KR101640974B1 - Metal complex pigment composition, photoelectric conversion element, photoelectrochemical cell, and method for producing metal complex pigment - Google Patents

Abstract

[PROBLEMS] To provide a metal complex coloring composition having high solubility in a solvent, and a photoelectric conversion element and a photoelectrochemical cell having high photoelectric conversion efficiency.
(Solution) A metal complex dye represented by the following general formula (1) and a metal complex dye having a specific structure are dissolved in a metal complex containing 0.5 to 5% of the area detected by HPLC (high performance liquid chromatography) at 254 nm Pigment composition.
_{^{M 1 (LL 1) m1 (}} LL 2) m2 (Z 1) 2 · (CI 1) m3 formula (1)
[In the general formula (1), M ¹ represents a metal atom, LL ¹ is a ligand at the 2-position, and LL ² is a ligand at the 2-position. Z ¹ represents a ligand and is at least one selected from an isothiocyanato group, an isocyanato group and an isoselenocyanato group. CI ¹ represents a counter ion when a counter ion is required to neutralize the charge. m1 and m2 are both 1, and m3 is an integer of 0 or more.]

Description

FIELD OF THE INVENTION [0001] The present invention relates to a metal complex dye composition, a photoelectric conversion element and a photoelectrochemical cell, and a method for producing a metal complex dye,

The present invention relates to a metal complex coloring composition having high solubility in a solvent and a photoelectric conversion element and a photoelectrochemical cell having high photoelectric conversion efficiency.

Photoelectric conversion elements are used in various optical sensors, copying machines, photoelectrochemical cells (for example, solar cells) and the like. This photoelectric conversion element has been put to practical use by various methods such as using a metal, a semiconductor, an organic pigment or a pigment, or a combination thereof. Among them, a solar cell using solar energy of a non-gable property uses a clean energy which is unnecessary for fuel and has been expected to be put into practical use in earnest. Among these, silicon-based solar cells have been undergoing research and development for a long time. There is policy consideration of each country and diffusion is proceeding. However, silicon is an inorganic material, and its throughput and molecular formula are naturally limited.

Therefore, the research of the dye-sensitized solar cell is energetically performed. In particular, Graetzel et al. Of Lausanne Institute of Technology in Switzerland developed a dye-sensitized solar cell in which a pigment consisting of a ruthenium complex was fixed on the surface of a porous titanium oxide thin film, and realized a conversion efficiency of the amorphous silicon level. As a result, a dye-sensitized solar cell has been attracting attention from a world-wide researcher.

Patent Document 1 describes a dye-sensitized photoelectric conversion element using semiconductor fine particles increased or decreased by a ruthenium complex dye by applying this technique. A photoelectric conversion device using an inexpensive organic dye as a sensitizer has also been reported. However, it is not sufficient to obtain a photoelectric conversion element having a high conversion efficiency.

Thus, a technique for improving the photoelectric conversion efficiency by adsorbing a photosensitizing dye of a specific structure to semiconductor fine particles has been proposed (see, for example, Patent Documents 2 and 3). However, since the photosensitizing dye (pure product) described in Patent Documents 2 and 3 is low in solubility in solvents, the adsorption amount of the dye to the semiconductor fine particles is insufficient under certain conditions, which is not sufficient in terms of photoelectric conversion efficiency , It is not sufficient from the viewpoint of productivity that the amount of the pigment used is large or it takes a long time to dissolve it.

U.S. Patent No. 5463057 Japanese Patent Publication No. 4576494 Japanese Patent Application Laid-Open No. 2001-291534

The object of the present invention is to provide a metal complex coloring composition having high solubility in a solvent, a photoelectric conversion element having high photoelectric conversion efficiency, and a photoelectrochemical cell. Another object of the present invention is to provide a method for producing a metal complex dye having high solubility in a solvent.

As a result of intensive studies, the inventors of the present invention have found that a metal complex dye containing a specific ligand has a high solubility in a solvent, so that the adsorption amount of the dye to semiconductor fine particles can be improved, And a photoelectrochemical cell can be provided. The present invention is based on this finding.

According to the present invention, the following means are provided.

