JP2011026412A - Pigment for photoelectric conversion element and photoelectric conversion element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photoelectric conversion element capable of improving conversion efficiency. <P>SOLUTION: The photoelectric conversion element includes a working electrode 10 having a pigment and a carrier that carries the pigment (for example, a metal oxide semiconductor layer 12). The pigment includes a cyanine compound. In the cyanine compound, at least one of heterocyclic ring skeletons bonded to both ends of a methine chain has a quinoline skeleton or a pyridine skeleton. Having the quinoline skeleton or the pyridine skeleton, the cyanine compound has broader light absorption wavelengths compared with the cyanine compound without those skeletons. Therefore, electronic injection efficiency to the carrier becomes high when light enters the pigment including the cyanine compound having the quinoline skeleton or the pyridine skeleton. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a photoelectric conversion element using a dye and a dye suitably used for the photoelectric conversion element.

  Conventionally, dyes are widely used in various technical fields. As an example, in the field of photoelectric conversion elements such as solar cells, they are used for dye-sensitized photoelectric conversion elements using a dye having a photosensitizing action. This dye-sensitized photoelectric conversion element can be expected to have a theoretically high efficiency, and is considered to be very advantageous in terms of cost compared to a conventional photoelectric conversion element using a silicon semiconductor.

  The dye-sensitized photoelectric conversion element has an electrode having an oxide semiconductor as a dye carrier. In this dye-sensitized photoelectric conversion element, the dye is absorbed and excited by the incident light, and the excited dye injects electrons into the carrier to perform photoelectric conversion.

  Thus, ruthenium complex dyes and organic dyes are known as dyes used in dye-sensitized photoelectric conversion elements. In particular, since organic dyes are relatively stable and can be easily synthesized, various studies have been made. Specifically, for the purpose of improving the conversion efficiency, a cyanine dye having a structure in which an indolenine skeleton is bonded to both ends of a methine chain skeleton and a carboxylic acid group as an anchor group for adsorbing to an oxide semiconductor electrode is provided. Used (see, for example, Patent Document 1). In addition, a technique using a cationic dye having a methine chain and an anionic dye having a methine chain in combination is also known (see, for example, Patent Document 2).

JP 2008-166119 A JP-A-11-167937

  However, a conventional photoelectric conversion element using a cyanine dye or a dye having a methine chain does not have a sufficient conversion efficiency, and further improvement of the conversion efficiency is desired.

  This invention is made | formed in view of this problem, The objective is to provide the pigment | dye for photoelectric conversion elements which can improve conversion efficiency, and a photoelectric conversion element.

  The pigment | dye for photoelectric conversion elements of this invention has a cyanine structure represented by Chemical formula (1). In addition, the photoelectric conversion element of the present invention includes an electrode having a dye and a carrier carrying the dye, and the dye contains a cyanine compound having the same structure as the cyanine structure shown in chemical formula (1).

（Ｒ１は化学式（２）〜化学式（６）で表される基のうちのいずれか１つであり、Ｒ２は化学式（７）〜化学式（１０）で表される基のうちのいずれか１つである。Ｑは炭素原子数１以上７以下のメチン鎖を骨格とする連結基である。Ｚ^p-はｐ価のアニオンであり、ｐは１あるいは２であり、ｑは電荷を中性に保つ係数である。）

(R1 is any one of groups represented by chemical formula (2) to chemical formula (6), and R2 is any one of groups represented by chemical formula (7) to chemical formula (10). Q is a linking group having a skeleton of a methine chain having 1 to 7 carbon atoms, Z ^p- is a p-valent anion, p is 1 or 2, and q neutralizes the charge. (The coefficient to keep.)

（Ｒ１０〜Ｒ１３は各々独立に水素原子、水酸基、ニトロ基、シアノ基あるいはハロゲン原子、またはアルキル基、アルコキシ基、アリール基、アリールアルキル基あるいはそれらの誘導体であり、Ｒ１０およびＲ１１のうちの少なくとも一方とＲ１２およびＲ１３のうちの少なくとも一方とはそれぞれ脱離して二重結合を形成してもよいし、それぞれ連結して環構造を形成してもよい。Ｒ１４はアルキレン基である。Ｘは−Ｃ（Ｒ１５）（Ｒ１６）−で表される基、−Ｎ（Ｒ１７）−で表される基、硫黄原子、酸素原子、セレン原子あるいはテルル原子である。Ｒ１５〜Ｒ１７は各々独立に水素原子あるいは化学式（１１）で表される基、または化学式（１１）に示した基に該当するものを除く、アルキル基、アルコキシ基、アリール基、アリールアルキル基あるいはそれらの誘導体である。Ｙ１はカルボン酸基（−Ｃ（＝Ｏ）−ＯＨ）あるいはカルボン酸イオン基（−Ｃ（＝Ｏ）−Ｏ^- ）である。）

(R10 to R13 are each independently a hydrogen atom, a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, or a derivative thereof, and at least one of R10 and R11 And at least one of R12 and R13 may be eliminated to form a double bond, or may be linked to form a ring structure, R14 is an alkylene group, and X is —C. A group represented by (R15) (R16)-, a group represented by -N (R17)-, a sulfur atom, an oxygen atom, a selenium atom or a tellurium atom, wherein R15 to R17 are each independently a hydrogen atom or a chemical formula; An alkyl group, an alkoxy group, an aryl group other than the group represented by (11) or the group represented by the chemical formula (11), .Y1 a reel alkyl group, or a derivative thereof is a carboxylic acid group (-C (= O) -OH) or carboxylic acid ion group ^{(-C (= O) -O -} ) is).

（Ｒ１８〜Ｒ２３およびＲ２５〜Ｒ３０は各々独立に水素原子、水酸基、ニトロ基、シアノ基あるいはハロゲン原子、またはアルキル基、アルコキシ基、アリール基、アリールアルキル基あるいはそれらの誘導体である。Ｒ２４およびＲ３１はアルキレン基である。Ｙ２およびＹ３はカルボン酸基あるいはカルボン酸イオン基である。）

(R18 to R23 and R25 to R30 are each independently a hydrogen atom, a hydroxyl group, a nitro group, a cyano group or a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, or a derivative thereof. R24 and R31 are An alkylene group, Y2 and Y3 are a carboxylic acid group or a carboxylic acid ion group.)

（Ｒ３２〜Ｒ３５およびＲ３７〜Ｒ４０は各々独立に水素原子、水酸基、ニトロ基、シアノ基あるいはハロゲン原子、またはアルキル基、アルコキシ基、アリール基、アリールアルキル基あるいはそれらの誘導体である。Ｒ３６およびＲ４１はアルキレン基である。Ｙ４およびＹ５はカルボン酸基あるいはカルボン酸イオン基である。）

(R32 to R35 and R37 to R40 are each independently a hydrogen atom, a hydroxyl group, a nitro group, a cyano group or a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, or a derivative thereof. R36 and R41 are Y4 and Y5 are carboxylic acid groups or carboxylic acid ion groups.

（Ｒ４２〜Ｒ６５は各々独立に水素原子、水酸基、ニトロ基、シアノ基あるいはハロゲン原子、またはアルキル基、アルコキシ基、アリール基、アリールアルキル基あるいはそれらの誘導体である。）

(R42 to R65 are each independently a hydrogen atom, a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, or a derivative thereof.)

（Ｌ１とＴ１との間の結合は二重結合あるいは三重結合であり、Ｌ１は炭素原子を表し、Ｔ１は炭素原子、酸素原子あるいは窒素原子を表し、ｘ、ｙおよびｚは各々独立に０または１である（ただし、Ｔ１が酸素原子である場合にはｘおよびｙは０であり、Ｔ１が窒素原子の場合には（ｙ＋ｚ）は０あるいは１である。）。Ｒ６６〜Ｒ６８は各々独立に水素原子、水酸基、ニトロ基、シアノ基、ハロゲン原子、炭素原子数１以上４以下のアルキル基あるいは炭素原子数１以上４以下のハロゲン化アルキル基であり、Ｒ６９は水素原子、水酸基、ニトロ基、シアノ基、ハロゲン原子、炭素原子数１以上４以下のアルキル基、炭素原子数１以上４以下のアルコキシ基、炭素原子数１以上４以下のハロゲン化アルキル基あるいは炭素原子数１以上４以下のハロゲン化アルコキシ基であり、Ｒ６６とＲ６９、Ｒ６７とＲ６８とはそれぞれ連結して環構造を形成してもよい。ｎは０以上４以下の整数である。）

(The bond between L1 and T1 is a double bond or a triple bond, L1 represents a carbon atom, T1 represents a carbon atom, an oxygen atom or a nitrogen atom, and x, y and z are each independently 0 or (However, when T1 is an oxygen atom, x and y are 0, and when T1 is a nitrogen atom, (y + z) is 0 or 1.) R66 to R68 are each independently A hydrogen atom, a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, R69 is a hydrogen atom, a hydroxyl group, a nitro group, A cyano group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms A halogenated alkoxy group of the lower, R66 and R69, R67 and may be to form a ring structure, respectively and R68 .n is zero or an integer of 4 or less.)

  The above-mentioned “derivative” refers to a group in which a hydrogen atom in a substituent is substituted with another atom or atomic group. Examples of the atom introduced instead of the hydrogen atom include a halogen atom and the like. Examples of the atomic group introduced instead of a hydrogen atom include a hydroxyl group, a nitro group, a cyano group, an acyl group, an acidic group, a saturated cyclic hydrocarbon group, an unsaturated cyclic hydrocarbon group, and an aromatic ring group. Or a heterocyclic group etc. are mentioned. In addition, “may be eliminated to form a double bond” means, for example, that one of R10 and R11 and one of R12 and R13 shown in chemical formula (2) is By desorption, the bond between the carbon atom into which R10 and R11 are introduced and the carbon atom into which R12 and R13 are introduced may be a double bond. Further, the “halogenation” of the halogenated alkyl group and the halogenated alkoxy group described in the chemical formula (11) means that a part or all of the hydrogen atoms contained in the alkyl group and the alkoxy group are one kind of halogen elements or A group substituted with two or more atoms.

  In the dye for photoelectric conversion element and photoelectric conversion element of the present invention, the cyanine structure represented by the chemical formula (1) has at least one of the heterocyclic skeletons (R1, R2) bonded to both ends of the methine chain skeleton (Q). Contains quinoline skeleton or pyridine skeleton. Thereby, as compared with a cyanine dye having a five-membered ring skeleton bonded to both ends of the methine chain, π conjugation as a whole molecule is broadened, so that a light absorption peak is broadened and a light absorption wavelength region is widened. Moreover, in the cyanine structure represented by the chemical formula (1), an alkylene group (R14, R24) having a carboxylic acid group or a carboxylic acid ion group (Y1 to Y5) with respect to the nitrogen atom contained in the heterocyclic skeleton in R1. , R31, R36 or R41) is introduced and functions as an anchor group contributing to the bond with the carrier. For this reason, the electron injection efficiency with respect to a support body becomes high compared with the pigment | dye which has an anchor group of another position and another structure. For these reasons, a compound having a cyanine structure represented by the chemical formula (1) (hereinafter referred to as a cyanine compound represented by the chemical formula (1)) has a wide wavelength when irradiated with light in a state of being carried on the carrier. In addition to being excited by absorbing light in the region, electrons can be efficiently injected into the carrier. Therefore, in the photoelectric conversion element using the cyanine compound represented by the chemical formula (1) as the dye, the ratio of the amount of electrons injected into the carrier with respect to the amount of light irradiated is increased, and the efficiency of photoelectric conversion is improved.

  In the photoelectric conversion element dye and the photoelectric conversion element of the present invention, R1 in the chemical formula (1) is preferably a group represented by the chemical formula (2-1). In general cyanine compounds (compounds having a structure in which a heterocyclic skeleton is bonded to both ends of the methine chain skeleton), a structure in which carbon atoms and heteroatoms constituting the methine chain skeleton and the heterocyclic skeleton are arranged in a plane (Structure with high flatness). When the planarity of the molecular structure is increased, molecules are likely to associate with each other to form an association such as a dimer, and the dye that has formed the association is less likely to contribute to photoelectric conversion. However, when R1 has the group represented by the chemical formula (2-1) including an indolenine skeleton, the benzyl group or alkyl group introduced as at least one of R15 and R16 includes a methine chain skeleton and a heterocyclic skeleton. It arrange | positions so that it may protrude in the space of both the upper surface side and lower surface side with respect to a plane. For this reason, the planarity of the whole molecule becomes low and it becomes difficult to associate. Therefore, in the photoelectric conversion element using the cyanine compound represented by the chemical formula (1) as the dye, when it has a group represented by the chemical formula (2-1) as R1 in the chemical formula (1), it was supported on the support. Since the ratio of the aggregate that hardly contributes to photoelectric conversion in the entire dye is decreased, the efficiency of photoelectric conversion is improved.

（Ｒ１４はアルキレン基である。Ｒ１５，Ｒ１６は各々独立に水素原子あるいは上記した化学式（１１）に示した基、または化学式（１１）に示した基に該当するものを除く、アルキル基、アルコキシ基、アリール基、アリールアルキル基あるいはそれらの誘導体である。ただし、Ｒ１５およびＲ１６のうちの少なくとも一方はベンジル基あるいはアルキル基である。Ｙ１はカルボン酸基あるいはカルボン酸イオン基である。環Ａはベンゼン環、ナフタレン環、フェナンスレン環あるいはそれらの誘導体である。）

(R14 is an alkylene group. R15 and R16 are each independently a hydrogen atom, an alkyl group or an alkoxy group other than the group shown in the chemical formula (11) or the group shown in the chemical formula (11). An aryl group, an arylalkyl group or a derivative thereof, wherein at least one of R15 and R16 is a benzyl group or an alkyl group, Y1 is a carboxylic acid group or a carboxylate ion group, and ring A is benzene. Ring, naphthalene ring, phenanthrene ring or derivatives thereof.)

  In the photoelectric conversion element dye and photoelectric conversion element of the present invention, Q in chemical formula (1) is a linking group having a skeleton of a methine chain having 3 carbon atoms, and R2 is chemical formula (7) or chemical formula (8). It is preferable that it is a group shown in (4). This is because the light absorption wavelength region becomes wider and the efficiency of electron injection into the carrier becomes higher. Further, Q in the chemical formula (1) may be a linking group in which a cyano group is introduced into a methine chain having 5 carbon atoms. Furthermore, R14, R24, R31, R36 and R41 of the groups represented by the chemical formulas (2) to (6) and (2-1) may be ethylene groups. In either case, the efficiency of electron injection into the carrier tends to be high, and photoelectric conversion is performed satisfactorily.

  Furthermore, in the photoelectric conversion element of the present invention, the support preferably contains zinc oxide (ZnO). Thereby, the efficiency of photoelectric conversion further improves.

  According to the dye for photoelectric conversion elements of the present invention, since it has the cyanine structure represented by the chemical formula (1), it is excited by absorbing light in a wide wavelength range as compared with a dye having no structure. The electron injection efficiency for the supported carrier is improved. Therefore, according to the photoelectric conversion element of the present invention, since the dye supported on the support contains the compound having the cyanine structure represented by the chemical formula (1), the conversion efficiency can be improved. In this case, if R1 in the chemical formula (1) is a group shown in the above chemical formula (2-1), formation of an aggregate is suppressed, so that the conversion efficiency can be further improved. In addition, when Q in chemical formula (1) is a linking group having a methine chain having 3 carbon atoms as a skeleton and R2 is a group represented by chemical formula (7) or chemical formula (8), Conversion efficiency can be further improved by enlarging and improving the efficiency of electron injection into the carrier.

