ and A ₂₄ are each independently an alkoxy group having 1 to 4 carbon atoms, and R ₂ is a combination of groups represented by the formula (3111).

The compound represented by the above formula (1) can be produced, for example, by the reaction formula shown below, but the present invention is not limited thereto. Synthetic method.

First, a method for synthesizing a compound represented by the formula (m) of an intermediate raw material will be described. The compound represented by the formula (a) and the compound represented by the formula (b) are reacted in a suitable solvent such as an alcohol to obtain a compound represented by the formula (c). Next, the compound represented by the formula (c), for example, in a suitable solvent such as tetrahydrofuran, is treated with lead tetraacetate to obtain a compound represented by the formula (d). Further, in the same procedure as described above, a compound represented by the formula (g) obtained by reacting a compound represented by the formula (e) of the starting material with a compound represented by the formula (f) is obtained to obtain a formula (h). ) the compound represented. Next, the compound represented by the formula (d) and the compound represented by the formula (h), for example, in a suitable mixed solvent of an alcohol and acetic acid, are added to aqueous ammonia to cause a reaction at room temperature, and are obtained by separation and purification. a compound represented by the formula (i). Next, a compound represented by the formula (i) is reacted with a halide of a metalloid M (boron trihalide or ruthenium, or osmium tetrahalide or ruthenium) to obtain a compound represented by the formula (j). Further, the compound represented by the formula (j) and the compound represented by the formula (k) are bonded by cross-coupling or the like to obtain a compound represented by the formula (m). Further, if Y _{3 is} necessary, it may be substituted by a substituent other than a hydrogen atom by a Grenadi reaction or the like.

Further, the compound represented by the formula (n) synthesized by a known method in advance and the compound represented by the formula (o) or the compound represented by the formula (p) synthesized by a known method in advance and the formula (q) The compound represented by the formula (i) obtained by reacting the compound represented by the acid catalyst such as bromohydrogen acid or hydrogen chloride in a solvent such as ethanol or tetrahydrofuran, and the same as described above. Processing, can also get (m) the compound represented.

The compound represented by the formula (t) is obtained by a reaction of a compound represented by the formula (r) with a boric acid represented by the formula (s). The compound represented by the formula (t) is treated with N-iodosuccinimide to give a compound represented by the formula (u). Here, the boric acid represented by the formula (v) is reacted to thereby derive the compound represented by the formula (w), and secondly by the reaction with the compound represented by the above formula (m), the formula (x) is obtained. a carbonyl compound represented. a compound having the compound represented by the formula (x) and the active methylene group represented by the formula (y), if necessary, by caustic soda, sodium methanolate, sodium acetate, diethylamine, triethylamine In the presence of an alkaline catalyst such as piperidine, piperazine or diazabicycloundecene, an alcohol such as methanol, ethanol, isopropanol or butanol or dimethylformamide or N-methyl An aprotic polar solvent such as a pyrrolidone or a solvent such as toluene, acetic anhydride or acetonitrile is usually at 20 ° C to 180 ° C, preferably 50 Condensation is carried out at a temperature of from ° C to 150 ° C to obtain a compound (pigment) represented by the formula (1) of the present invention. In the above reaction, the compound having an active methylene group represented by the formula (y) may have an ester group, and after the condensation reaction, a carboxylic acid body may be obtained by hydrolysis or the like.

Also, especially in the case where the compound of formula (1) is 0 In the case where the compound represented by the formula (r) is reacted with the boric acid represented by the formula (s), the compound represented by the formula (t) is replaced by the compound represented by the formula (t'). Can be synthesized.

Specific examples of the compound represented by the following formula (1-1) (the compound in which R ₁ of the formula (1) is a residue of the compound represented by the formula (3)) are shown in Tables 1 to 19. In each of the tables, the Ph system means a phenyl group. The (2001) to (2017) reporters indicate that the ring formed by the X ₁ and X ₂ bonds corresponds to the above formula (2001) to (2017). The expressions (3109) to (3114) correspond to the above equations (3109) to (3114).

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 a compound (dye) represented by the formula (1) is carried on the thin film.