(1) A metal complex dye comprising a metal complex dye represented by the following general formula (1), a metal complex dye represented by the following general formula (5) and / or a metal complex dye represented by the following general formula (6)

The content of the metal complex dye represented by the general formula (5) and the content of the metal complex dye represented by the general formula (6) is 0.5 to 5% in terms of the area detected at 254 nm of HPLC (high performance liquid chromatography) A metal complex coloring composition.

_{^{M 1 (LL 1) m1 (}} LL 2) m2 (Z 1) 2 · (CI 1) m3 formula (1)

[Formula (1) of, M ¹ represents a metal atom, LL ¹ is to a 2 L ligand represented by formula (2), LL ² is a ligand of the two left and represented by the following formula (3).

m1 represents 1. m2 represents 1.

Z ¹ represents a ligand and is at least one selected from an isothiocyanato group, an isocyanato group and an isoselenocyanato group.

CI ¹ represents a counter ion when a counter ion is required to neutralize the charge, and m 3 is an integer of 0 or more.

[Chemical Formula 1]

In the general formula (2), R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ independently represent an acidic group or a salt or a hydrogen atom, and R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ may be the same or different, do. Provided that at least one of R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ is an acid group or a salt thereof]

(2)

[, N1 in the general formula (3), n2 is independently an integer of ^{0 ~ 3, Y 1, Y} 2 are respectively independently a heteroaryl group represented by formula (4) or a hydrogen atom. Provided that Ar ¹ and Ar ² independently represent a heteroaryl group represented by the following general formula (4):

(3)

[In the general formula (4), R ³¹ to R ³³ independently represent a hydrogen atom, an alkyl group, an alkoxy group or an alkynyl group, and at least one of R ³¹ to R ³³ is an alkyl group, an alkoxy group or an alkynyl group. X is a sulfur atom, an oxygen atom, a selenium atom or NR ⁴ , and R ⁴ is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

_{^{M 1 (LL 1) m1 (}} LL 2) m2 (Z 1) (CN) · (CI 1) m3 general formula (5)

(In the general formula (5), M ¹ , LL ¹ , LL ² , Z ¹ , CI ¹ , m1, m2 and m3 have the same meanings as in formula (1)

_{^{M 1 (LL 1) m1 (}} LL 2) m2 (CN) 2 · (CI 1) m3 general formula (6)

(In the general formula (6), M ¹ , LL ¹ , LL ² , Z ¹ , CI ¹ , m1, m2 and m3 have the same meanings as in formula (1)

<2> The metal complex coloring composition according to <1>, wherein LL ² is represented by the following general formula (7) in the general formula (1).

[Chemical Formula 4]

[In the general formula (7), R ⁴¹ to R ⁴³ and R ⁵¹ to R ⁵³ independently represent a hydrogen atom, an alkyl group, an alkoxy group or an alkynyl group. At least one of R ⁴¹ to R ⁴³ is an alkyl group, an alkoxy group or an alkynyl group. At least one of R ⁵¹ to R ⁵³ is an alkyl group, an alkoxy group or an alkynyl group. X ¹ and X ² are each independently a sulfur atom, an oxygen atom, a selenium atom or NR ⁷ , and R ⁷ is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

<3> The metal complex coloring composition according to <2>, wherein X ¹ and X ² in the general formula (7) are sulfur atoms.

<4> The metal complex dye composition according to any one of <1> to <3>, wherein the metal complex dye represented by the general formula (1) is represented by the following general formula (8)

[Chemical Formula 5]

[Wherein, in formula (8), R ⁶¹ and R ⁶² independently represent an alkyl group, an alkoxy group or an alkynyl group, and A ¹ and A ² independently represent a carboxyl group or a salt thereof]

&Lt; 5 > A metal complex dye represented by the general formula (5) is represented by the following general formula (9), and a metal complex dye represented by the general formula (6) The metal complex coloring composition according to any one of < 4 > to < 4 >.

[Chemical Formula 6]

[In the formula (9), R ⁷¹ and R ⁷² independently represent an alkyl group, an alkoxy group or an alkynyl group, and A ⁵ and A ⁶ independently represent a carboxyl group or a salt thereof.

In the general formula (10), R ⁷³ and R ⁷⁴ independently represent an alkyl group, an alkoxy group or an alkynyl group, and A ⁷ and A ⁸ independently represent a carboxyl group or a salt thereof.