  In particular, the conversion efficiency can be further improved if the carrier carrying the dye contains zinc oxide.

It is sectional drawing showing the structure of the photoelectric conversion element using the pigment | dye which concerns on one embodiment of this invention. It is sectional drawing which extracts and expands and shows the principal part of the photoelectric conversion element shown in FIG. It is a characteristic view showing the relationship between the wavelength and IPCE in the dye-sensitized photoelectric conversion element of an experimental example.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

  A dye according to an embodiment of the present invention is used for a dye-sensitized photoelectric conversion element (for a photoelectric conversion element) and has a cyanine structure represented by the chemical formula (1) (hereinafter, chemical formula). (Referred to as the cyanine compound shown in (1)). The cyanine compound represented by the chemical formula (1) has, for example, an adsorptive property (bonding property) to a support including a metal oxide semiconductor material, and is excited by absorbing light to the electron. It is a compound that can be injected.

In the chemical formula (1), the cyanine compound has a resonance structure between the methine chain skeleton (Q) and two nitrogen atoms in the heterocyclic skeleton (R1, R2) introduced at both ends thereof. Represents. Therefore, the chemical formula (1) represents a structural formula in which the nitrogen atom contained in the heterocyclic skeleton of R1 is positively charged (N ⁺ ). The cyanine compound represented by the chemical formula (1) It is not limited to the structure represented by the structural formula. For example, the nitrogen atom contained in the heterocyclic skeleton of R2 in the chemical formula (1) may be in a positively charged state. In this case, the bond between the carbon atoms in the methine chain skeleton so as to form a double bond between the nitrogen atom contained in the heterocyclic skeleton of R2 and the carbon atom adjacent to the Q side of the nitrogen atom. And a resonance structure represented by a structural formula in which double bonds and single bonds are alternated in a bond between a nitrogen atom contained in the heterocyclic skeleton of R1 and a carbon atom adjacent to the Q side of the nitrogen atom. It may be taken. Moreover, you may represent with another structural formula so that it may have a resonance structure. The same applies to chemical formulas and the like described later.

（Ｒ１は化学式（２）〜化学式（６）で表される基のうちのいずれか１つであり、Ｒ２は化学式（７）〜化学式（１０）で表される基のうちのいずれか１つである。Ｑは炭素原子数１以上７以下のメチン鎖を骨格とする連結基である。Ｚ^p-はｐ価のアニオンであり、ｐは１あるいは２であり、ｑは電荷を中性に保つ係数である。）

(R1 is any one of groups represented by chemical formula (2) to chemical formula (6), and R2 is any one of groups represented by chemical formula (7) to chemical formula (10). Q is a linking group having a skeleton of a methine chain having 1 to 7 carbon atoms, Z ^p- is a p-valent anion, p is 1 or 2, and q neutralizes the charge. (The coefficient to keep.)

（Ｒ１０〜Ｒ１３は各々独立に水素原子、水酸基、ニトロ基、シアノ基あるいはハロゲン原子、またはアルキル基、アルコキシ基、アリール基、アリールアルキル基あるいはそれらの誘導体であり、Ｒ１０およびＲ１１のうちの少なくとも一方とＲ１２およびＲ１３のうちの少なくとも一方とはそれぞれ脱離して二重結合を形成してもよいし、それぞれ連結して環構造を形成してもよい。Ｒ１４はアルキレン基である。Ｘは−Ｃ（Ｒ１５）（Ｒ１６）−で表される基、−Ｎ（Ｒ１７）−で表される基、硫黄原子、酸素原子、セレン原子あるいはテルル原子である。Ｒ１５〜Ｒ１７は各々独立に水素原子あるいは化学式（１１）で表される基、または化学式（１１）に示した基に該当するものを除く、アルキル基、アルコキシ基、アリール基、アリールアルキル基あるいはそれらの誘導体である。Ｙ１はカルボン酸基（−Ｃ（＝Ｏ）−ＯＨ）あるいはカルボン酸イオン基（−Ｃ（＝Ｏ）−Ｏ^- ）である。）

(R10 to R13 are each independently a hydrogen atom, a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, or a derivative thereof, and at least one of R10 and R11 And at least one of R12 and R13 may be eliminated to form a double bond, or may be linked to form a ring structure, R14 is an alkylene group, and X is —C. A group represented by (R15) (R16)-, a group represented by -N (R17)-, a sulfur atom, an oxygen atom, a selenium atom or a tellurium atom, wherein R15 to R17 are each independently a hydrogen atom or a chemical formula; An alkyl group, an alkoxy group, an aryl group other than the group represented by (11) or the group represented by the chemical formula (11), .Y1 a reel alkyl group, or a derivative thereof is a carboxylic acid group (-C (= O) -OH) or carboxylic acid ion group ^{(-C (= O) -O -} ) is).

（Ｒ１８〜Ｒ２３およびＲ２５〜Ｒ３０は各々独立に水素原子、水酸基、ニトロ基、シアノ基あるいはハロゲン原子、またはアルキル基、アルコキシ基、アリール基、アリールアルキル基あるいはそれらの誘導体である。Ｒ２４およびＲ３１はアルキレン基である。Ｙ２およびＹ３はカルボン酸基あるいはカルボン酸イオン基である。）

(R18 to R23 and R25 to R30 are each independently a hydrogen atom, a hydroxyl group, a nitro group, a cyano group or a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, or a derivative thereof. R24 and R31 are An alkylene group, Y2 and Y3 are a carboxylic acid group or a carboxylic acid ion group.)

（Ｒ３２〜Ｒ３５およびＲ３７〜Ｒ４０は各々独立に水素原子、水酸基、ニトロ基、シアノ基あるいはハロゲン原子、またはアルキル基、アルコキシ基、アリール基、アリールアルキル基あるいはそれらの誘導体である。Ｒ３６およびＲ４１はアルキレン基である。Ｙ４およびＹ５はカルボン酸基あるいはカルボン酸イオン基である。）

(R32 to R35 and R37 to R40 are each independently a hydrogen atom, a hydroxyl group, a nitro group, a cyano group or a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, or a derivative thereof. R36 and R41 are Y4 and Y5 are carboxylic acid groups or carboxylic acid ion groups.

（Ｒ４２〜Ｒ６５は各々独立に水素原子、水酸基、ニトロ基、シアノ基あるいはハロゲン原子、またはアルキル基、アルコキシ基、アリール基、アリールアルキル基あるいはそれらの誘導体である。）

(R42 to R65 are each independently a hydrogen atom, a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, or a derivative thereof.)

（Ｌ１とＴ１との間の結合は二重結合あるいは三重結合であり、Ｌ１は炭素原子を表し、Ｔ１は炭素原子、酸素原子あるいは窒素原子を表し、ｘ、ｙおよびｚは各々独立に０または１である（ただし、Ｔ１が酸素原子である場合にはｘおよびｙは０であり、Ｔ１が窒素原子の場合には（ｙ＋ｚ）は０あるいは１である。）。Ｒ６６〜Ｒ６８は各々独立に水素原子、水酸基、ニトロ基、シアノ基、ハロゲン原子、炭素原子数１以上４以下のアルキル基あるいは炭素原子数１以上４以下のハロゲン化アルキル基であり、Ｒ６９は水素原子、水酸基、ニトロ基、シアノ基、ハロゲン原子、炭素原子数１以上４以下のアルキル基、炭素原子数１以上４以下のアルコキシ基、炭素原子数１以上４以下のハロゲン化アルキル基あるいは炭素原子数１以上４以下のハロゲン化アルコキシ基であり、Ｒ６６とＲ６９、Ｒ６７とＲ６８とはそれぞれ連結して環構造を形成してもよい。ｎは０以上４以下の整数である。）

(The bond between L1 and T1 is a double bond or a triple bond, L1 represents a carbon atom, T1 represents a carbon atom, an oxygen atom or a nitrogen atom, and x, y and z are each independently 0 or (However, when T1 is an oxygen atom, x and y are 0, and when T1 is a nitrogen atom, (y + z) is 0 or 1.) R66 to R68 are each independently A hydrogen atom, a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, R69 is a hydrogen atom, a hydroxyl group, a nitro group, A cyano group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms A halogenated alkoxy group of the lower, R66 and R69, R67 and may be to form a ring structure, respectively and R68 .n is zero or an integer of 4 or less.)

The cyanine compound represented by the chemical formula (1) includes R1, R2 and a structural part having a methine chain skeleton (Q) that connects R1 and R2 and an anion (Z ^p− ) contained depending on the structural part. It is comprised by. In the cyanine compound represented by the chemical formula (1), the number of carbon atoms of the methine chain skeleton (Q), which is the chromophore, is in the range of 1 to 7, so that the light absorption peak wavelength of the cyanine compound is from the ultraviolet region. It will be in the near infrared region. This light absorption peak is larger than the light absorption peak of a cyanine compound having no quinoline skeleton and pyridine skeleton because at least one of R1 and R2 includes a quinoline skeleton or a pyridine skeleton so that π conjugation as a whole molecule is expanded. In the state where the peak intensity is secured, it is broadened. That is, by having a quinoline skeleton or a pyridine skeleton, the width of the light absorption wavelength region of the cyanine compound represented by the chemical formula (1) is wider than the width of the light absorption wavelength region of the cyanine compound having no quinoline skeleton or the like. . In addition, the alkyl chain having a carboxylic acid group or a carboxylic acid ion group, which is introduced into the nitrogen atom of the heterocyclic skeleton in R1, functions as an anchor group that contributes to the bond with the carrier. Thereby, when light is absorbed and excited while being carried on the carrier, electrons are efficiently injected into the carrier. As a result, when the cyanine compound represented by the chemical formula (1) is irradiated with light containing components in the ultraviolet light region, visible light region, and near infrared light region in a state of being supported on the carrier, a wide wavelength of the light The light component in the region is absorbed and excited, and electrons are efficiently injected into the carrier. Therefore, in the photoelectric conversion element using the cyanine compound represented by the chemical formula (1) as the dye, the ratio of the amount of electrons injected into the carrier with respect to the irradiated light amount is increased, and the conversion efficiency is improved. The cyanine compound represented by the chemical formula (1) has the same effect as long as it has the structure represented by the chemical formula (1), even if it is an enantiomer, a diastereomer or a mixture thereof. can get. The above-mentioned “anchor group” refers to a group having chemical or electrostatic affinity and binding ability for a support for supporting a compound. As long as this anchor group is introduced into the nitrogen atom of the heterocyclic skeleton contained in R1 in the chemical formula (1), it may be contained in the cyanine structure shown in the chemical formula (1).

  Next, the structure of the cyanine compound represented by the chemical formula (1) will be described in detail.

  R1 described in the chemical formula (1) has a heterocyclic skeleton containing a nitrogen atom as a hetero atom. This R1 is a group having a 5-membered ring skeleton represented by chemical formula (2), a group that is single-bonded to the end of Q at the 2-position of the quinoline skeleton represented by chemical formula (3), and represented by chemical formula (4). A group that is single-bonded to the end of Q at the 4-position of the quinoline skeleton, a group that is single-bonded to the end of Q at the 2-position of the pyridine skeleton shown in chemical formula (5), or a pyridine shown in chemical formula (6) One of the groups that is single-bonded to the end of Q at the 4-position of the skeleton.

  First, the group represented by the chemical formula (2) will be described. R10 to R13 described in the chemical formula (2) are groups introduced into carbon atoms contained in the 5-membered ring. Specific examples of R10 to R13 include the following. When R10 to R13 are halogen atoms, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Further, when R10 to R13 are an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, or a derivative thereof, the number of carbon atoms constituting the skeleton is also arbitrary. Examples of the alkyl group, alkoxy group, aryl group, arylalkyl group or derivatives thereof in this case include the following. That is, examples of the alkyl group and derivatives thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, second butyl group, third butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, and cyclohexyl. Group, cyclohexylmethyl group, cyclohexylethyl group, heptyl group, isoheptyl group, third heptyl group, n-octyl group, isooctyl group, third octyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, dodecyl group Alkyl groups having 1 to 25 carbon atoms such as hexadecyl group, docosyl group or tetracosyl group, halogenated groups thereof, aromatic ring groups such as phenyl groups, thiophene groups, etc. Heterocyclic groups, acyl groups such as acetyl groups or acidic groups such as carboxylic acid groups Etc. introduced group. Alkoxy groups and derivatives thereof include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, second butyloxy group, third butyloxy group, isobutyloxy group, amyloxy group, isoamyloxy group, third amyloxy group Hexyloxy group, cyclohexyloxy group, cyclohexylmethyloxy group, cyclohexylethyloxy group, heptyloxy group, isoheptyloxy group, third heptyloxy group, n-octyloxy group, isooctyloxy group, third octyloxy group , 2-ethylhexyloxy group, nonyloxy group, isononyloxy group, decyloxy group, dodecyloxy group, hexadecyloxy group or docosyloxy group, etc., and alkoxy groups having 1 to 20 carbon atoms, and their halogenation Groups in which an aromatic group such as a phenyl group, a heterocyclic group such as a thiophene group, an acyl group such as an acetyl group, or an acidic group such as a carboxylic acid group is introduced. Can be mentioned. Examples of the aryl group and derivatives thereof include 6 to 6 carbon atoms such as phenyl group, naphthyl group, anthracen-1-yl group, tetracenyl group, pentacenyl group, chrysenyl group, triphenylenyl group, pyrenyl group, picenyl group, and perylenyl group. 30 aryl groups, halogenated groups thereof, alkyl groups such as methyl groups, alkoxy groups such as methoxy groups, aromatic ring groups such as phenyl groups, and heterocyclic rings such as thiophene groups Group, an acyl group such as an acetyl group, or a group into which an acidic group such as a carboxylic acid group has been introduced. As the arylalkyl group and derivatives thereof, for example, the number of carbon atoms such as benzyl group, phenethyl group, 2-phenylpropane group, diphenylmethyl group, triphenylmethyl group, styryl group, cinnamyl group, naphthylmethyl group or biphenylmethyl group 7-30 arylalkyl groups, halogenated groups thereof, alkyl groups such as methyl groups, alkoxy groups such as methoxy groups, aromatic ring groups such as phenyl groups, thiophene groups, etc. A heterocyclic group, an acyl group such as an acetyl group, or a group introduced with an acidic group such as a carboxylic acid group.