As a substrate on which a thin film of oxide semiconductor fine particles is provided, it is preferable that the surface thereof is electrically conductive, but such a substrate can be easily obtained on the market. For example, a conductive metal oxide such as tin oxide doped with indium, fluorine or antimony may be provided on the surface of a transparent polymer material such as glass, polyethylene terephthalate or polyether oxime or the like. A metal film such as copper, silver or gold is used as a substrate. The conductivity is usually 1000 Ω or less, and particularly preferably 100 Ω or less.

Further, as the fine particles of the oxide semiconductor, a metal oxide is preferable, and specific examples thereof include oxides of titanium, tin, zinc, tungsten, zirconium, gallium, indium, lanthanum, cerium, lanthanum, and vanadium. Among these, oxides such as titanium, tin, zinc, antimony, and indium are preferable, and titanium oxide, zinc oxide, and tin oxide are preferable. Although these oxide semiconductors can be used singly, they can be used in combination and can be applied to a semiconductor surface. The particle diameter of the fine particles of the oxide semiconductor is usually from 1 to 500 nm, preferably from 1 to 100 nm, as the average particle diameter. Further, the fine particles of the oxide semiconductor can be used in a case where a large particle size can be mixed with a small particle size, or can be used in a plurality of layers.

The thin film of the oxide semiconductor fine particles can be formed by directly spraying the oxide semiconductor fine particles onto the substrate to form a thin film of the semiconductor fine particles, using the substrate as an electrode, and electrically depositing the semiconductor fine particles into a thin film. Will contain by hydrolyzing the semiconductor The paste of the fine particles obtained from the precursor of the semiconductor fine particles such as the slurry of the fine particles or the semiconductor alkane alumina is applied onto the substrate, and then dried, cured, or fired. In terms of the performance of an electrode using an oxide semiconductor, a method using a slurry is preferred. In the case of this method, the oxide semiconductor fine particles which are agglomerated twice in the slurry system are obtained by dispersing the average primary particle diameter into 1 to 200 nm in a dispersion medium by a usual method.

As the dispersing medium for dispersing the slurry, any of the semiconductor fine particles may be dispersed, such as alcohol such as water or ethanol, ketone such as acetone or acetamidine acetone, or hydrocarbon such as hexane, etc., which may be mixed. It is preferred to use, and to use water to reduce the viscosity change of the slurry. Further, for the purpose of stabilizing the dispersion state of the oxide semiconductor fine particles, a dispersion stabilizer can be used. Examples of the dispersion stabilizer to be used include an acid such as acetic acid, hydrochloric acid or nitric acid, or an organic solvent such as acetonitrile acetone, acrylic acid, polyethylene glycol or polyvinyl alcohol.

The substrate to which the slurry is applied may be fired, and the firing temperature is usually 100 ° C or higher, preferably 200 ° C or higher, and the upper limit is about the melting point (softening point) of the substrate material, and the upper limit is usually 900 ° C, preferably Below 600 °C. The firing time is not particularly limited, but is preferably within about 4 hours. The thickness of the film on the substrate is usually from 1 to 200 μm, preferably from 1 to 50 μm.

The film can be treated twice in the thin film of the oxide semiconductor fine particles. That is, for example, by thinning or re-sintering the film of each substrate by a solution of an alkoxide, a chloride, a nitrate, a sulfide, or the like of the same metal as the semiconductor, the semiconductor fine particles are lifted. thin Membrane properties. Examples of the metal alkoxides include titanium ethoxide, titanium isopropoxide, titanium t-butoxide, n-dibutyl-diethyl fluorenyl, and the like, and these alcohol solutions 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 formed of fine particles of an oxide semiconductor.

Next, a method of supporting the compound represented by the above formula (1) of the present invention on a thin film of the oxide semiconductor fine particles will be described.

The method of supporting the compound represented by the above formula (1) includes a solution obtained by dissolving the compound, a solution obtained by dissolving the compound, or a compound having low solubility, and the dispersion obtained by dispersing the compound is immersed in the oxidation. A method of providing a substrate provided by a thin film of semiconductor fine particles. The concentration in the solution or dispersion is appropriately determined depending on the compound. A thin film of semiconductor fine particles formed on the substrate is immersed in the solution. The immersion temperature is from about room temperature to the boiling point of the solvent, and the immersion time is from about 1 minute to 48 hours. Specific examples of the solvent which can be used for dissolving the compound include methanol, ethanol, isopropanol, tetrahydrofuran (THF), acetonitrile, dimethyl hydrazine (DMSO), dimethylformamide (DMF), and Acetone, n-butanol, t-butanol, water, n-hexane, chloroform, dichloromethane, toluene, etc., and the solubility of the compound may be used singly or in combination. The concentration of the compound in the solution is usually from 1 × 10 ^-6 M to 1 M, preferably from 1 × 10 ^-5 M to 1 × 10 ^-1 M.