(6) The metal complex dye represented by the above general formula (5) is represented by the following general formula (11) and the metal complex dye represented by the general formula (6) is represented by the general formula The metal complex coloring composition according to any one of < 5 > to < 5 >.

(7)

[In formulas (11) and (12), R ⁸¹ to R ⁸⁴ independently represent an alkynyl group. A ¹³ to A ¹⁶ independently represent a carboxyl group or a salt thereof.

(7) A process for producing a metal complex dye represented by the following general formula (14), which comprises the step of raising the temperature of the mixed liquid by external heating of a mixed solution containing a metal complex dye of the following general formula (13) 1). &Lt; / RTI >

_{^{M 1 (LL 1) m1 (}} LL 2) m2 (Z 2) m4 · (CI 1) m5 general formula (13)

[In the general formula (13), M ¹ , LL ¹ , LL ² , CI ¹ , m ¹ and m 2 have the same meanings as in the general formula (1). Z ² is a 1-left or 2-left ligand. m4 is when an integer of 1 ~ ^2, Z 2 is L 1 ligand m4 represents a 2, Z ² is L 2 represents a ligand days when m4 is 1. m5 is an integer of 0 or more.]

M ¹¹ QCN In general formula (14)

Wherein M ¹¹ represents an inorganic or organic ammonium ion, a proton or an alkali metal ion, and Q represents a sulfur atom, an oxygen atom or a selenium atom,

_{^{M 1 (LL 1) m1 (}} LL 2) m2 (Z 1) 2 · (CI 1) m3 formula (1)

[In the formula (1), M ¹ represents a metal atom, LL ¹ is a two-coordinate ligand represented by the following formula (2), and LL ² is a two-coordinate ligand represented by the following formula (3).

m1 represents 1, m2 represents 1, and m3 represents an integer of 0 or more.

Z ¹ represents a ligand and is at least one selected from an isothiocyanato group, an isocyanato group and an isoselenocyanato group.

CI ¹ represents a counter ion when a counter ion is required to neutralize the charge.

[Chemical Formula 8]

In the general formula (2), R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ independently represent an acidic group or a salt or a hydrogen atom, and R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ may be the same or different, do. Provided that at least one of R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ is an acid group or a salt thereof]

[Chemical Formula 9]

[, N1 in the general formula (3), n2 is independently an integer of ^{0 ~ 3, Y 1, Y} 2 are respectively independently a heteroaryl group represented by formula (4) or a hydrogen atom. Provided that Ar ¹ and Ar ² independently represent a heteroaryl group represented by the following general formula (4):

[Chemical formula 10]

[In the general formula (4), R ³¹ to R ³³ independently represent a hydrogen atom, an alkyl group, an alkoxy group or an alkynyl group, and at least one of R ³¹ to R ³³ is an alkyl group, an alkoxy group or an alkynyl group. X is a sulfur atom, an oxygen atom, a selenium atom or NR ⁴ , and R ⁴ is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

<8> The method for producing a metal complex dye according to <7>, wherein LL ² in the general formula (1) is represented by the following general formula (7).

(11)

[In the general formula (7), R ⁴¹ to R ⁴³ and R ⁵¹ to R ⁵³ independently represent a hydrogen atom, an alkyl group, an alkoxy group or an alkynyl group. At least one of R ⁴¹ to R ⁴³ is an alkyl group, an alkoxy group or an alkynyl group. At least one of R ⁵¹ to R ⁵³ is an alkyl group, an alkoxy group or an alkynyl group. X ¹ and X ² are each independently a sulfur atom, an oxygen atom, a selenium atom or NR ⁷ , and R ⁷ is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

<9> The method for producing a metal complex coloring matter according to <8>, wherein X ¹ and X ² in the general formula (7) are sulfur atoms.

<10> The organic electroluminescent device according to <10>, wherein the compound represented by the formula (1) is represented by the following formula (8), the compound represented by the formula (13) is represented by the following formula (15) Wherein the metal complex dye is a metal complex dye.

[Chemical Formula 12]

Wherein R ⁶¹ , R ⁶² , R ⁹¹ and R ⁹² independently represent a hydrogen atom, an alkyl group, an alkoxy group or an alkynyl group, A ¹ to A ⁴ independently represent a carboxyl group Or a salt thereof. In the general formula (16), M ¹² represents an inorganic or organic ammonium ion, a proton or an alkali metal ion.]