  Among them, at least one of R10 to R13 in the chemical formula (2) is an alkyl group having 1 to 25 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group, an arylalkyl group, or a group thereof. Derivatives are preferred. In general cyanine compounds (compounds having a structure in which a heterocyclic skeleton is bonded to both ends of the methine chain skeleton), a structure in which carbon atoms and heteroatoms constituting the methine chain skeleton and the heterocyclic skeleton are arranged in a plane It tends to be a structure with high so-called flatness. When the planarity of the molecular structure is high, molecules are associated with each other so as to overlap each other, and an aggregate such as a dimer is easily formed. The dye that forms the aggregate is less likely to contribute to photoelectric conversion because the electron injection efficiency is low even when it is supported on the support. However, R10 to R13 introduced into the carbon atoms included in the heterocyclic skeleton are on the upper surface side and the lower surface with respect to the plane including the methine chain skeleton and the heterocyclic skeleton unless a double bond is formed between the carbon atoms. It arrange | positions so that it may overhang into the space of both sides. For this reason, when the above-described group is introduced as any one of R10 to R13, the planarity of the molecule as a whole is lowered and the molecules are less likely to associate with each other. Therefore, when used in a photoelectric conversion element, the ratio of the aggregate that hardly contributes to photoelectric conversion in the entire supported dye is reduced, so that high conversion efficiency is obtained. In particular, at least one of R10 to R13 is sterically bulky such as an alkyl group having 6 to 25 carbon atoms, an alkoxy group having 5 to 20 carbon atoms, an aryl group, an arylalkyl group, or a derivative thereof. A high group is preferred. This is because the formation of aggregates is further suppressed and a high effect is obtained.

  However, as explained in chemical formula (2), at least one of R10 and R11 and at least one of R12 and R13 may be eliminated to form a double bond, or each Thus, a ring structure may be formed. Of course, one of R10 and R11 and one of R12 and R13 are eliminated to form a double bond, and the other of R10 and R11 that is not eliminated and the other of R12 and R13 are They may be linked to form a ring structure. Examples of the ring structure formed by linking in this way include, for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, cyclohexane ring, cyclobutane ring, cyclopentane ring, cyclohexene ring, cycloheptane ring, piperidine ring, and piperazine. Ring, pyrrolidine ring, morpholine ring, thiomorpholine ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, quinoline ring, isoquinoline ring, imidazole ring, oxazole ring or imidazolidine ring. In addition to these, the ring structure may be a structure obtained by further condensing the plurality of ring structures described above, or may be a derivative thereof having one or more substituents. Especially, as a ring structure in the case of being connected by R10 to R13, a benzene ring, a naphthalene ring, a phenanthrene ring or a derivative thereof is preferable. This is because the electron injection efficiency into the carrier is likely to be higher than in the case where other ring structures are formed.

The group represented by -R14-Y1 described in the chemical formula (2) is an anchor group that imparts chemical or electrostatic affinity and binding ability to the support as described above. As a result, electrons are efficiently injected into the carrier while being carried by the carrier. If R14 is an alkylene group, its structure and the number of carbon atoms are arbitrary. The reason why R14 is an alkylene group is that the adsorbing ability or electron injecting ability to the carrier as an anchor group is enhanced as compared with other divalent groups such as an arylene group. Y1 is a carboxylic acid group or a carboxylic acid ion group because the adsorption ability and electron injection ability for the carrier are higher than those of acidic groups such as sulfonic acid groups. Among them, R14 is preferably an ethylene group. That is, a group represented by - R14-Y1 _{is, -CH 2 -CH 2 -C (=} O) group represented by -OH or _{-CH 2 -CH 2 -C (= O} ) -O - Table It is preferred that This is because a higher effect can be obtained.

  X described in chemical formula (2) is arbitrary as long as it is any of the above-described divalent groups. When X is a divalent group containing a carbon atom (—C (R15) (R16) —) or a divalent group containing a nitrogen atom (—N (R17) —), R15 to R17 Specific examples of the alkyl group, alkoxy group, aryl group, arylalkyl group described above in R10 to R13 described above, excluding those corresponding to the group represented by chemical formula (11) in addition to a hydrogen atom, The thing similar to a derivative is mentioned.

In addition, R15 to R17 in the chemical formula (2) may be groups represented by the chemical formula (11). As a halogen atom demonstrated in Chemical formula (11), the thing similar to the halogen atom demonstrated in Chemical formula (2) is mentioned. Examples of the group represented by the chemical formula (11) include a vinyl group (—CH═CH ₂ ), an allyl group (—CH ₂ —CH═CH ₂ ), a 1-propenyl group (—CH═CH—CH ₃ ), Isopropenyl group (—C (CH ₃ ) ═CH ₂ ), 1-butenyl group (—CH═CH—CH ₂ —CH ₃ ), 2-butenyl group (—CH ₂ —CH═CH—CH ₃ ), 2 - methylallyl group _{(-CH 2 -C (CH 3)} = CH 2), 2- pentenyl group _{(-CH 2 -CH = CH-CH} 2 -CH 3), ethynyl (-C≡CH), 2-propynyl Group (—CH ₂ —C≡CH), 1-propynyl group (—C≡C—CH ₃ ), 2-butynyl group (—CH ₂ —C≡C—CH ₃ ) or 3-butynyl group (—CH ₂₎ -CH ₂ -C≡CH) and unsaturated chain hydrocarbon groups such as formyl group, acetyl group, propionyl , Butyryl group, valeryl group, isovaleryl group, pivaloyl group, hexanoyl group, or other acyl group or a group having such an acyl group at the terminal of an alkyl chain having 1 to 4 carbon atoms, or a carboxylate ester bond (-C ( A group having ═O) —O—), a group having a C═N bond, a cyano group or a group having a cyano group at the terminal of an alkyl chain having 1 to 4 carbon atoms. Examples of the group represented by the chemical formula (11) when R66 and R69 or R67 and R68 are linked to form a ring structure include, for example, a cyclohexenyl group, a phenethyl group, and a chemical formula (11-1). Benzyl group represented, tolylmethyl group (methylbenzyl group) represented by chemical formula (11-2), other groups represented by chemical formula (11-3) to chemical formula (11-7), and the like. . Note that some or all of the hydrogen atoms contained in these groups may be substituted with halogen atoms.

  X in the chemical formula (2) is preferably a group represented by -C (R15) (R16)-or -N (R17)-. This is because the planarity of the molecule as a whole is lowered, so that the formation of aggregates is suppressed and the conversion efficiency is easily improved. In this case, in particular, R15 to R17 are preferably such a sterically bulky group as described above so that the steric size of the entire molecule is increased. This is because the flatness becomes lower and higher effects can be obtained. In particular, X is preferably a group represented by -C (R15) (R16)-. As a result, R15 and R16 are arranged so as to protrude into both the upper surface side and the lower surface side with respect to the plane including the methine chain skeleton and the heterocyclic skeleton, so that the planarity of the entire molecule is low. Thus, the molecules are less likely to associate with each other, thereby contributing to an improvement in conversion efficiency. In this case, at least one of R15 and R16 is sterically bulky, and among them, an alkyl group having 6 to 25 carbon atoms or a group represented by the chemical formula (11) is preferable. This is because the planarity of the whole molecule is further lowered, and a high association inhibitory action can be obtained. In this case, the group represented by the chemical formula (11) is preferably a benzyl group. Further, R15 and R16 in this case are preferably both bulky groups. This is because a higher association inhibitory effect can be obtained.

  Next, the groups represented by chemical formulas (3) to (6) will be described. Specific examples of R18 to R23, R25 to R30, R32 to R35, and R37 to R40 in the chemical formulas (3) to (6) include, for example, the same as R10 to R13 in the above chemical formula (2). It is done. In addition, in the chemical formulas (3) to (6), a group represented by -R24-Y2, a group represented by -R31-Y3, a group represented by -R36-Y4, and a group represented by -R41-Y5. These groups are also anchor groups in the same manner as -R14-Y1 in chemical formula (2), and specific examples and preferred structures thereof are the same as those in -R14-Y1 in chemical formula (2). In the chemical formulas (3) to (6), it is preferable that an electron-donating substituent is introduced into the quinoline skeleton or the pyridine skeleton. That is, at least one of R18 to R23, at least one of R25 to R30, at least one of R32 to R35, and at least one of R37 to R40 is an electron donating group, or It preferably contains an electron donating group. This is because, since Y2 to Y5 in the anchor group are electron withdrawing, if an electron donating substituent is introduced into the quinoline skeleton or pyridine skeleton, the efficiency of electron injection into the carrier is easily improved.

  R1 described above is particularly preferably a group represented by the chemical formula (2-1) among the groups represented by the chemical formula (2). This is because since at least one of R15 and R16 in the chemical formula (2-1) is a benzyl group or an alkyl group, a high association inhibitory action can be obtained. In addition, since the ring A has a benzene ring or the like, the π conjugation as a whole molecule of the cyanine compound is likely to spread as compared with the case of the group represented by the chemical formula (2) not having the ring A.

（Ｒ１４はアルキレン基である。Ｒ１５，Ｒ１６は各々独立に水素原子あるいは上記した化学式（１１）に示した基、または化学式（１１）に示した基に該当するものを除く、アルキル基、アルコキシ基、アリール基、アリールアルキル基あるいはそれらの誘導体である。ただし、Ｒ１５およびＲ１６のうちの少なくとも一方はベンジル基あるいはアルキル基である。Ｙ１はカルボン酸基（−Ｃ（＝Ｏ）−ＯＨ）あるいはカルボン酸イオン基（−Ｃ（＝Ｏ）−Ｏ^- ）である。環Ａはベンゼン環、ナフタレン環、フェナンスレン環あるいはそれらの誘導体である。）

(R14 is an alkylene group. R15 and R16 are each independently a hydrogen atom, an alkyl group or an alkoxy group other than the group shown in the chemical formula (11) or the group shown in the chemical formula (11). , An aryl group, an arylalkyl group or a derivative thereof, provided that at least one of R15 and R16 is a benzyl group or an alkyl group, and Y1 is a carboxylic acid group (—C (═O) —OH) or a carboxylic group. An acid ion group (—C (═O) —O ⁻ ). Ring A is a benzene ring, a naphthalene ring, a phenanthrene ring, or a derivative thereof.

  The group represented by -R14-Y1 described in chemical formula (2-1) is an anchor group like -R14-Y1 in chemical formula (2), and specific examples and preferred structures thereof are also represented by chemical formula ( It is the same as -R14-Y1 in 2). Specific examples of R15 and R16 excluding the case where they are an alkyl group and a benzyl group include the same as R15 and R16 in the above chemical formula (2). Among these, when at least one of R15 and R16 is an alkyl group, the number of carbon atoms is preferably 5 or more. This is because a higher association inhibitory action can be obtained. Ring A is optional as long as it has a benzene ring, naphthalene ring or phenanthrene ring skeleton, and may have one or more substituents. When ring A is a naphthalene ring or a phenanthrene ring, the position at which the ring is condensed with a 5-membered heterocyclic ring is also arbitrary. The substituent introduced into ring A is arbitrary, for example, an alkyl group such as a methyl group, an ethyl group or a butyl group, an alkoxy group such as a methoxy group or an ethoxy group, an aryl group such as a phenyl group, or a phenyl group such as a benzyl group Examples thereof include alkyl groups or derivatives thereof. Among them, the ring A is preferably a ring in which an electron-donating substituent is introduced into a benzene ring, a naphthalene ring, or a phenanthrene ring. This is because Y1 in the anchor group is electron-withdrawing, and therefore, if the ring A has an electron-donating substituent, the efficiency of electron injection into the carrier is easily improved.

  Next, R2 in the chemical formula (1) will be described. R2 is a group that double-bonds to the Q terminal at the 2-position of the quinoline skeleton shown in chemical formula (7), and double-bonds to the Q terminal at the 4-position of the quinoline skeleton shown in chemical formula (8). A group that double bonds with the terminal of Q at the 2-position of the pyridine skeleton shown in chemical formula (9), or a group that double-bonds with the terminal of Q at the 4-position of the pyridine skeleton shown in chemical formula (10). Any of the groups to which it is attached.

  Specific examples of R42 to R65 in the chemical formula (7) to chemical formula (10) are, for example, the same as the specific examples of R10 to R13 in the chemical formula (2) described above, in addition to carboxylic acid groups or sulfonic acids. Examples thereof include an anchor group having an acidic group such as a group. Among these, R42 to R65 are preferably electron donating substituents. Since R1 having an anchor group attracts electrons to the chromophore methine chain skeleton (Q), if R2 functions so as to donate electrons, electron transfer in the cyanine compound is improved. As a result, the efficiency of electron injection into the carrier increases. Among them, it is preferable that the group introduced into the nitrogen atom in the quinoline skeleton or the pyridine skeleton is an electron donating alkyl group, that is, R48, R53, R60, and R63 are alkyl groups. This is because the transfer of electrons in the cyanine compound becomes better, and the efficiency of electron injection into the support increases.

  Next, Q in the chemical formula (1) will be described. Q is a linking group having a skeleton of a methine chain (monomethine to heptamethine) having 1 to 7 carbon atoms, of which the methine chain has an odd number of carbon atoms. That is, Q has -C =, -C = C-C =, -C = C-C = C-C =, or -C = C-C = C-C = C-C = as its carbon skeleton. It is what has. Incidentally, when the cyanine compound represented by the chemical formula (1) is its resonance structure, for example, the carbon skeleton of Q is = C-, = C-C = C-, = C-C = C-C = C-, or = C-C = C-C = C-C = C-. The reason why the number of carbon atoms in the methine chain is 1 or more and 7 or less is that light absorption in a wide range from ultraviolet light to near infrared light becomes good as described above. Examples of Q include -CH =, -CH = CH-CH =, -CH = CH-CH = CH-CH =, or -CH = CH-CH = CH-CH = CH-CH =. Q may further have one or more substituents, and the substituents may be bonded to each other to form a ring structure. Examples of the substituent introduced into Q include a cyano group, a nitro group, a halogen group, an alkyl group, and an alkenyl group. In Q, examples of the linking group having a ring structure include linking groups represented by chemical formulas (12-1) to (12-8). Note that one or a plurality of substituents may be further introduced into the linking group represented by the chemical formula (12-1) to the chemical formula (12-8). In addition, when a substituent is introduced in Q, it is preferable that the substituent is introduced into the carbon atom that is the center of the methine chain skeleton. This is because the balance of charge bias as a whole molecule is good, and the electron injection efficiency to the carrier is likely to increase.

  In particular, Q in the chemical formula (1) preferably has one or more cyano groups introduced to the carbon atoms constituting the methine chain skeleton. In a state where the anchor group in R1 is adsorbed on the carrier, if Q has a cyano group, the physical distance between the cyano group and the carrier is reduced. Thereby, the interaction between the unshared electron pair of the cyano group introduced into the methine chain and the carrier reduces the resistance at the time of electron injection from the cyanine compound to the carrier. Thus, when used in a photoelectric conversion element, the form factor (FF; Fill Factor) of IV characteristics (current-voltage characteristics) is improved, and it is considered that this contributes to improvement in conversion efficiency. In addition to this, when Q has a cyano group, the fixing property to the support becomes high, which contributes to the improvement of the conversion efficiency. When Q has a cyano group, it is preferably introduced into the carbon atom that is the center of the methine chain skeleton. In this case, the number of carbon atoms in the methine chain skeleton is preferably 5 (pentamethine) because it is easy to synthesize.