After the completion of the immersion, air drying or heating as necessary is necessary to remove the solvent. In this way, a compound represented by the formula (1) is obtained. A photoelectric conversion element of the present invention which is a film of (pigment) sensitized oxide semiconductor fine particles.

The compound represented by the above formula (1) may be used alone or in combination of several kinds. Further, in the case of mixing, the compounds (pigments) represented by the formula (1) of the present invention may be mixed with other dyes or metal complex dyes. In particular, by mixing and absorbing dyes having different wavelengths, it is possible to obtain a solar cell having high conversion efficiency by using an absorption wavelength having a wide range of amplification. The example of the metal complex dye which can be mixed is not particularly limited, but is preferably a ruthenium complex represented by Non-Patent Document 2 or a quaternary ammonium salt compound thereof, phthalocyanine, ruthenium or the like as a mixture. Examples of the organic coloring matter include a metal-free phthalocyanine, a purple or cyan, a merocyanine, an oxophthalocyanine, a triphenylmethane, and a methine group such as an acrylic dye represented by Patent Document 2 (Methine). A pigment such as a pigment or a xanthene, an azo, an anthraquinone or a quinone. Preferably, a methicone-based dye such as a ruthenium complex, a merocyanine or an acrylic is mentioned. When two or more kinds of dyes are used, the dye may be sequentially adsorbed to the thin film of the semiconductor fine particles, or may be mixed and dissolved to be adsorbed.

The ratio of the pigment to be mixed is not particularly limited, and the optimum conditions can be appropriately selected for the individual dyes. In general, it is preferable to mix from the molars, and about 10% of moules or more per dye is used. When a solution in which two or more kinds of dyes are dissolved or dispersed is used, and a film of the oxide semiconductor fine particles is adsorbed to the dye, the total concentration of the dyes in the solution can be the same as in the case of carrying only one type of the dye. As the solvent in the case of using the mixed dye, a solvent as described above may be used, and the solvent used for each dye may be the same or different.

When the dye is applied to the thin film of the oxide semiconductor fine particles, it is advantageous to carry the dye in the presence of the inclusion compound in order to prevent the dyes from meeting each other. Here, examples of the inclusion compound include a steroid-based compound such as cholic acid, a crown ether, a cyclodextrin, a calixarene, and a polyethylene oxide. Specific examples of preferred examples include deoxycholic acid and deacetylation. Dehydro Deoxycholic acid, chenodeoxycholic acid, cholic acid methyl ester, cholic acid, etc., bile acids, polyethylene oxide, and the like. Further, after the dye is carried, the thin film of the semiconductor fine particles may be treated with an amine compound such as 4-t-butylpyridine. The method of the treatment is, for example, a method of impregnating a substrate provided with a film of a semiconductor fine particle carrying a dye in an ethanol solution of an amine.

In the solar cell of the present invention, the photoelectric conversion element carrying the compound (dye) of the present invention on the thin film of the oxide semiconductor fine particles is used as an electrode on one side, and a counter electrode, a redox electrolyte or a hole transport material or a p-type semiconductor. And so on. As a form of a redox electrolyte, a hole transporting material, a p-type semiconductor, or the like, a liquid, a solidified body (gel or gel), a solid, or the like can be used. In the liquid state, each of the redox electrolyte, the molten salt, the hole transporting material, and the p-type semiconductor is dissolved in a solvent or a normal temperature molten salt or the like as a solidified body (gel or gel). These are included in a polymer matrix or a low molecular gelling agent or the like. As the solid, a redox electrolyte, a molten salt, a hole transporting material, a p-type semiconductor or the like can be used. Examples of the hole transporting material include an amine derivative, a conductive polymer such as polyacetylene, polyaniline or polythiophene, and a triazine-based compound. P-type semi-conductor Examples of the body include CuI and CuSCN. As the counter electrode already has conductivity, it is preferred that the reduction reaction of the redox electrolyte be a catalytic action. For example, those which vaporize platinum, carbon, ruthenium, iridium, or the like, or apply conductive fine particles can be used for the glass or the polymer film.