Z ^p- in the chemical formula (1) will be described. Z ^p− is a counter anion for keeping the entire charge of the cyanine compound represented by the chemical formula (1) neutral, and is arbitrary as long as it is a monovalent or divalent anion. As an anion (monovalent anion; Z ⁻ ) when p = 1, for example, fluoride ion (F ⁻ ), chloride ion (Cl ⁻ ), bromide ion (Br ⁻ ) or iodide ion (I ⁻ ) Halide ions such as hexafluorophosphate ion (PF ₆ ⁻ ), hexafluoroantimonate ion (SbF ₆ ⁻ ), perchlorate ion (ClO ₄ ⁻ ), tetrafluoroborate ion (BF ₄ ⁻ ). Inorganic anions such as chlorate ion or thiocyanate ion, benzenesulfonate ion, toluenesulfonate ion, trifluoromethanesulfonate ion, diphenylamine-4-sulfonate ion, 2-amino-4-methyl-5- Chlorobenzenesulfonate ion, 2-amino-5-nitrobenzenesulfonate ion, N-alkyldiphenyl Organic sulfonate anions such as amine-4-sulfonate ion or N-aryldiphenylamine-4-sulfonate ion, octyl phosphate ion, dodecyl phosphate ion, octadecyl phosphate ion, phenyl phosphate ion, nonyl phenyl phosphorus Organic phosphate anions such as acid ions or 2,2'-methylenebis (4,6-di-t-butylphenyl) phosphonate ions, bistrifluoromethylsulfonylimide ions, bisperfluorobutanesulfonylimide ions Perfluoro-4-ethylcyclohexanesulfonate ion, tetrakis (pentafluorophenyl) borate ion or tris (fluoroalkylsulfonyl) carboanion. Examples of the anion (divalent anion; Z ²⁻ ) in the case of p = 2 include sulfate ion (SO ₄ ²⁻ ), benzenedisulfonate ion, naphthalenedisulfonate ion, and the like. Moreover, q demonstrated in Chemical formula (1) is a coefficient which keeps an electric charge neutral as the whole cyanine compound shown in Chemical formula (1), and may be 0. When q = 0, for example, Y1 (or Y2 to Y5) in R1 is a carboxylate ion group, and a salt is formed in the molecule to form a so-called internal salt. When q = 1, Z ^p− becomes a monovalent anion Z ⁻ , and a salt is formed so as to keep the charge of the whole compound neutral. In addition, when Z ^p− is Z ²⁻ which is a divalent anion, q = ½. That is, q here is 0, 1 or 1/2.

Examples of the cyanine compound represented by the above chemical formula (1) include compounds having a structural part represented by chemical formula (1-1) to chemical formula (1-303). In the chemical formulas below, Me represents a methyl group, and Et represents an ethyl group. Also, structure shown in the following chemical formula (1-1) to formula (1-303) represents the chemical formula (1) portion which does not include the Z ^p-in (cationic moiety), these structures For example, the above-described monovalent or divalent anions can be arbitrarily combined, and the same applies to other anions. Furthermore, in these structural parts, for example, acidic groups such as carboxylic acid groups can be ionized to form internal salts.

  In addition, as long as it is a compound which has the cyanine structure shown to Chemical formula (1), it is not limited to the compound containing the structure part shown to Chemical formula (1-1)-Chemical formula (1-303).

  In the cyanine compound represented by the chemical formula (1) described above, R1 is preferably a group represented by any one of the chemical formula (2) to the chemical formula (4). In the case where R2 is a group represented by the chemical formula (9) or the chemical formula (10), R1 is a group represented by any one of the chemical formula (2) to the chemical formula (4). This is because the light absorption wavelength region is wider than the compound which is the group represented by (5) or chemical formula (6). In the cyanine compound represented by the chemical formula (1), when Q is a linking group having a methine chain having 3 carbon atoms as a skeleton, R2 may be a group represented by the chemical formula (7) or the chemical formula (8). preferable. This is because R2 in this case contributes to the improvement of the conversion efficiency as compared with the cyanine compound which is the group represented by the chemical formula (9) or the chemical formula (10).

  Next, a method for synthesizing the cyanine compound represented by the chemical formula (1) will be described with reference to the chemical reaction formulas (I) to (III). The cyanine compound represented by the above chemical formula (1) can be synthesized, for example, by the following three methods.

In the first synthesis method, a compound having 1 carbon atom in the methine chain skeleton contained in Q in the chemical formula (1) is synthesized. Specifically, as shown in the chemical reaction formula (I), a compound represented by the chemical formula (13) having a leaving group R100 and a carbon atom (R70) constituting the carbon skeleton of monomethine was bonded later. The compound represented by the chemical formula (14) having a carbon atom) is reacted in the presence of a base (Base) by adding a predetermined amount of Z ^p- as a counter anion as necessary. As a result, a cyanine compound (chemical formula (1A)) having 1 carbon atom in the methine chain skeleton contained in Q in chemical formula (1) is synthesized.

（Ｒ７０は水素原子あるいは１価の置換基であり、化学式（１）中のＱに含まれるメチン鎖骨格の炭素原子に導入される水素原子あるいは置換基に相当するものである。Ｒ１００はチオアルキル基あるいはハロゲン原子などの脱離基である。Ｒ１０１およびＲ１０２は上記した化学式（２）〜化学式（６）に示した基あるいは化学式（７Ａ）〜化学式（１０Ａ）で表される基である。ただし、Ｒ１０１およびＲ１０２のうちの一方が化学式（２）〜化学式（６）に示した基のうちのいずれか１種であり、他方が化学式（７Ａ）〜化学式（１０Ａ）に示した基のうちのいずれか１種である。Ｒ１，Ｒ２，Ｚ^p-およびｑは化学式（１）中のＲ１，Ｒ２，Ｚ^p-およびｑと同様である。）

(R70 is a hydrogen atom or a monovalent substituent, and corresponds to a hydrogen atom or a substituent introduced into a carbon atom of the methine chain skeleton contained in Q in chemical formula (1). R100 is a thioalkyl group. Alternatively, it is a leaving group such as a halogen atom, etc. R101 and R102 are groups represented by the chemical formulas (2) to (6) or groups represented by the chemical formulas (7A) to (10A). One of R101 and R102 is any one of the groups represented by chemical formula (2) to chemical formula (6), and the other is any of the groups represented by chemical formula (7A) to chemical formula (10A). whether it is one .R1, R2, Z ^p- and q are the same as R1, R2, Z ^p- and q in formula (1).)

（Ｒ４２〜Ｒ６５は上記した化学式（７）〜化学式（１０）中のＲ４２〜Ｒ６５と同様である。）

(R42 to R65 are the same as R42 to R65 in the chemical formulas (7) to (10)).

In the second synthesis method, a compound in which the number of carbon atoms in the methine chain skeleton contained in Q in the chemical formula (1) is 3 or more and the structures of R1 and R2 are asymmetric is synthesized. Specifically, as shown in the chemical reaction formula (II), a compound represented by the chemical formula (15) having a leaving group (—NH—C ₆ H ₅ ) and a carbon skeleton of the methine chain are later formed. a compound represented by formula (16) having a terminal carbon atom (the carbon atom to which R72 is bonded) of the carbon atoms constituting, Z ^p-added predetermined quantity of a counter anion if necessary, a base The reaction is carried out in the presence of (Base). As a result, among the cyanine compounds represented by chemical formula (1), a cyanine compound (chemical formula (1B)) in which the number of carbon atoms in the methine chain skeleton contained in Q is 3 or more and R1 and R2 are asymmetric structures is synthesized. Is done. In addition, the cyanine compound in which R1 and R2 are asymmetric is a compound having a structure except when R1 and R2 are the following combinations. In the combinations to be removed, when R1 is the group represented by the chemical formula (3) and R2 is the group represented by the chemical formula (7), R1 is the group represented by the chemical formula (4) and R2 is represented by the chemical formula ( In the case of the group shown in 8), R1 is the group shown in chemical formula (5) and R2 is the group shown in chemical formula (9), and R1 is the group shown in chemical formula (6). And R2 is a group represented by the chemical formula (10).

（Ｒ７１，Ｒ７２は水素原子あるいは１価の置換基であり、化学式（１）中のＱに含まれるメチン鎖骨格の炭素原子のうち両末端の炭素原子に結合する水素原子あるいは置換基に相当するものである。Ｒ１０１およびＲ１０２は上記した化学式（２）〜化学式（６）に示した基あるいは化学式（７Ａ）〜化学式（１０Ａ）に示した基である。ただし、Ｒ１０１およびＲ１０２のうちの一方が化学式（２）〜化学式（６）に示した基のうちのいずれか１種であり、他方が化学式（７Ａ）〜化学式（１０Ａ）に示した基のうちのいずれか１種である。Ｑ１は炭素原子数１以上５以下のメチン鎖を骨格とする連結基である。Ｒ１，Ｒ２，Ｚ^p-およびｑは化学式（１）中のＲ１，Ｒ２，Ｚ^p-およびｑと同様である。）

(R71 and R72 are hydrogen atoms or monovalent substituents, and correspond to hydrogen atoms or substituents bonded to carbon atoms at both ends of the carbon atoms of the methine chain skeleton contained in Q in chemical formula (1). R101 and R102 are the groups represented by the chemical formulas (2) to (6) or the chemical formulas (7A) to (10A), provided that one of R101 and R102 is one of R101 and R102. Q1 is any one of the groups represented by chemical formula (2) to chemical formula (6), and the other is any one of the groups represented by chemical formula (7A) to chemical formula (10A). is a linking group that 1 or more carbon atoms 5 the following methine chain skeleton .R1, R2, Z ^p- and q are the same as R1, R2, Z ^p- and q in formula (1).)

In the third synthesis method, a compound in which the number of carbon atoms in the methine chain skeleton contained in Q in chemical formula (1) is 3 or more and the structures of R1 and R2 are symmetric is synthesized. Specifically, as shown in the chemical reaction formula (III), the chemical formula (17) having a terminal carbon atom (carbon atom to which R73 is bonded) among the carbon atoms constituting the carbon skeleton of the methine chain later. The compound represented by the chemical formula (18) as the bridging agent is reacted in the presence of a base (Base) by adding a predetermined amount of Z ^p- as a counter anion as necessary. As a result, among the cyanine compounds represented by chemical formula (1), a cyanine compound (chemical formula (1C)) in which the number of carbon atoms in the methine chain skeleton contained in Q is 3 or more and R1 and R2 are symmetrical is synthesized. Is done. In the chemical reaction formula (III), examples of the compound represented by the chemical formula (18) used as the bridging agent include compounds represented by the chemical formula (18-1) to the chemical formula (18-4). Examples of the bridging agent include compounds represented by chemical formula (18-5) to chemical formula (18-7).

（Ｒ７３は水素原子あるいは１価の置換基であり、化学式（１）中のＱに含まれるメチン鎖骨格の炭素原子のうち両末端の炭素原子に結合する水素原子あるいは置換基に相当するものである。Ｒ１０３は上記した化学式（３）〜化学式（６）に示した基である。Ｒ１０４は、化学式（３）〜化学式（６）に示した基であり、Ｒ１０５は化学式（７）〜化学式（１０）に示した基である。ただし、Ｒ１０４が化学式（３）に示した基である場合のＲ１０５は化学式（７）に示した基であり、Ｒ１０４が化学式（４）に示した基である場合のＲ１０５は化学式（８）に示した基であり、Ｒ１０４が化学式（５）に示した基である場合のＲ１０５は化学式（９）に示した基であり、Ｒ１０４が化学式（６）に示した基である場合のＲ１０５は化学式（１０）に示した基である。Ｑ２は炭素原子数１以上５以下のメチン鎖を骨格とする連結基である。Ｚ^p-およびｑは化学式（１）中のＺ^p-およびｑと同様である。）

(R73 is a hydrogen atom or a monovalent substituent, and corresponds to a hydrogen atom or a substituent bonded to carbon atoms at both ends of the carbon atoms of the methine chain skeleton contained in Q in chemical formula (1). R103 is a group represented by the above chemical formula (3) to chemical formula (6), R104 is a group represented by chemical formula (3) to chemical formula (6), and R105 is a chemical formula (7) to chemical formula (6). 10) However, when R104 is the group shown in chemical formula (3), R105 is the group shown in chemical formula (7), and R104 is the group shown in chemical formula (4). R105 in the case is the group shown in chemical formula (8), R105 is the group shown in chemical formula (9) when R104 is the group shown in chemical formula (5), and R104 is shown in chemical formula (6). R105 in the case of a radical is a chemical formula 10) in a group shown .Q2 is the same as Z ^p-and q in a linking group .Z ^p-and q has the formula (1) for the methine chain having 1 to 5 carbon atoms as a skeleton is there.)

（Ｒ７４〜Ｒ８８は水素原子あるいは１価の置換基である。）

(R74 to R88 are a hydrogen atom or a monovalent substituent.)

  The photoelectric conversion element dye according to the present embodiment has a cyanine structure represented by the chemical formula (1), and therefore has no dye (for example, a cyanine having a 5-membered heterocyclic skeleton bonded to both ends of the methine chain). Compared with the compound), it absorbs light in a wide wavelength region from the ultraviolet light region to the near infrared light region and is excited, and in addition, it is more efficient for the carrier when it is supported on the carrier. Electrons can be injected well. Therefore, when used for a photoelectric conversion element, the amount of electrons injected from the dye to the carrier increases with respect to the amount of light irradiated, IPCE (Incident Photons to Current conversion Efficiency) is improved, and conversion efficiency can be improved. . Note that IPCE represents the ratio of photocurrent converted to the number of electrons with respect to the number of photons irradiated in the photoelectric conversion element, and IPCE (%) = Isc × 1240 / λ × 1 / φ (formula Where Isc is a short circuit current, λ is a wavelength, and φ is an incident light intensity.

  In this case, R1 in the chemical formula (1) is preferably a group represented by the chemical formula (2-1). Thereby, the benzyl group or the alkyl group introduced as at least one of R15 and R16 in the chemical formula (2-1) is a space on both the upper surface side and the lower surface side with respect to the plane including the methine chain skeleton and the heterocyclic skeleton. Therefore, the entire molecule has low planarity and is difficult to associate. Therefore, when it uses for a photoelectric conversion element, conversion efficiency can be improved more.

  Further, Q in the chemical formula (1) is preferably a linking group having a methine chain having 3 carbon atoms as a skeleton, and R2 is preferably a group represented by the chemical formula (7) or the chemical formula (8). Since the light absorption wavelength range becomes wider and the electron injection efficiency into the carrier becomes higher, the conversion efficiency can be further improved when used in a photoelectric conversion element.

  Next, the usage example of the pigment | dye for photoelectric conversion elements which concerns on this Embodiment is demonstrated.

  FIG. 1 schematically shows a cross-sectional configuration of a photoelectric conversion element, and FIG. 2 shows an extracted and enlarged main part of the photoelectric conversion element shown in FIG. The photoelectric conversion element shown in FIGS. 1 and 2 is a main part of a so-called dye-sensitized solar cell. In this photoelectric conversion element, the working electrode 10 and the counter electrode 20 are disposed to face each other with the electrolyte-containing layer 30 interposed therebetween, and at least one of the working electrode 10 and the counter electrode 20 is an electrode having optical transparency. It is.

  The working electrode 10 is, for example, supported on a conductive substrate 11, a metal oxide semiconductor layer 12 provided on one surface thereof (surface on the counter electrode 20 side), and the metal oxide semiconductor layer 12 as a carrier. Pigment 13. The working electrode 10 functions as a negative electrode for the external circuit. For example, the conductive substrate 11 is obtained by providing a conductive layer 11B on the surface of an insulating substrate 11A.