Examples of the redox electrolyte used in the solar cell of the present invention include a halogen compound having a halogen ion as a counter ion and a halogen redox electrolyte composed of a halogen molecule, ferrocyanide-ferrocyanate or Ferrocene. An organic redox system such as a metal redox electrolyte such as a metal complex such as a ferricinium ion or a cobalt complex, an alkylthio-alkyl disulfide, a Viologen dye, or a hydroquinone-hydrazine An electrolyte or the like is preferred, but a halogen redox-based electrolyte is preferred. The halogen molecule of the halogen redox-based electrolyte composed of a halogen compound-halogen molecule is, for example, an iodine molecule or a bromine molecule, and is preferably an iodine molecule. Further, examples of the halogen compound having a halogen ion as a counter ion include a halogenated metal salt such as LiBr, NaBr, KBr, LiI, NaI, KI, CsI, CaI ₂ , MgI ₂ or CuI or a tetraalkylammonium iodine. A halogen, an organic quaternary ammonium salt such as an imidazolium iodide or a pyridinium iodide, or the like, preferably a salt of a relative ion. Further, in addition to the above-described iodide ion, it is also preferable to use an iridium imide ion such as bis(trifluoromethanesulfonyl) sulfinium ion or a dicyanoquinone imine ion as a counter ion.

Further, when the redox electrolyte is composed of a form containing the solution, an electrochemically inert one is used in the solvent. Examples thereof include acetonitrile, propylene carbonate, ethyl carbonate, 3-methoxypropionitrile, and methoxy group. Acetonitrile, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, γ-butyrolactone, dimethoxyethane, diethyl carbonate, diethyl ether, diethyl carbonate, dimethyl Carbonate, 1,2-dimethoxyethane, dimethylformamide, dimethylhydrazine, 1,3-dioxolan (Dioxolan), methylformate, 2-methyl Tetrahydrofuran, 3-methyl-oxazolidine-2-one, Sulfolane, tetrahydrofuran, water, etc., among others, especially acetonitrile, propylene carbonate, ethyl carbonate, 3-methoxy Preferred are acrylonitrile, methoxyacetonitrile, ethylene glycol, 3-methyl-oxazolidine-2-one, γ-butyrolactone and the like. These may be used alone or in combination of two or more. In the case of a gel electrolyte, those containing an electrolyte or an electrolyte solution in a matrix such as an oligomer or a polymer, or an electrolyte or an electrolyte solution in the same manner as a low molecular gelling agent may be mentioned. The concentration of the redox electrolyte is usually from 0.01 to 99% by mass, preferably from about 0.1 to 90% by mass.

In the solar cell of the present invention, the film of the oxide semiconductor fine particles on the substrate is placed on the counter electrode as in the case of the electrode of the photoelectric conversion element carrying the compound (pigment) represented by the formula (1) of the present invention. This is obtained by filling a solution containing a redox electrolyte.

[Examples]

Hereinafter, the present invention will be described in more detail based on the examples, but the present invention is not limited to the examples. In the examples, the parts are referred to as parts by mass unless otherwise specified. Indicates the concentration of the solution, and M represents mol/L. The maximum absorption wavelength was measured by an ultraviolet-visible spectrophotometer (UV-3100PC, manufactured by Shimadzu Corporation). NMR by JNM-ECS400 (manufactured by JEOL Ltd.).

Synthesis Example 1

5 parts of 2,3-dibromothiophene, 5.5 parts of 5'-formamido-2,2'-bithiophene-5-borate, 0.22 parts of bis(tri-tert-butylphosphine)palladium(0), fluorine 6.4 parts of hydrazine and 126 parts of 1,4-dioxane were added to 28 parts of water, and allowed to react at 80 ° C for 3 hours. The reaction mixture was extracted with chloroform-water, and the chloroform phase was concentrated, and then purified by column chromatography (chloroform-hexane) to afford 2.8 parts of the compound of formula (800) as a yellow solid.

Synthesis Example 2

2.5 parts of the compound represented by the formula (800) obtained in Synthesis Example 1 was dissolved in a solution of 250 parts of acetic acid and 375 parts of chloroform, and 1.6 parts of N-iodosuccinimide was added thereto, and the mixture was stirred at room temperature for 5 hours under light-shielding. . 0.8 parts of N-iodosuccinimide was added, and the mixture was stirred at room temperature for 19 hours under light-shielding. After the reaction, the precipitate was filtered and hexane was washed to obtain 2.9 parts of a compound represented by the following formula (801) as a thin orange solid.

Synthesis Example 3

[1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane addition 1.6 parts, potassium acetate 2 parts and bis(pinacolate) diboron 22 parts of dimethyl hydrazine were added in 2 portions, and stirred under a nitrogen atmosphere. And adding 5 parts of 9,9-dibutyl-N-(9,9-dibutylindol-2-yl)-N-(4-iodophenyl)indol-2-amine to dimethylene A solution of 66 parts was stirred at 80 ° C for 5 hours. The reaction mixture was extracted with toluene-water and the toluene phase was concentrated, and then purified and purified by column chromatography (chloroform-hexane) to afford 3.5 parts of the compound represented by the following formula (802) as a white solid.

Synthesis Example 4

2.1 parts of the compound represented by the formula (801) obtained in Synthesis Example 2, 4.1 parts of the compound represented by the formula (802) obtained in Synthesis Example 3, ruthenium (triphenylphosphine)palladium (0) 0.15 part and 20%. To a solution of 16 parts of sodium carbonate aqueous solution, 300 parts of 1,2-dimethoxyethane was added, and the mixture was reacted under reflux for 4 hours. 2.0 parts of the compound represented by the formula (802) and 0.08 parts of hydrazine (triphenylphosphine)palladium (0) were further added, and the mixture was further reacted under reflux for 3 hours. The reaction mixture was extracted with chloroform-water, and the chloroform phase was concentrated, and then separated and purified by column chromatography (chloroform-hexane, and toluene-hexane) to give a thick orange solid, which is represented by the following formula (803). The compound was 1.2 parts.

Synthesis Example 5

Using 4-bromo-2-hydroxyacetophenone and 2-methoxybenzhydrylhydrazine, according to the synthesis method described in Non-Patent Document 3, the following formula is obtained. (805) The compound represented.

Synthesis Example 6

2.3 parts of 2-hydroxyacetophenone and 2.4 parts of 2-methoxybenzhydrylhydrazine were added to 24 parts of absolute ethanol, and the mixture was reacted at 85 ° C for 2 days under a nitrogen atmosphere. After the completion of the reaction, the precipitated solid was washed with a small amount of ethanol, and dried under reduced pressure to give a compound (yield: s.

Synthesis Example 7

4.1 parts of the compound represented by the formula (806) obtained in Synthesis Example 6 was dissolved and ice-cooled to 230 parts of tetrahydrofuran. After adding a small amount of 8.0 parts of lead tetraacetate, the mixture was stirred at room temperature for about 5 hours. After the reaction is over, Filtration was carried out by adding a cerium oxide gel to a Kiriyama funnel, and the filtrate was distilled off under reduced pressure to give 4.4 parts of a compound represented by the following formula (807) as a yellow earth solid.

Synthesis Example 8

1.6 parts of the compound represented by the formula (805) obtained in Synthesis Example 5 and 1.2 parts of the compound represented by the formula (807) obtained in Synthesis Example 7 were stirred and dissolved in a mixture of 37 parts of methanol and 28 parts of acetic acid. A homogeneous solution is obtained. The solution was ice-cooled, and after adding 19 parts of aqueous ammonia, it was stirred at 45 ° C overnight. It was quenched with a saturated aqueous solution of sodium hydrogencarbonate, and the precipitated solid was filtered. The obtained solid was separated and purified by column chromatography (hexane-benzene) to obtain 0.31 part of the compound represented by the following formula (808) as a solid cyan solid.