  Examples of the material of the substrate 11A include insulating materials such as glass, plastic, and transparent polymer film. Examples of the transparent polymer film include tetraacetyl cellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate ( PAR), polysulfone (PSF), polyester sulfone (PES), polyetherimide (PEI), cyclic polyolefin or brominated phenoxy.

As the conductive layer 11B, for example, a conductive metal oxide thin film containing indium oxide, tin oxide, indium-tin composite oxide (ITO), or tin oxide doped with fluorine (FTO: F-SnO ₂ ), etc. , A metal thin film containing gold (Au), silver (Ag), platinum (Pt), or the like, or a conductive thin film.

  In addition, the conductive substrate 11 may be configured to have a single-layer structure with, for example, a conductive material. In that case, examples of the material of the conductive substrate 11 include indium oxide, tin oxide, Examples thereof include conductive metal oxides such as indium-tin composite oxide or tin oxide doped with fluorine, metals such as gold, silver or platinum, and conductive polymers.

  The metal oxide semiconductor layer 12 is a carrier that supports the dye 13 and has, for example, a porous structure as shown in FIG. The metal oxide semiconductor layer 12 is formed of a dense layer 12A and a porous layer 12B. The dense layer 12A is formed at the interface with the conductive substrate 11, is preferably dense and has few voids, and more preferably is a film. The porous layer 12B is preferably formed on the surface in contact with the electrolyte-containing layer 30, has a large space and a large surface area, and more preferably has a structure in which porous fine particles are attached. Note that the metal oxide semiconductor layer 12 may be formed to have, for example, a film-like single layer structure.

  Examples of the material (metal oxide semiconductor material) included in the metal oxide semiconductor layer 12 include titanium oxide, zinc oxide, tin oxide, niobium oxide, indium oxide, zirconium oxide, tantalum oxide, vanadium oxide, yttrium oxide, and oxide. Examples thereof include aluminum and magnesium oxide. Among these, zinc oxide is preferable as the metal oxide semiconductor material. This is because high conversion efficiency can be obtained. These metal oxide semiconductor materials may be used alone or in combination of two or more (mixed, mixed crystal, solid solution, etc.), for example, zinc oxide and A combination of tin oxide, titanium oxide and niobium oxide can also be used.

  Examples of a method for forming the metal oxide semiconductor layer 12 having a porous structure include an electrolytic deposition method, a coating method, and a firing method. In the case where the metal oxide semiconductor layer 12 is formed by electrolytic deposition, the fine particles are deposited on the conductive layer 11B of the conductive substrate 11 in the electrolytic bath liquid containing the fine particles of the metal oxide semiconductor material and the metal. An oxide semiconductor material is deposited. When the metal oxide semiconductor layer 12 is formed by a coating method, a dispersion liquid (metal oxide slurry) in which fine particles of a metal oxide semiconductor material are dispersed is applied on the conductive substrate 11, and then in the dispersion liquid. Dry to remove the dispersion medium. When the metal oxide semiconductor layer 12 is formed by the sintering method, the metal oxide slurry is applied onto the conductive substrate 11 and dried, as in the coating method, and then fired. In particular, if the metal oxide semiconductor layer 12 is formed by an electrolytic deposition method or a coating method, a plastic material or a polymer film material having low heat resistance can be used as the substrate 11A, and thus a highly flexible electrode is manufactured. Can do.

  The dye 13 is, for example, adsorbed to the metal oxide semiconductor layer 12, and is capable of injecting electrons into the metal oxide semiconductor layer 12 by absorbing light and being excited. Contains more than one type of dye (sensitizing dye). The pigment | dye 13 contains the cyanine compound shown to above-mentioned Chemical formula (1) as this pigment | dye. By including the cyanine compound represented by the chemical formula (1), since the ratio of the amount of electrons injected into the metal oxide semiconductor layer 12 with respect to the amount of light irradiated as the entire dye 13 is increased, the conversion efficiency is improved.

  The dye 13 may contain other dyes in addition to the cyanine compound represented by the chemical formula (1). The other dye is preferably a dye having an anchor group that can be chemically bonded to the metal oxide semiconductor layer 12. Examples of other dyes include eosin Y, dibromofluorescein, fluorescein, rhodamine B, pyrogallol, dichlorofluorescein, erythrosine B (erythrocin is a registered trademark), fluorescin, mercurochrome, cyanine dye, merocyanine disazo dye, trisazo dye, Anthraquinone dyes, polycyclic quinone dyes, indigo dyes, diphenylmethane dyes, trimethylmethane dyes, quinoline dyes, benzophenone dyes, naphthoquinone dyes, perylene dyes, fluorenone dyes, squarylium dyes, azurenium dyes And organic dyes such as perinone dyes, quinacridone dyes, metal-free phthalocyanine dyes and metal-free porphyrin dyes.

  Examples of other dyes include organometallic complex compounds. For example, an ionic coordinate bond formed by a nitrogen anion and a metal cation in an aromatic heterocyclic ring, and a nitrogen atom or Organometallic complex compounds having both nonionic coordination bonds formed between chalcogen atoms and metal cations, ionic coordination bonds formed by oxygen anions or sulfur anions and metal cations, and nitrogen And organometallic complex compounds having both nonionic coordination bonds formed between an atom or chalcogen atom and a metal cation. Specifically, metal phthalocyanine dyes such as copper phthalocyanine and titanyl phthalocyanine, metal naphthalocyanine dyes, metal porphyrin dyes, bipyridyl ruthenium complexes, terpyridyl ruthenium complexes, phenanthroline ruthenium complexes, bicinchonirate ruthenium complexes, and azo ruthenium complexes Alternatively, a ruthenium complex such as a quinolinol ruthenium complex can be used.

  Moreover, the pigment | dye 13 may contain the 1 type (s) or 2 or more types of additive other than the above-mentioned pigment | dye. Examples of the additive include an association inhibitor that suppresses association of the dye in the dye 13, and specifically, a cholic acid compound represented by the chemical formula (19). These may be used alone or in combination of two or more.

（Ｒ９１は酸性基を有するアルキル基である。Ｒ９２は化学式中のステロイド骨格を構成する炭素原子のいずれかに結合する基を表し、水酸基、ハロゲン基、アルキル基、アルコキシ基、アリール基、複素環基、アシル基、アシルオキシ基、オキシカルボニル基、オキソ基あるいは酸性基またはそれらの誘導体であり、それらは同一であってもよいし異なっていてもよい。ｔは１以上５以下の整数である。化学式中のステロイド骨格を構成する炭素原子と炭素原子との間の結合は、単結合であってもよいし、二重結合であってもよい。）

(R91 is an alkyl group having an acidic group. R92 represents a group bonded to any of the carbon atoms constituting the steroid skeleton in the chemical formula, and is a hydroxyl group, a halogen group, an alkyl group, an alkoxy group, an aryl group, a heterocyclic ring. A group, an acyl group, an acyloxy group, an oxycarbonyl group, an oxo group, an acidic group, or a derivative thereof, which may be the same or different, and t is an integer of 1 to 5. (The bond between the carbon atoms constituting the steroid skeleton in the chemical formula may be a single bond or a double bond.)

  The counter electrode 20 is, for example, a conductive substrate 21 provided with a conductive layer 22 and functions as a positive electrode for an external circuit. Examples of the material of the conductive substrate 21 include the same materials as those of the conductive substrate 11 of the working electrode 10. The conductive layer 22 includes one type or two or more types of conductive material and a binder as necessary. Examples of the conductive material used for the conductive layer 22 include platinum, gold, silver, copper (Cu), rhodium (Rh), ruthenium (Ru), aluminum (Al), magnesium (Mg), and indium (In). Examples include metals, carbon (C), and conductive polymers. Examples of the binder used for the conductive layer 22 include acrylic resin, polyester resin, phenol resin, epoxy resin, cellulose, melamine resin, fluoroelastomer, and polyimide resin. The counter electrode 20 may have a single layer structure of the conductive layer 22, for example.

The electrolyte-containing layer 30 includes, for example, a redox electrolyte having a redox pair. Examples of the redox electrolyte include I ⁻ / I ₃ ⁻ system, Br ⁻ / Br ₃ ⁻ system, and quinone / hydroquinone system. Specifically, it is a combination of a halide salt and a simple halogen substance, such as a combination of an iodide salt and simple iodine, or a combination of a bromide salt and bromine. Examples of the halide salts include cesium halides, quaternary alkyl ammonium halides, imidazolium halides, thiazolium halides, oxazolium halides, quinolinium halides and pyridinium halides. Specifically, these iodide salts include, for example, cesium iodide, tetraethylammonium iodide, tetrapropylammonium iodide, tetrabutylammonium iodide, tetrapentylammonium iodide, tetrahexylammonium iodide, tetra Quaternary alkylammonium iodides such as heptylammonium iodide or trimethylphenylammonium iodide, imidazolium iodides such as 3-methylimidazolium iodide or 1-propyl-2,3-dimethylimidazolium iodide 3-ethyl-2-methyl-2-thiazolium iodide, 3-ethyl-5- (2-hydroxyethyl) -4-methylthiazolium iodide, or 3-ethyl-2-methylbenzothiazo Liuyo Thiazolium iodides such as iodine, oxazolium iodides such as 3-ethyl-2-methyl-benzoxazolium iodide, and keys such as 1-ethyl-2-methylquinolinium iodide Examples include norinium iodides and pyridinium iodides. Examples of the bromide salt include quaternary alkyl ammonium bromide. Among the combinations of halide salts and simple halogens, combinations of at least one of the above-described iodide salts and simple iodine are preferable.

  The redox electrolyte may be, for example, a combination of an ionic liquid and a halogen simple substance. In this case, the above-described halide salt and the like may be further included. Examples of the ionic liquid include those that can be used in a battery, a solar battery, and the like. For example, “Inorg. Chem” 1996, 35, p 1168 to 1178, “Electrochemistry” 2002, 2, p 130 to 136, and JP 9 And those disclosed in JP-A No. 507334 or JP-A-8-259543. Among them, as the ionic liquid, a salt having a melting point lower than room temperature (25 ° C.), or a salt that has a melting point higher than room temperature and is liquefied at room temperature by dissolving with another molten salt is preferable. . Specific examples of this ionic liquid include the following anions and cations.

  Examples of the cation of the ionic liquid include ammonium, imidazolium, oxazolium, thiazolium, oxadiazolium, triazolium, pyrrolidinium, pyridinium, piperidinium, pyrazolium, pyrimidinium, pyrazinium, triazinium, phosphonium, sulfonium, carbazolium, indolium, or those And derivatives thereof. These may be used alone or as a mixture of plural kinds. Specific examples include 1-methyl-3-propylimidazolium, 1-butyl-3-methylimidazolium, 1,2-dimethyl-3-propylimidazolium, 1-ethyl-3-methylimidazolium, and the like. .

Examples of the anion of the ionic liquid, AlCl ₄ ^- or Al ₂ Cl ₇ ^-, metal chlorides such ^{_{as, PF 6 -, BF 4 -}} , CF 3 SO 3 -, N (CF 3 SO 2) 2 -, F ( HF) _n ^- or CF ₃ COO ^- or a fluorine-containing substance such as ^{_{ion, NO 3 -, CH 3 COO}} -, C 6 H 11 COO -, CH 3 OSO 3 -, CH 3 OSO 2 -, CH 3 SO 3 - Non-fluorine compound ions such as CH ₃ SO ₂ ⁻ , (CH ₃ O) ₂ PO ₂ ⁻ , N (CN) ₂ ⁻ or SCN ^−, and halide ions such as iodide ions or bromide ions. These may be used alone or as a mixture of plural kinds. Among these, iodide ions are preferable as the anions of the ionic liquid.

  The electrolyte-containing layer 30 may be a liquid electrolyte (electrolytic solution) obtained by dissolving the above-described redox electrolyte in a solvent, or a solid polymer electrolyte in which the electrolytic solution is held in a polymer substance. May be. Alternatively, a quasi-solid (paste-like) electrolyte containing a mixture of an electrolytic solution and a particulate carbon material such as carbon black may be used. Note that in a quasi-solid electrolyte containing a carbon material, since the carbon material has a function of catalyzing a redox reaction, the electrolyte may not contain a single halogen. Such a redox electrolyte may contain any one kind or two or more kinds of organic solvents that dissolve the above-described halide salts, ionic liquids, and the like. Examples of the organic solvent include electrochemically inert ones such as acetonitrile, propionitrile, butyronitrile, methoxyacetonitrile, 3-methoxypropionitrile, valeronitrile, dimethyl carbonate, ethyl methyl carbonate, ethylene carbonate. , Propylene carbonate, N-methylpyrrolidone, pentanol, quinoline, N, N-dimethylformamide, γ-butyrolactone, dimethyl sulfoxide or 1,4-dioxane.

  In this photoelectric conversion element, when light (sunlight or ultraviolet light, visible light, or near infrared light equivalent to sunlight) is applied to the dye 13 carried on the working electrode 10, the light is absorbed. The excited dye 13 injects electrons into the metal oxide semiconductor layer 12. After the electrons move to the adjacent conductive layer 11B, they reach the counter electrode 20 via an external circuit. On the other hand, in the electrolyte-containing layer 30, the electrolyte is oxidized so that the oxidized dye 13 is returned (reduced) to the ground state as the electrons move. This oxidized electrolyte is reduced by receiving the above-described electrons. In this way, the movement of electrons between the working electrode 10 and the counter electrode 20 and the accompanying oxidation-reduction reaction in the electrolyte-containing layer 30 are repeated. Thereby, continuous movement of electrons occurs, and photoelectric conversion is constantly performed.

  This photoelectric conversion element can be manufactured as follows, for example.

  First, the working electrode 10 is produced. First, the metal oxide semiconductor layer 12 having a porous structure is formed on the surface of the conductive substrate 11 on which the conductive layer 11B is formed by electrolytic deposition or firing. In the case of forming by electrolytic deposition, for example, an electrolytic bath containing a metal salt to be a metal oxide semiconductor material is set to a predetermined temperature while bubbling with oxygen or air, and the conductive substrate 11 is placed therein. Immerse and apply a constant voltage between the counter electrode. Thereby, a metal oxide semiconductor material is deposited on the conductive layer 11B so as to have a porous structure. At this time, the counter electrode may be appropriately moved in the electrolytic bath. In the case of forming by a firing method, for example, a metal oxide slurry prepared by dispersing a powder of a metal oxide semiconductor material in a dispersion medium is applied to the conductive substrate 11 and dried, followed by firing. Have a porous structure. Subsequently, a dye solution in which the dye 13 containing the cyanine compound represented by the chemical formula (1) is dissolved in an organic solvent is prepared. By immersing the conductive substrate 11 on which the metal oxide semiconductor layer 12 is formed in this dye solution, the metal oxide semiconductor layer 12 carries the dye 13.

  Next, the counter electrode 20 is produced by forming the conductive layer 22 on one surface of the conductive substrate 21. The conductive layer 22 is formed, for example, by sputtering a conductive material.

  Finally, a spacer (not shown) such as a sealant so that the surface of the working electrode 10 carrying the dye 13 and the surface of the counter electrode 20 on which the conductive layer 22 is formed face each other while maintaining a predetermined distance. For example, the whole is sealed except for the electrolyte inlet. Subsequently, the electrolyte containing layer 30 is formed by injecting an electrolyte between the working electrode 10 and the counter electrode 20 and then sealing the injection port. Thereby, the photoelectric conversion element shown in FIGS. 1 and 2 is completed.