Synthesis Example 9

1.2 parts of the compound represented by the formula (808) obtained in Synthesis Example 8 was dissolved in 72 parts of anhydrous toluene under a nitrogen atmosphere, and then 0.58 parts of triethylamine was added thereto and heated to 80 °C. After slowly dropping 3.4 parts of trifluoroboron diethyl ether complex, it was stirred at 100 ° C overnight. After adding 40 parts of water for quenching, extracting with 110 parts of ethyl acetate, and washing with 300 parts of water, sodium sulfate was added to the organic layer and dried. The sodium sulfate was filtered and concentrated. The obtained solid was separated and purified by column chromatography (hexane-benzene) to obtain 1.1 parts of the compound represented by the following formula (809) as a solid cyan solid.

Synthesis Example 10

The formula (809) obtained in Synthesis Example 9 is shown in a nitrogen atmosphere. 1.1 parts of the compound shown and 1.9 parts of potassium acetate were dissolved in 29 parts of anhydrous dimethoxyethane, and subjected to three freeze degassing. To the glove box, 1.3 parts of bis(pinacol) diboron was added to the solution. After adding 29 parts of anhydrous dimethoxyethane to other vessels and performing three freeze degassing, [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (II) was added to the glove box. ) 0.38 parts. This solution was added to the previous solution, and stirred at 80 ° C for 10 hours under a nitrogen atmosphere. The reaction mixture was quenched with 10 parts of water, and extracted with ethyl acetate (90 parts), and washed with water (200 parts), and then sodium sulfate was added to the organic layer and dried. The sodium sulfate was filtered and concentrated. The obtained solid was separated and purified by column chromatography (hexane-dichloromethane) to obtain 1.0 part of the compound represented by the following formula (810) as a solid cyan solid.

Synthesis Example 11

0.084 parts of the compound represented by the formula (803) obtained in Synthesis Example 4, 0.19 parts of the compound represented by the formula (810) obtained in Synthesis Example 10, and 0.013 parts of bis(tri-tert-butylphosphine)palladium (0), 0.026 parts of cesium fluoride and 0.23 parts of water were added to 2.7 parts of 1,4-dioxane, and refluxed for 3.5 hours. The reaction mixture was extracted with chloroform-water and concentrated with chloroform. Chromatography (chloroform-hexane) was separated and purified to give 0.11 part of the compound represented by the following formula (811) as a black-green solid.

Example 1

0.13 parts of the compound represented by the formula (811) obtained in Synthesis Example 11 and 0.047 parts of cyanoacetic acid were dissolved in 18 parts of a mixture of ethanol and toluene (2:1), and 0.005 part of anhydrous piperazine was added thereto, followed by refluxing. 1 hour. 0.047 parts of cyanoacetic acid was added, and the mixture was further reacted for 3 hours under reflux. Further, 0.047 parts of cyanoacetic acid and 0.005 parts of anhydrous piperazine were added, and the mixture was reacted for 3 hours under reflux. The reaction mixture was extracted with chloroform-water, and the chloroform phase was concentrated, and then separated and purified by column chromatography (chloroform-methanol) to obtain the present invention represented by the following formula (812) as a black-green solid. The compound (Compound 1 of Table 1) was 0.051 part.

The maximum absorption wavelength of the compound represented by the formula (812) and the measured value of the nuclear magnetic resonance apparatus are as follows.

Maximum absorption wavelength; λmax=634nm (1.6×10 ^-5 M, tetrahydrofuran solution)

NMR measurement; ¹ H-NMR (PPM: DMSO-d6): 0.53 (m.8H), 0.61 (m.12H), 0.98 (m.8H), 1.85 (m.8H), 3.07 (d. 6H), 6.90 (m.1H), 6.95 (m.1H), 7.01 (m.5H), 7.06 (m.1H), 7.14 (d.2H), 7.16 (m.1H), 7.28 (m.9H) ), 7.37 (m.4H), 7.45 (m.2H), 7.56 (m.5H), 7.72 (m.5H), 7.95 (s, 1H), 8.14 (d, 1H), 8.18 (d, 1H) , 8.63 (s, 1H)

Example 2

The compound of the present invention (Compound 1 of Table 1) represented by the formula (812) obtained in Example 1 and the cholic acid represented by the following formula (z) are, for example, 3.2 × 10 ^-4 M and 4 ×, respectively. 10 ^-2 M is dissolved in ethanol. This solution was immersed in a porous substrate (semiconductor thin film electrode which was sintered at 450 ° C for 30 minutes on a transparent conductive glass electrode) at room temperature, and then washed with a solvent and dried. The photoelectric conversion element of the present invention is obtained. The semiconductor thin film layer of the photoelectric conversion element obtained as described above and the platinum layer of the conductive glass on which platinum is sputtered are disposed opposite to each other, and a solution containing an electrolyte is injected into the void, and sealed to obtain a solar cell of the present invention. The electrolytic solution was used for acetonitrile: ethyl carbonate (2:3) to dissolve iodine/tetrapropylammonium iodide to 0.05 M/0.5 M, respectively.