  In this photoelectric conversion element, since the dye 13 includes the cyanine compound represented by the chemical formula (1), compared to the case where the cyanine compound having no structure represented by the chemical formula (1) is used, Since the ratio of the amount of electrons injected from the dye 13 into the metal oxide semiconductor layer 12 is increased, the conversion efficiency can be improved. In this case, in particular, if the metal oxide semiconductor layer 12 includes zinc oxide, the conversion efficiency is improved as compared with the case where zinc oxide is not included (when titanium oxide or tin oxide is included instead of zinc oxide). It can be improved further.

  Other functions and effects of the photoelectric conversion element are the same as those of the photoelectric conversion element dye described above.

  In the above-described photoelectric conversion element, the case where the electrolyte-containing layer 30 is provided between the working electrode 10 and the counter electrode 20 has been described, but a solid charge transfer layer may be provided instead of the electrolyte-containing layer 30. In this case, the solid charge transfer layer includes, for example, a material in which carrier movement in the solid is related to electric conduction. As this material, an electron transport material, a hole transport material, or the like is preferable.

  As the hole transport material, aromatic amines, triphenylene derivatives, and the like are preferable. For example, oligothiophene compounds, polypyrrole, polyacetylene or derivatives thereof, poly (p-phenylene) or derivatives thereof, and poly (p-phenylene vinylene). Alternatively, organic conductive polymers such as derivatives thereof, polythienylene vinylene or derivatives thereof, polythiophene or derivatives thereof, polyaniline or derivatives thereof, polytoluidine or derivatives thereof, and the like can be given.

  Further, as the hole transport material, for example, a p-type inorganic compound semiconductor may be used. The p-type inorganic compound semiconductor preferably has a band gap of 2 eV or more, and more preferably 2.5 eV or more. Further, the ionization potential of the p-type inorganic compound semiconductor needs to be smaller than the ionization potential of the working electrode 10 from the condition that the holes of the dye can be reduced. The preferred range of the ionization potential of the p-type inorganic compound semiconductor varies depending on the dye used, but the ionization potential is preferably in the range of 4.5 eV to 5.5 eV, and more preferably 4.7 eV to 5. More preferably, it is within the range of 3 eV or less.

Examples of the p-type inorganic compound semiconductor include a compound semiconductor containing monovalent copper. Examples of the compound semiconductor containing monovalent copper, there _{CuI, CuSCN, CuInSe 2, Cu} (In, Ga) Se 2, CuGaSe 2, Cu 2 O, CuS, etc. _{CuGaS 2, CuInS 2, CuAlSe 2} . Examples of other p-type inorganic compound semiconductors include GaP, NiO, CoO, FeO, Bi ₂ O ₃ , MoO _{2, and} Cr ₂ O ₃ .

  As a method of forming such a solid charge transfer layer, for example, there is a method of forming a solid charge transfer layer directly on the working electrode 10, and then the counter electrode 20 may be formed and applied.

  A hole transport material containing an organic conductive polymer may be introduced into the electrode by a technique such as vacuum deposition, casting, coating, spin coating, dipping, electrolytic polymerization, or photoelectrolytic polymerization. Can do. Also in the case of an inorganic solid compound, it can be introduced into the electrode by a technique such as a casting method, a coating method, a spin coating method, a dipping method, or an electrolytic plating method. A part of the solid charge transfer layer (particularly, having a hole transport material) formed in this way partially penetrates into the gap of the porous structure of the metal oxide semiconductor layer 12 and is in direct contact with it. It is preferable to become.

  In the photoelectric conversion element in which the solid charge transfer layer is provided instead of the electrolyte containing layer 30, the conversion efficiency can be improved as in the case where the electrolyte containing layer 30 is provided.

  Specific examples of the present invention will be described in detail.

(Experimental example 1-1)
As a specific example of the dye for the photoelectric conversion element described in the above embodiment, as shown in the chemical reaction formula (II-1), it is shown in the chemical formula (1-1) which is the cyanine compound shown in the chemical formula (1). A compound consisting of a structure part and iodide ion was synthesized.

First, 0.002 mol (0.80 g) of the compound represented by the chemical formula (15-1), 2.36 g of pyridine, and 0.008 mol (0.41 g) of acetic anhydride (Ac ₂ O) were allowed to stand at room temperature for 1 hour. Mixed. Thereafter, 0.002 mol (0.72 g) of the compound represented by the chemical formula (16-1) was added to the mixture, and the mixture was stirred at room temperature for 5 hours to obtain the chemical reaction formula (II-1). It was made to react.

  Next, 30 g of chloroform, 30 g of water, and 1 g of sodium iodide were added to the reaction product, followed by oil-liquid separation, and an oily substance was obtained by removing a solvent (such as chloroform) from the oil layer. To this oily substance, 10 g of acetone was added, and the precipitated solid was filtered off and dried at 80 ° C., whereby 0.47 g (yield: 40%) of the final product (compound represented by the chemical formula (1B-1)). )

(Experimental example 1-2)
As shown in the chemical reaction formula (II-2), a compound composed of the structural part shown in the chemical formula (1-2) and iodide ions was synthesized.

  First, 0.003 mol (1.21 g) of the compound represented by the chemical formula (15-2), 3.54 g of pyridine, and 0.003 mol (0.31 g) of acetic anhydride were mixed at room temperature for 1 hour. Subsequently, 20 g of chloroform was added to the mixture, and the chloroform solution was washed three times with liquid-liquid extraction with water. Subsequently, an oily substance was obtained by distilling off the solvent from the washed chloroform solution with an evaporator. Next, 3.54 g of pyridine, 0.0045 mol (0.46 g) of triethylamine (TEA), and 0.003 mol (1.08 g) of the compound represented by the chemical formula (16-1) were added to this oily substance. After the addition, this mixture was stirred at room temperature for 5 hours to be reacted as shown in chemical reaction formula (II-2). Next, 12 g of chloroform, 12 g of water, and 0.003 mol (0.45 g) of sodium iodide were added to the reaction product, followed by oil-liquid separation. Thereafter, this oil layer was washed with an acetic acid aqueous solution (acetic acid: water = 2 g: 25 g) and water in this order by liquid-liquid extraction, and the solvent (such as chloroform) of the washed oil layer was distilled off. Subsequently, 10 g of acetone was added to the residue after the solvent was distilled off to precipitate a solid, followed by washing under reflux. Finally, the solid after reflux washing was filtered off and dried at 80 ° C. to obtain 0.8 g (yield 45%) of the final product (compound represented by the chemical formula (1B-2)).

(Experimental Example 1-3)
As shown in the chemical reaction formula (II-3), a compound composed of the structural part shown in the chemical formula (1-3) and iodide ions was synthesized.

First, 0.0015 mol (0.61 g) of the compound represented by the chemical formula (15-3), 1.76 g of acetonitrile (CH ₃ CN), and 0.0015 mol (0.15 g) of acetic anhydride were added at room temperature for 2 hours. Mixed. Thereafter, 0.0015 mol (0.44 g) of the compound represented by the chemical formula (16-2) was added to this mixture, and the mixture was stirred at 55 ° C. for 3 hours. Thereafter, 0.5 g of ethanol (EtOH) and 0.1 g of TEA were added to the stirred product, and the mixture was further stirred at 55 ° C. for 3 hours to cause a reaction as shown in chemical reaction formula (II-3). Next, after adding 30 g of chloroform and 30 g of water to the reaction product, oil-liquid separation was performed, and an oily substance was obtained by removing a solvent (such as chloroform) from the oil layer. This oily substance was separated and purified by silica gel chromatography. At this time, as the moving layer, a mixture of chloroform, methanol and acetic acid in a volume ratio (chloroform: methanol: acetic acid) of 10: 1: 1 was used. Subsequently, 10 g of chloroform, 10 g of water, 1 g of acetic acid, and 1 g of sodium iodide were added to the oily substance after separation and purification, followed by oil-liquid separation, and the solvent (such as chloroform) in the oil layer was distilled off. Finally, 1 g of acetone is added to the residue after the solvent is distilled off, and the precipitated solid is filtered off and dried at 60 ° C. to obtain the final product (compound represented by the chemical formula (1B-3)) 0 0.04 g (yield 4%) was obtained.

(Experimental Example 1-4)
As shown in the chemical reaction formula (II-4), a compound composed of the structural part shown in the chemical formula (1-4) and iodide ion was synthesized.

  First, 0.00075 mol (0.30 g) of the compound represented by the chemical formula (15-1), 0.92 g of acetonitrile, and 0.00075 mol (0.08 g) of acetic anhydride were mixed at room temperature for 1 hour. Thereafter, 0.00075 mol (0.29 g) of the compound represented by the chemical formula (16-3) and 0.2 g of ethanol are added to the mixture, and the mixture is stirred at 50 ° C. for 3 hours, whereby the chemical reaction formula ( The reaction was carried out as shown in II-4). Next, 30 g of chloroform, 30 g of water, and 1 g of sodium iodide were added to the reaction product, followed by oil-liquid separation, and the solvent (such as chloroform) in the oil layer was distilled off. Finally, the residue after evaporation of the solvent is separated and purified by column chromatography, 3 g of acetone is added to the separated and purified material, the precipitated solid is filtered off and dried at 80 ° C. to obtain the final product ( 0.05 g (yield 11%) of the compound represented by the chemical formula (1B-4) was obtained.

(Experimental Example 1-5)
As shown in chemical reaction formula (II-5A) and chemical reaction formula (II-5B), a compound composed of the structure shown in chemical formula (1-5) and tetrafluoroborate ion (BF ₄ ⁻ ) was synthesized. did.

First, 0.002 mol (0.93 g) of the compound represented by the chemical formula (15-3), 4 g of acetonitrile, and 0.0024 mol (0.24 g) of acetic anhydride were mixed at 40 ° C. for 1 hour. After that, 0.0022 mol (0.46 g) of the compound represented by the chemical formula (16-4A) was added to this mixture, and the mixture was stirred at 50 ° C. for 4 hours, whereby the chemical reaction formula (II-5A) was shown. The compound represented by the chemical formula (16-4B) was synthesized. Subsequently, after adding 30 g of chloroform and 30 g of water to the reaction product containing the compound represented by the chemical formula (16-4B), the oil-liquid separation is performed, and the solvent (chloroform or the like) in the oil layer is distilled off to obtain an oily state. Obtained material. Subsequently, diethyl ether was added to the oily substance, and the precipitated solid was filtered off. Thereafter, the solid is dissolved in a mixed solution in which acetonitrile, water, acetic acid, and TEA are mixed at a volume ratio of 80: 20: 0.2: 0.2 (acetonitrile: water: acetic acid: TEA), By separation using high performance liquid chromatography, a solution containing the compound represented by the chemical formula (16-4B) was obtained. At this time, as the moving layer of high performance liquid chromatography, the above-mentioned mixed solution of acetonitrile, water, acetic acid and TEA (acetonitrile: water: acetic acid: TEA (volume ratio) = 80: 20: 0.2: 0.2) A composition having the same composition as in Example 1 was used. Subsequently, after the solvent was distilled off from the solution containing the compound represented by the chemical formula (16-4B), 2 cm ³ of dimethyl sulfoxide (DMSO) was added to the residue after the distillation and dissolved. Furthermore, 0.15 g of glycine represented by the chemical formula (16-4C) was added to the DMSO solution, and the mixture was stirred at 60 ° C. for 3 hours to cause a reaction as shown in the chemical reaction formula (II-5B). Next, 50 g of chloroform and 50 g of water were added to the reaction product, followed by oil-liquid separation, and the solvent (such as chloroform) in the oil layer was distilled off to obtain an oily substance. Subsequently, the oily substance was separated using a high performance liquid chromatography method to obtain a solution containing the compound represented by the chemical formula (1B-5). The moving bed of the high performance liquid chromatography used here is also the above-mentioned mixed solution of acetonitrile, water, acetic acid and TEA (acetonitrile: water: acetic acid: TEA (volume ratio) = 80: 20: 0.2: 0.2). It was set as the same composition. Finally, from the solution containing the compound represented by the chemical formula (1B-5), the compound represented by the chemical formula (1B-5) was extracted with chloroform, and then the chloroform was distilled off from the extract to obtain the final product ( 4 mg (yield 4%) of the compound represented by the chemical formula (1B-5) was obtained.

(Experimental example 1-6)
As shown in the chemical reaction formula (II-6), a compound composed of the structure part shown in the chemical formula (1-6) and bromide ions was synthesized.

  First, 0.0008 mol (0.36 g) of the compound represented by the chemical formula (15-4), 2.44 g of acetonitrile, and 0.001 mol of acetic anhydride were mixed at room temperature for 30 minutes. Thereafter, 0.009 mol (0.32 g) of a compound represented by the chemical formula (16-5), 0.6 g of pyridine, and 3 g of ethanol are added to the mixture, and the mixture is stirred at 50 ° C. for 5 hours. The reaction was carried out as shown in chemical reaction formula (II-6). Next, after adding 30 g of chloroform and 30 g of water to the reaction product, oil-liquid separation was performed, and an oily substance was obtained by distilling off the solvent (such as chloroform) in the oil layer. After that, 10 g of acetic acid and 1 g of 65% aqueous hydrobromic acid solution were added to the oily substance, mixed for 2 hours at 40 ° C., then chloroform and water were added to the mixture to separate the oil and liquid, The solvent (such as chloroform) in the oil layer was distilled off under reduced pressure. Subsequently, the residue after evaporation of the solvent was separated and purified by silica gel chromatography. At this time, as the moving layer, a mixture of acetone and methanol at a volume ratio (acetone: methanol) of 10: 1 was used. Finally, the solvent was distilled off from the separated and purified product to obtain 7 mg (yield 1.1%) of the final product (compound represented by the chemical formula (1B-6)).

(Experimental Example 1-7)
As shown in the chemical reaction formula (II-7), a compound composed of the structural part shown in the chemical formula (1-7) and iodide ion was synthesized.

First, 0.0015 mol (0.75 g) of the compound represented by the chemical formula (15-5), 2.12 g of acetonitrile, and 0.0015 mol of acetic anhydride (Ac ₂ O) were mixed at room temperature for 2 hours. Thereafter, 0.0015 mol (0.67 g) of the compound represented by the chemical formula (16-6), 1.06 g of pyridine, and 0.5 g of ethanol were added to the mixture, followed by stirring at 55 ° C. for 5 hours. As a result, the reaction was carried out as shown in the chemical reaction formula (II-7). Next, 30 g of chloroform, 30 g of water, and 1 g of acetic acid were added to the reaction product, followed by oil-liquid separation, and an oily substance was obtained by removing a solvent (such as chloroform) from the oil layer. 3 g of acetone was added to this oily substance, and the precipitated solid was filtered off and dried at 80 ° C. to obtain 0.12 g (yield 12%) of the final product (compound represented by the chemical formula (1B-7)). )

(Experimental Example 1-8)
As shown in the chemical reaction formula (II-8), a compound composed of the structure part shown in the chemical formula (1-8) and bromide ions was synthesized.

  First, in a mixture of 0.001 mol (0.45 g) of the compound represented by the chemical formula (15-6), 12 g of acetonitrile, and 0.0011 mol (0.33 g) of the compound represented by the chemical formula (16-7). On the other hand, 0.002 mol (0.2 g) of TEA was added dropwise. After that, the mixture was stirred for 3 hours at 50 ° C. to react as shown in the chemical reaction formula (II-8). As a result, a precipitate was formed. Next, after filtering this deposit, 10 g of acetone was added to the obtained solid, followed by reflux washing. The washed solid was filtered off and dried at 65 ° C. for 1 hour to obtain 0.12 g (yield 19.6%) of the final product (compound represented by the chemical formula (1B-8)). .

(Experimental example 1-9)
As shown in the chemical reaction formula (III-1), a compound composed of the structural part and the chloride ion shown in the chemical formula (1-9) was synthesized.

  First, 0.005 mol (1.48 g) of the compound represented by the chemical formula (17-1), 10 g of acetonitrile, 0.0002 mol of the compound represented by the chemical formula (18-2-1) as a bridging agent, and 1 g of TEA And the mixture was stirred at 60 ° C. for 5 hours to cause a reaction as shown in chemical reaction formula (III-1). At this time, a precipitate was formed, and when this precipitate was filtered off, 3 g of a reaction product (solid) was obtained. Subsequently, 10 g of chloroform and 10 g of water were added to 1.5 g of the reaction product of 3 g to dissolve the reaction product, and then 1 g of sodium chloride and 1 g of acetic acid were added to this solution to precipitate. The resulting solid was filtered off. Finally, the filtered solid was washed with acetone and dried at 75 ° C. for 1 hour to obtain 0.20 g (yield 31%) of the final product (compound represented by the chemical formula (1C-9)). Obtained.

  For the final products of these experimental examples 1-1 to 1-9, the structure was identified by nuclear magnetic resonance (NMR), and the maximum absorption wavelength (λmax), molar absorption coefficient (ε), and decomposition were determined. When the points were examined, the results shown in Table 1 and Table 2 were obtained.

When performing NMR measurement, Lambda-400 manufactured by JOEL was used as a measuring instrument. In this case, in Experimental Examples 1-1, 1-2, and 1-9, ³ to 10 mg of the final product was dissolved in 1 cm ^{3 of} deuterated dimethyl sulfoxide (DMSO-d ₆ ) as a deuterated solvent. Using the solution as a measurement sample, a ¹ H-NMR spectrum was measured at room temperature. In Experimental Examples 1-3 to 1-7, the same procedure as in Experimental Example 1-1 was performed except that deuterated chloroform (CDCl ₃ ) was used instead of DMSO-d ₆ as the deuterated solvent. Measured. Furthermore, in Experimental Example 1-8, the same procedure as in Experimental Example 1-1 was performed except that deuterated dimethylformamide (DMF-d ₇ ) was used instead of DMSO-d ₆ as the deuterated solvent. It was measured.

When examining the maximum absorption wavelength (λmax) and the molar absorption coefficient (ε), a UV spectrum meter (U-3010) manufactured by Hitachi, Ltd. was used. In this case, the final product was prepared for methanol (CH ₃ OH; solvent) so that the absorbance was in the range of 0.5 to 1.0 and used for measurement. In Experimental Example 1-9, measurement was not possible because the solubility of the final product in methanol was low.

When measuring the decomposition point, a calorimeter TG / DTA6200 manufactured by Shimadzu Corporation was used. In this case, the measurement was performed by increasing the temperature from room temperature to 550 ° C. at a rate of 10 ° C./min with the flow rate of nitrogen gas being 100 cm ³ / min. In Experimental Example 1-5, measurement was not performed because the yield of the final product was small.

  As shown in Tables 1 and 2, in Experimental Examples 1-1 to 1-9, the compounds represented by chemical formula (1B-1) to chemical formula (1B-8) and chemical formula (1C-9) were synthesized, respectively. It was confirmed that

(Experimental example 2-1)
Using the compound represented by the chemical formula (1B-1) synthesized in Experimental Example 1-1, a dye-sensitized solar cell was produced according to the following procedure as a specific example of the photoelectric conversion element described in the above embodiment.

First, the working electrode 10 was produced. First, a conductive substrate 11 made of a conductive glass substrate (F-SnO ₂ ) having a length of 2.0 cm, a width of 1.5 cm, and a thickness of 1.1 mm was prepared. Subsequently, a masking tape having a thickness of 70 μm is pasted on the conductive substrate 11 so as to surround a square of 0.5 cm in length and 0.5 cm in width, and 3 cm ^{3 of} metal oxide slurry is made to have a uniform thickness on this portion. And dried. In this case, as the metal oxide slurry, zinc oxide powder (average particle size 20 nm; FINEX-50 manufactured by Sakai Chemical Industry Co., Ltd.) is used so as to be 10% by weight, and Triton X-100 (Triton X100) as a nonionic surfactant. Was prepared by suspending in water to which 1 drop of registered trademark) was added. Subsequently, the masking tape on the conductive substrate 11 was peeled off, and this substrate was baked at 450 ° C. in an electric furnace to form a metal oxide semiconductor layer 12 having a thickness of about 5 μm. Subsequently, the compound represented by the chemical formula (1B-1) and deoxycholic acid are dissolved in absolute ethanol so as to have concentrations of 3 × 10 ⁻⁴ mol / dm ³ and 1 × 10 ⁻² mol / dm ³ , respectively. A dye solution was prepared. Subsequently, the conductive substrate 11 on which the metal oxide semiconductor layer 12 was formed was immersed in the above dye solution, and the dye 13 was supported.

Next, a conductive film having a thickness of 100 nm made of platinum is formed on one surface of a conductive substrate 21 made of a conductive glass substrate (F-SnO ₂ ) having a length of 2.0 cm, a width of 1.5 cm, and a thickness of 1.1 mm. The counter electrode 20 was produced by forming the layer 22. In this case, two holes (φ1 mm) for injecting an electrolytic solution were formed in the conductive substrate 21 in advance.

Next, an electrolytic solution was prepared. It adjusted so that it might become a density | concentration of dimethylhexyl imidazolium iodide (0.6 mol / dm < ³ >), lithium iodide (0.1 mol / dm < ³ >), and iodine (0.05 mol / dm < ³ >) with respect to acetonitrile.

  Next, after arranging a spacer having a thickness of 50 μm so as to surround the metal oxide semiconductor layer 12, the surface of the working electrode 10 carrying the dye 13 and the surface of the counter electrode 20 on which the conductive layer 22 is formed are formed. It was made to oppose and it bonded together through the spacer. After that, an electrolyte prepared from an injection port opened in the counter electrode 20 was injected to form the electrolyte containing layer 30. Finally, the whole was sealed to complete a dye-sensitized solar cell.

(Experimental Examples 2-2 to 2-9)
Instead of the compound represented by the chemical formula (1B-1) as the dye, the chemical formula (1B-2) to the chemical formula (1B-8) synthesized in Experimental Examples 1-2 to 1-9 as shown in Table 3, A procedure similar to that of Experimental Example 2-1 was performed, except that the compound represented by the chemical formula (1C-9) was used.

(Comparative Examples 1-1 to 1-7)
Experimental Example 2-1 except that the compounds shown in Chemical Formula (20) to Chemical Formula (26) were used as the dye instead of the compound shown in Chemical Formula (1B-1) as shown in Table 3. The same procedure was followed. The compounds represented by chemical formula (20) to chemical formula (26) are as follows.

  When the conversion efficiencies were examined for the dye-sensitized solar cells of Experimental Examples 2-1 to 2-9 and Comparative Examples 1-1 to 1-7, the results shown in Table 3 were obtained. Moreover, when IPCE was investigated about the dye-sensitized solar cell of Experimental example 2-1 and Comparative example 1-1 on behalf of these experimental examples, the result shown in FIG. 3 was obtained.

The conversion efficiency was calculated | required with the following calculation methods using the solar simulator of light source AM1.5 (1000 W / m < ² >). First, the voltage of the dye-sensitized solar cell was swept with a source meter, and the response current was measured. As a result, a value obtained by multiplying the value obtained by dividing the maximum output, which is the product of voltage and current, by the light intensity per 1 cm ² and multiplying by 100 was defined as conversion efficiency (η:%). That is, the conversion efficiency is expressed by (maximum output / 1 light intensity per 1 cm ² ) × 100. Moreover, when measuring IPCE, SM-10AC made from Peccell Technology was used as a measuring device. In FIG. 3, the measurement result of Experimental Example 2-1 is shown as a curve C11, and the measurement result of Comparative Example 1-1 is shown as a curve C21.

  As shown in Table 3, when the metal oxide semiconductor layer 12 is formed by a baking method and contains zinc oxide, the chemical formula (1B-1) to the chemical formula (1B- 8) In Experimental Examples 2-1 to 2-9 using the compounds represented by the chemical formula (1C-9), comparisons using the compounds represented by the chemical formulas (20) to (23) having no skeleton thereof Conversion efficiency became higher than Examples 1-1 to 1-4. In Experimental Examples 2-1 to 2-9, the compounds represented by chemical formula (24) and chemical formula (25) having a quinoline skeleton or a pyridine skeleton but not having an alkyl chain having a carboxylic acid group as an anchor group were used. Conversion efficiency became higher than Comparative Examples 1-5 and 1-6. Furthermore, in Experimental Examples 2-1 to 2-9, the conversion efficiency is higher than that of Comparative Example 1-7 using the compound represented by the chemical formula (26) in which no anchor group is introduced into the nitrogen atom of the indolenine skeleton. It was.

  Moreover, as shown in FIG. 3, in Experimental Example 2-1 (curve C11) using a cyanine compound having a quinoline skeleton, compared to Comparative Example 1-1 (curve C21) using a cyanine compound having no quinoline skeleton. It absorbed light in a wide wavelength range and converted it into current.

  These results represent the following. That is, in the compound represented by the chemical formula (1B-1), the inclusion of a quinoline skeleton or a pyridine skeleton spreads the π conjugation as a whole molecule. Therefore, a cyanine containing an indolenine skeleton or a thiazole skeleton instead of the quinoline skeleton or the like. Compared with compounds (compounds represented by chemical formula (20) to chemical formula (23)), the light absorption wavelength range is widened. Moreover, in the compound or the like represented by the chemical formula (1B-1), an alkyl chain having a carboxylic acid group as an anchor group for adsorbing to the metal oxide semiconductor layer 12 includes a complex included in R1 in the chemical formula (1). It is introduced into the nitrogen atom of the ring skeleton. Therefore, in the compound represented by the chemical formula (1B-1), cyanine compounds having other anchor groups (compounds represented by the chemical formula (24) and chemical formula (25)), and cyanines that do not contain an anchor group in R1. Compared with the compound (the compound represented by the chemical formula (26)), the electron injection efficiency into the metal oxide semiconductor layer 12 when excited by absorbing light is improved.

  Further, from the comparison between Experimental Examples 2-1 to 2-4 and Experimental Example 2-5, in the case of having a methine chain having 3 carbon atoms, in the cyanine compound having a quinoline skeleton rather than the cyanine compound having a pyridine skeleton. There was a trend toward higher conversion efficiency. This result indicates that the electron injection efficiency into the metal oxide semiconductor layer 12 is improved by having a quinoline skeleton rather than a pyridine skeleton in the cyanine compound.

  Further, from the comparison between Experimental Examples 2-1 to 2-3 and Experimental Example 2-4, and the comparison between Experimental Examples 2-6 and 2-7 and Experimental Examples 2-8 and 2-9, the chemical formula (1) In the case where a cyanine compound in which R1 is a group represented by the chemical formula (2-1) is used, the conversion efficiency is higher than when a cyanine compound having no group represented by the chemical formula (2-1) is used. It showed a tendency to increase. This result indicates that the association inhibitory action was exhibited by having a bulky group together with the indolenine skeleton in the cyanine compound.

  From these things, the following was confirmed in the photoelectric conversion element in which the metal oxide semiconductor layer 12 is formed by a firing method and contains zinc oxide. That is, by including the cyanine compound represented by the chemical formula (1) in the dye 13, the conversion efficiency can be improved without depending on the type of the cyanine compound. In this case, if R1 in the chemical formula (1) is a group represented by the chemical formula (2-1), the conversion efficiency can be further improved. If Q in chemical formula (1) is a linking group having a methine chain having 3 carbon atoms as a skeleton and R2 is a group shown in chemical formula (7) or chemical formula (8), the conversion efficiency is further improved. Can be made.

(Experimental examples 3-1 to 3-9)
Except that the metal oxide semiconductor layer 12 was formed by electrolytic deposition, the same procedure as in Experimental Examples 2-1 to 2-9 was performed. When forming the metal oxide semiconductor layer 12 by the electrolytic deposition method, the following procedure was used. First, 40 ml of an electrolytic bath solution prepared to have a concentration of eosin Y (30 μmol / dm ³ ), zinc chloride (5 mmol / dm ³ ), potassium chloride (0.09 mol / dm ³ ) with respect to water, and a zinc plate And a reference electrode made of a silver / silver chloride electrode. Subsequently, after bubbling the electrolytic bath with oxygen for 15 minutes, the temperature of the solution in the electrolytic bath is set to 70 ° C., and the constant potential electrolysis of −1.0 V is bubbled for 60 minutes, and the surface of the conductive substrate 11 is manufactured. Filmed. Finally, this substrate was immersed in an aqueous potassium hydroxide solution (pH 11) without drying, and then washed with water to desorb eosin Y. Subsequently, it was dried at 150 ° C. for 30 minutes.

(Comparative Examples 2-1 to 2-7)
The same procedure as Comparative Examples 1-1 to 1-7 was performed except that the metal oxide semiconductor layer 12 was formed in the same manner as in Experimental Examples 3-1 to 3-9.

  When conversion efficiency was calculated | required about the dye-sensitized solar cell of these Experimental Examples 3-1 to 3-9 and Comparative Examples 2-1 to 2-7, the result shown in Table 4 was obtained.

  As shown in Table 4, when the metal oxide semiconductor layer 12 was formed by electrolytic deposition, the same results as those shown in Table 3 were obtained. That is, in Experimental Examples 3-1 to 3-9 using the compound shown in the chemical formula (1B-1) having a quinoline skeleton or a pyridine skeleton as a dye, the chemical formulas (20) to (9) having no such skeleton The conversion efficiency was higher than Comparative Examples 2-1 to 2-4 using the compound shown in 23). In Experimental Examples 3-1 to 3-9, the compounds represented by chemical formula (24) and chemical formula (25) having a quinoline skeleton or a pyridine skeleton but not having an alkyl chain having a carboxylic acid group as an anchor group were used. Conversion efficiency became higher than Comparative Examples 2-5 and 2-6. Furthermore, in Experimental Examples 3-1 to 3-9, the conversion efficiency is higher than that of Comparative Example 2-7 using the compound represented by the chemical formula (26) in which the anchor group is not introduced into the nitrogen atom of the indolenine skeleton. It was.

  Also in this case, from the comparison between Experimental Examples 3-1 to 3-4 and Experimental Example 3-5, when a cyanine compound having a methine chain having 3 carbon atoms is used, it is more effective than a cyanine compound having a pyridine skeleton. There was a tendency for the conversion efficiency to increase in cyanine compounds having a quinoline skeleton. Further, from the comparison between Experimental Examples 3-1 to 3-3 and Experimental Example 3-4 and the comparison between Experimental Examples 3-6 and 3-7 and Experimental Examples 3-8 and 3-9, the chemical formula (1) When a cyanine compound in which R1 is a group represented by chemical formula (2-1) is used, the conversion efficiency is higher than when a cyanine compound having no group represented by chemical formula (2-1) is used. Showed a trend.