Comparative example 1

The compound of the present invention represented by the following formula (A) (the compound (160) described in Patent Document 3) is used instead of the compound of the present invention represented by the formula (812) obtained in the first embodiment, and other examples are 2, and get the solar cell for comparison.

(IPCE measurement of solar cells)

The IPCE of 300 to 800 nm of the solar cells obtained in Example 2 and Comparative Example 1 was measured by DC method using SM-25YD manufactured by Spectrophotometer Co., Ltd., and the obtained IPCE spectrum is shown in Fig. 1 . In Fig. 1, "1" indicates the measurement result of the solar cell of the present invention obtained in Example 2, and "A" indicates the measurement result of the comparative solar cell obtained by using the compound represented by the above formula (A).

(Evaluation of photoelectric conversion characteristics of solar cells)

The size of the battery measured by the photoelectric conversion characteristics of the solar cells obtained in Example 2 and Comparative Example 1 was evaluated, and the effective portion was set to 0.25 cm ² . The light source was set to 100 mW/cm ² by a 500 (xenon air passing) 1.5 filter using a 500 W xenon lamp. It was measured using a potent constant current (Potentiometer galvanostat). The results are shown in Table 20.

From the results of Fig. 1, it is understood that the compound of the present invention can be used for a solar cell of a sensitizing dye, and the visible light in a long wavelength region can be efficiently converted into electricity as compared with a solar cell for comparison.

Further, from the results of Table 20, it is understood that the compound of the present invention is used in a solar cell of a sensitizing dye, and is excellent in photoelectric conversion characteristics as compared with a solar cell for comparison.

[Industrial Applicability]

By using a compound of the present invention having a specific partial structure for a sensitizing dye, it is possible to improve a photoelectric conversion element and a solar cell which can efficiently convert a wide range of visible light into electricity and exhibit high conversion efficiency.

Claims (20)

a compound represented by the following formula (1), (In the formula (1), m represents an integer of 1 to 5, l and n each independently represent an integer of 0 to 6, and j represents an integer of 0 to 3; and X ₁ and X ₂ independently represent a hydrogen atom, a carboxyl group, a hydroxyl group, a phosphate group, a sulfonic acid group, a cyano group, a decyl group, a decylamino group, an alkoxycarbonyl group or a sulfonylphenyl group, and X ₁ and X ₂ may be bonded to each other to form a ring; and Q ₁ and Q ₂ each independently represent an oxygen atom or a sulfur atom. a selenium atom or NR ₁₁ ; R ₁₁ represents a hydrogen atom, an aromatic residue or an aliphatic hydrocarbon residue; and when m is 2 or more and Q ₁ is a plural, individual Q ₁ may be the same or different from each other. j is 2 or more and Q ₂ is plural; individual Q ₂ may be the same or different from each other; A ₁ , A ₂ , A ₃ , A ₅ and A ₆ respectively represent a hydrogen atom, an aromatic residue, an aliphatic group. a hydrocarbon residue, a cyano group, a halogen atom, a carboxy oxime amino group, a decylamino group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an arylcarbonyl group or a fluorenyl group; 1 is 2 or more and A ₂ and A ₃ are plural In the case where the individual A ₂ and A ₃ may be the same or different from each other, and n is 2 or more and A ₅ and A ₆ are plural, the individual A ₅ and A ₆ may be the same or different from each other. ; or, l is 0 to In the case of the above, any one of A ₁ , A ₂ and A ₃ may form a plurality of rings, and A ₄ represents a hydrogen atom, an aliphatic hydrocarbon residue, a cyano group, a halogen atom, a carboxy oxime group, an alkoxy group, Amidino group, alkoxycarbonyl group or fluorenyl group; when m is 2 or more and A ₄ is plural, individual A ₄ may be the same or different from each other; A ₇ and A ₈ each independently represent a hydrogen atom, an aliphatic group a hydrocarbon residue, a cyano group, a halogen atom, a carboguanamine group, an alkoxy group, an alkoxycarbonyl group or a fluorenyl group; wherein j is 2 or more and A ₇ and A ₈ are plural, and individual A ₇ and A _{8 are present.} May be the same or different from each other; R ₁ represents the following formula (2) (In the formula (2), M represents a metalloid atom; Y ₁ , Y ₂ and Y ₃ each independently represent a hydrogen atom or an aromatic residue; Z ₁ and Z ₂ each independently represent a halogen atom; and Ar ₁ and Ar ₂ are each independently a residue in which one hydrogen atom is removed from the aromatic ring Ar ₁ of the compound represented by the aromatic ring); when m is 2 or more and R ₁ is plural, the individual R ₁ may be the same or different from each other; ₂ is the following formula (3003) (In the formula (3003), R ₁₄ and R ₁₅ each independently represent a hydrogen atom, an aromatic residue or an aliphatic hydrocarbon residue; and R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ each independently represent a hydrogen atom or an aromatic residue. a group represented by an aliphatic hydrocarbon residue, a cyano group, a decyl group, a decylamino group, an alkoxy group, an alkoxycarbonyl group or a sulfonylphenyl group; or, when n is other than 0, A ₅ , A ₆ And any one of R ₂ may form a plurality of rings). The compound of claim 1, wherein m in the formula (1) is 1 to 3. The compound of claim 2, wherein m in the formula (1) is 1. The compound of claim 1, wherein Q ₁ and Q ₂ in the formula (1) are a sulfur atom. The compound of claim 1, wherein l and n in the formula (1) are 0. The compound of claim 1, wherein one of X ₁ and X ₂ in the formula (1) is a carboxyl group, and the other is a carboxyl group, a cyano group or a fluorenyl group. The compound of claim 6, wherein one of X ₁ and X ₂ in the formula (1) is a carboxyl group and the other is a cyano group. The compound of claim 1, wherein X ₁ and X ₂ in the formula (1) are bonded to form a ring structure. The compound of claim 1, wherein A ₁ to A ₈ in the formula (1) are a hydrogen atom. The compound of claim 1, wherein the R ₁ in the formula (1) is from the following formula (3) (In the formula (3), Z ₃ and Z ₄ each independently represent a halogen atom; and A ₂₃ and A ₂₄ each independently represent a benzene ring of a compound represented by a hydrogen atom, a halogen atom, an aliphatic hydrocarbon residue or an alkoxy group) ₁ removes the residue of one hydrogen atom. The compound of claim 10, wherein Z ₃ and Z ₄ in the formula (3) are fluorine atoms, and A ₂₃ and A ₂₄ are methoxy groups. The compound of claim 1, wherein R ₁₄ and R ₁₅ in formula (3003) are the following formula (3001) (In the formula (3001), R ₁₂ and R ₁₃ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), and R ₁₆ to R ₁₉ are each independently a hydrogen atom or a carbon number of 1 to 4. Alkoxy. The compound of claim 12, wherein R ₂ in formula (1) is represented by the following formula (3109) to (3114) The basis of any one of them. The compound of claim 13, wherein R ₂ in the formula (1) is a group represented by the formula (3110), (3111), (3113) or (3114). The compound of claim 14, wherein the R ₂ formula (3111) represented by the formula (1) is a group represented by the formula (3111). The compound of claim 1, which is represented by the following formula (812) Expressed. A photoelectric conversion element which carries a film of one or more kinds of oxide semiconductor fine particles provided on a substrate, which is a compound represented by the formula (1) described in Claim 1. A photoelectric conversion element which carries one or more compounds represented by the formula (1) described in the claim 1 and an oxide semiconductor provided on the substrate with a sensitizing dye compound having a structure other than the formula (1) A film of microparticles. The photoelectric conversion element according to claim 17 or 18, wherein the oxide semiconductor fine particle system contains titanium oxide, zinc oxide or tin oxide. A solar cell comprising the photoelectric conversion element according to any one of claims 17 to 19.