  From these things, the following was confirmed in the photoelectric conversion element in which the metal oxide semiconductor layer 12 is formed by electrolytic deposition and contains zinc oxide. That is, by including the cyanine compound represented by the chemical formula (1) in the dye 13, the conversion efficiency can be improved without depending on the type of the cyanine compound. In this case, if R1 in the chemical formula (1) is a group represented by the chemical formula (2-1), the conversion efficiency can be further improved. If Q in chemical formula (1) is a linking group having a methine chain having 3 carbon atoms as a skeleton and R2 is a group shown in chemical formula (7) or chemical formula (8), the conversion efficiency is further improved. Can be made.

(Experimental examples 4-1 to 4-9)
When forming the metal oxide semiconductor layer 12 by the firing method, instead of using the zinc oxide powder, a metal oxide slurry containing titanium oxide (TiO ₂ ) powder was used, and Experimental Examples 2-1 to 2- The same procedure as 9 was performed. In this case, a metal oxide slurry containing titanium oxide powder was prepared as follows. First, titanium isopropoxide 125 cm ^3, was added with stirring to 0.1 mol / dm ³ aqueous solution of nitric acid 750 cm ^3, and 8 hours vigorously stirred at 80 ° C.. The obtained liquid was poured into a pressure vessel made of Teflon (registered trademark), and the pressure vessel was treated in an autoclave at 230 ° C. for 16 hours. After that, the liquid (sol solution) containing the autoclaved precipitate was resuspended by stirring. Subsequently, the suspension was subjected to suction filtration to remove precipitates that were not resuspended, and the sol-like filtrate was concentrated with an evaporator until the titanium oxide concentration became 11% by mass. After that, 1 drop of Triton X-100 was added to the concentrated solution in order to improve the paintability to the substrate. Subsequently, titanium oxide powder having an average particle size of 30 nm (P-25 manufactured by Nippon Aerosil Co., Ltd.) was added to the sol-like concentrated solution so that the total content of titanium oxide was 33% by mass, and rotation revolution was utilized. Centrifugal stirring was performed for 1 hour to disperse.

(Comparative Examples 3-1 to 3-7)
A procedure similar to that of Comparative Examples 1-1 to 1-7 was performed except that the metal oxide semiconductor layer 12 was formed in the same manner as in Experimental Examples 4-1 to 4-9.

  For the dye-sensitized solar cells of Experimental Examples 4-1 to 4-9 and Comparative Examples 3-1 to 3-7, the conversion efficiency was examined. The results illustrated in Table 5 were obtained.

  As shown in Table 5, when the metal oxide semiconductor layer 12 was formed by the firing method and contained titanium oxide, the same results as those shown in Table 3 were obtained. That is, in Experimental Examples 4-1 to 4-9 using the compound shown in the chemical formula (1B-1) having a quinoline skeleton or a pyridine skeleton as a dye, the chemical formulas (20) to (9) having no such skeleton The conversion efficiency was higher than those of Comparative Examples 3-1 to 3-4 using the compound shown in 23). In Experimental Examples 4-1 to 4-9, the compounds represented by chemical formula (24) and chemical formula (25) having a quinoline skeleton or a pyridine skeleton but not having an alkyl chain having a carboxylic acid group as an anchor group were used. Conversion efficiency became higher than Comparative Examples 3-5 and 3-6. Furthermore, in Experimental Examples 4-1 to 4-9, the conversion efficiency is higher than that of Comparative Example 3-7 using the compound represented by Chemical Formula (26) in which no anchor group is introduced into the nitrogen atom of the indolenine skeleton. It was.

  Also in this case, from the comparison between Experimental Examples 4-1 to 4-4 and Experimental Example 4-5, when a cyanine compound having a methine chain having 3 carbon atoms is used, it is more effective than a cyanine compound having a pyridine skeleton. There was a tendency for the conversion efficiency to increase in cyanine compounds having a quinoline skeleton. Further, from the comparison between Experimental Examples 4-1 to 4-3 and Experimental Example 4-4, and the comparison between Experimental Examples 4-6 and 4-7 and Experimental Examples 4-8 and 4-9, the chemical formula (1) When a cyanine compound in which R1 is a group represented by chemical formula (2-1) is used, the conversion efficiency is higher than when a cyanine compound having no group represented by chemical formula (2-1) is used. Showed a trend.

  From these things, the following was confirmed in the photoelectric conversion element in which the metal oxide semiconductor layer 12 is formed by a firing method and contains titanium oxide. That is, by including the cyanine compound represented by the chemical formula (1) in the dye 13, the conversion efficiency can be improved without depending on the type of the cyanine compound. In this case, if R1 in the chemical formula (1) is a group represented by the chemical formula (2-1), the conversion efficiency can be further improved. If Q in chemical formula (1) is a linking group having a methine chain having 3 carbon atoms as a skeleton and R2 is a group shown in chemical formula (7) or chemical formula (8), the conversion efficiency is further improved. Can be made.

  Further, from the results shown in Tables 3 to 5, in the photoelectric conversion element in this example, when the dye 13 contains the cyanine compound represented by the chemical formula (1), the type of the cyanine compound and the metal oxidation It was confirmed that the conversion efficiency was improved without depending on the method for forming the physical semiconductor layer 12 and the type of the metal oxide semiconductor material. In this case, when zinc oxide was used as the metal oxide semiconductor material (see Tables 3 and 4), the conversion efficiency was higher than when titanium oxide was used (see Table 5). From this, it was confirmed that the conversion efficiency is further improved particularly when the metal oxide semiconductor layer 12 contains zinc oxide.

  The present invention has been described with reference to the embodiments and examples. However, the present invention is not limited to the embodiments described in the above embodiments and examples, and various modifications can be made. For example, the usage application of the photoelectric conversion element of the present invention is not necessarily limited to the usage already described, and may be other usages. Other applications include, for example, an optical sensor.

  DESCRIPTION OF SYMBOLS 10 ... Working electrode, 11, 21 ... Conductive substrate, 11A ... Substrate, 11B ... Conductive layer, 12 ... Metal oxide semiconductor layer, 12A ... Dense layer, 12B ... Porous layer, 13 ... Dye, 20 ... Counter electrode, 22 ... conductive layer, 30 ... electrolyte-containing layer.

Claims (13)

An electrode having a dye and a carrier carrying the dye;
The said pigment | dye contains the cyanine compound represented by Chemical formula (1). The photoelectric conversion element characterized by the above-mentioned.

(R1 is any one of groups represented by chemical formula (2) to chemical formula (6), and R2 is any one of groups represented by chemical formula (7) to chemical formula (10). Q is a linking group having a skeleton of a methine chain having 1 to 7 carbon atoms, Z ^p- is a p-valent anion, p is 1 or 2, and q neutralizes the charge. (The coefficient to keep.)

(R10 to R13 are each independently a hydrogen atom, a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, or a derivative thereof, and at least one of R10 and R11 And at least one of R12 and R13 may be eliminated to form a double bond, or may be linked to form a ring structure, R14 is an alkylene group, and X is —C. A group represented by (R15) (R16)-, a group represented by -N (R17)-, a sulfur atom, an oxygen atom, a selenium atom or a tellurium atom, wherein R15 to R17 are each independently a hydrogen atom or a chemical formula; An alkyl group, an alkoxy group, an aryl group other than the group represented by (11) or the group represented by the chemical formula (11), .Y1 a reel alkyl group, or a derivative thereof is a carboxylic acid group (-C (= O) -OH) or carboxylic acid ion group ^{(-C (= O) -O -} ) is).

(R18 to R23 and R25 to R30 are each independently a hydrogen atom, a hydroxyl group, a nitro group, a cyano group or a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, or a derivative thereof. R24 and R31 are An alkylene group, Y2 and Y3 are a carboxylic acid group or a carboxylic acid ion group.)

(R32 to R35 and R37 to R40 are each independently a hydrogen atom, a hydroxyl group, a nitro group, a cyano group or a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, or a derivative thereof. R36 and R41 are Y4 and Y5 are carboxylic acid groups or carboxylic acid ion groups.

(R42 to R65 are each independently a hydrogen atom, a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, or a derivative thereof.)

(The bond between L1 and T1 is a double bond or a triple bond, L1 represents a carbon atom, T1 represents a carbon atom, an oxygen atom or a nitrogen atom, and x, y and z are each independently 0 or (However, when T1 is an oxygen atom, x and y are 0, and when T1 is a nitrogen atom, (y + z) is 0 or 1.) R66 to R68 are each independently A hydrogen atom, a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, R69 is a hydrogen atom, a hydroxyl group, a nitro group, A cyano group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms A halogenated alkoxy group of the lower, R66 and R69, R67 and may be to form a ring structure, respectively and R68 .n is zero or an integer of 4 or less.) Wherein R14, R24, R31, R36 and R41 is an ethylene group - photoelectric conversion element according to claim 1, wherein it is a (-CH ₂ -CH _2). Said R1 is group represented by Chemical formula (2-1). The photoelectric conversion element of Claim 1 characterized by the above-mentioned.

(Ring A is a benzene ring, naphthalene ring, phenanthrene ring or a derivative thereof. R14 is an alkylene group. R15 and R16 are each independently a hydrogen atom, a group represented by the chemical formula (11), or a chemical formula (11 And an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, or a derivative thereof, except that at least one of R15 and R16 is a benzyl group or an alkyl group. Y1 is a carboxylic acid group (—C (═O) —OH) or a carboxylic acid ion group (—C (═O) —O ⁻ ).

(The bond between L1 and T1 is a double bond or a triple bond, L1 represents a carbon atom, T1 represents a carbon atom, an oxygen atom or a nitrogen atom, and x, y and z are each independently 0 or (However, when T1 is an oxygen atom, x and y are 0, and when T1 is a nitrogen atom, (y + z) is 0 or 1.) R66 to R68 are each independently A hydrogen atom, a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, R69 is a hydrogen atom, a hydroxyl group, a nitro group, A cyano group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms A halogenated alkoxy group of the lower, R66 and R69, R67 and may be to form a ring structure, respectively and R68 .n is zero or an integer of 4 or less.) Wherein R14 is an ethylene group - photoelectric conversion element according to claim 3, wherein it is a (-CH ₂ -CH _2). Q is a linking group having a skeleton of a methine chain having 3 carbon atoms,
5. The photoelectric conversion element according to claim 1, wherein R 2 is a group represented by the chemical formula (7) or the chemical formula (8). 5. The photoelectric conversion element according to claim 1, wherein Q is a linking group in which a cyano group is introduced into a methine chain having 5 carbon atoms. The photoelectric conversion element according to any one of claims 1 to 6, wherein the carrier includes zinc oxide (ZnO). It has the cyanine structure represented by Chemical formula (1). The pigment | dye for photoelectric conversion elements characterized by the above-mentioned.

(R1 is any one of groups represented by chemical formula (2) to chemical formula (6), and R2 is any one of groups represented by chemical formula (7) to chemical formula (10). Q is a linking group having a skeleton of a methine chain having 1 to 7 carbon atoms, Z ^p- is a p-valent anion, p is 1 or 2, and q neutralizes the charge. (The coefficient to keep.)

(R10 to R13 are each independently a hydrogen atom, a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, or a derivative thereof, and at least one of R10 and R11 And at least one of R12 and R13 may be eliminated to form a double bond, or may be linked to form a ring structure, R14 is an alkylene group, and X is —C. A group represented by (R15) (R16)-, a group represented by -N (R17)-, a sulfur atom, an oxygen atom, a selenium atom or a tellurium atom, wherein R15 to R17 are each independently a hydrogen atom or a chemical formula; An alkyl group, an alkoxy group, an aryl group other than the group represented by (11) or the group represented by the chemical formula (11), .Y1 a reel alkyl group, or a derivative thereof is a carboxylic acid group (-C (= O) -OH) or carboxylic acid ion group ^{(-C (= O) -O -} ) is).

(R18 to R23 and R25 to R30 are each independently a hydrogen atom, a hydroxyl group, a nitro group, a cyano group or a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, or a derivative thereof. R24 and R31 are An alkylene group, Y2 and Y3 are a carboxylic acid group or a carboxylic acid ion group.)

(R32 to R35 and R37 to R40 are each independently a hydrogen atom, a hydroxyl group, a nitro group, a cyano group or a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, or a derivative thereof. R36 and R41 are Y4 and Y5 are carboxylic acid groups or carboxylic acid ion groups.

(R42 to R65 are each independently a hydrogen atom, a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, or a derivative thereof.)

(The bond between L1 and T1 is a double bond or a triple bond, L1 represents a carbon atom, T1 represents a carbon atom, an oxygen atom or a nitrogen atom, and x, y and z are each independently 0 or (However, when T1 is an oxygen atom, x and y are 0, and when T1 is a nitrogen atom, (y + z) is 0 or 1.) R66 to R68 are each independently A hydrogen atom, a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, R69 is a hydrogen atom, a hydroxyl group, a nitro group, A cyano group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms A halogenated alkoxy group of the lower, R66 and R69, R67 and may be to form a ring structure, respectively and R68 .n is zero or an integer of 4 or less.) Wherein R14, R24, R31, R36 and R41 are an ethylene group (-CH ₂ -CH ₂ -) according to claim 8, wherein dye for a photoelectric conversion device, characterized in that. The dye for a photoelectric conversion element according to claim 8, wherein R1 is a group represented by the chemical formula (2-1).

(Ring A is a benzene ring, naphthalene ring, phenanthrene ring or a derivative thereof. R14 is an alkylene group. R15 and R16 are each independently a hydrogen atom, a group represented by the chemical formula (11), or a chemical formula (11 And an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, or a derivative thereof, except that at least one of R15 and R16 is a benzyl group or an alkyl group. Y1 is a carboxylic acid group or a carboxylic acid ion group.)

(The bond between L1 and T1 is a double bond or a triple bond, L1 represents a carbon atom, T1 represents a carbon atom, an oxygen atom or a nitrogen atom, and x, y and z are each independently 0 or (However, when T1 is an oxygen atom, x and y are 0, and when T1 is a nitrogen atom, (y + z) is 0 or 1.) R66 to R68 are each independently A hydrogen atom, a hydroxyl group, a nitro group, a cyano group, a halogen atom, an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, R69 is a hydrogen atom, a hydroxyl group, a nitro group, A cyano group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms A halogenated alkoxy group of the lower, R66 and R69, R67 and may be to form a ring structure, respectively and R68 .n is zero or an integer of 4 or less.) Wherein R14 is an ethylene group (-CH ₂ -CH ₂ -) of claim 10, wherein the dye for a photoelectric conversion device, characterized in that. Q is a linking group having a skeleton of a methine chain having 3 carbon atoms,
The dye for a photoelectric conversion element according to any one of claims 8 to 11, wherein R2 is a group represented by the chemical formula (7) or the chemical formula (8). 12. The dye for a photoelectric conversion element according to claim 8, wherein Q is a linking group in which a cyano group is introduced into a methine chain having 5 carbon atoms.

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