(11) is represented by the following general formula (17), the general formula (13) is represented by the following general formula (18) Wherein the metal complex dye is a metal complex dye.

[Chemical Formula 13]

In the general formulas (17) and (18), R ¹⁰¹ , R ¹⁰² , R ¹¹¹ and R ¹¹² independently represent an alkynyl group, and A ⁹ to A ¹² independently represent a carboxyl group or a salt thereof. In the general formula (19), M ¹³ represents an inorganic or organic ammonium ion, a proton or an alkali metal ion.

<12> A photoelectric conversion element characterized by using the metal complex coloring composition according to any one of <1> to <6> as a sensitizing dye.

<13> A photoelectric conversion element characterized by using a metal complex dye produced by the method for producing a metal complex dye according to any one of <7> to <11>.

&Lt; 14 > A photoelectrochemical cell comprising the photoelectric conversion element according to any one of < 1 > to < 13 >.

According to the present invention, it is possible to provide a photoelectric conversion element and a photoelectrochemical cell having high conversion efficiency and excellent durability.

These and other features and advantages of the present invention will become more apparent from the following description, with reference to the appended drawings, as appropriate.

1 is a cross-sectional view schematically showing an embodiment of a photoelectric conversion element manufactured by the present invention.

As a result of intensive studies, the inventors of the present invention have found that a metal complex dye containing a specific ligand has a high solubility in a solvent, so that the adsorption amount of the dye to semiconductor fine particles can be improved, And a photoelectrochemical cell can be provided. The present invention is based on this finding.

A preferred embodiment of the photoelectric conversion element of the present invention will be described with reference to a schematic sectional view of Fig.

1, the photoelectric conversion element 10 includes an electroconductive substrate 1, a photoconductor layer 2, a charge carrier layer 3, and a counter electrode 3, which are arranged in this order on the electroconductive substrate 1, (4). The light receiving electrode 5 is constituted by the conductive support 1 and the photosensitive layer 2. The photoconductor layer 2 has semiconductor fine particles 22 and a sensitizing dye (hereinafter, simply referred to as dye) 21. The sensitizing dyes 21 are adsorbed to the semiconductor fine particles 22 in at least a part of them (the sensitizing dyes 21 are in an adsorption equilibrium state and may be present in some of the charge transporting layer 3). The charge transporting layer 3 functions as, for example, a hole transporting layer for transporting holes (holes). The electroconductive support 1 on which the photoconductor layer 2 is formed functions as a working electrode in the photoelectric conversion element 10. [ The photoelectric conversion element 10 can be operated as the photoelectrochemical cell 100 by causing the external circuit 6 to work.

The light receiving electrode 5 is an electrode consisting of a conductive support 1 and a photoconductor layer 2 (semiconductor film) of the semiconductor fine particles 22 on which the sensitizing dye 21 applied on the conductive support 1 is adsorbed . Light incident on the photoconductor layer 2 (semiconductor film) excites the dye. Here, the dye has high energy electrons. Therefore, the electrons are transferred from the sensitizing dye 21 to the conduction band of the semiconductor fine particles 22, and further reach the conductive support 1 by diffusion. At this time, the molecules of the sensitizing dyes 21 are oxidized. Electrons on the electrode return to the oxidized body while working in the external circuit 6, thereby acting as the photoelectrochemical cell 100. At this time, the light-receiving electrode 5 acts as a negative electrode of the battery.

The photoconductor layer 2 is composed of a porous semiconductor layer composed of a layer of semiconductor fine particles 22 to which a dye is adsorbed, which will be described later. This dye may be dissociated in some electrolytes. The photoconductor layer 2 is designed according to purposes, and has a multilayer structure.

As described above, the photoreceptor layer 2 has high light-receiving sensitivity in that it contains the semiconductor fine particles 22 to which a specific dye is adsorbed. When the photoreceptor layer 2 is used as a photo-electrochemical cell 100, And has higher durability.

(Metal complex coloring composition)

The metal complex colorant composition of the present invention comprises a metal complex coloring matter represented by the following general formula (1), a metal complex coloring matter represented by the following general formula (5) and / or a metal complex coloring matter represented by the following general formula (6)

The content of the metal complex dye represented by the general formula (5) and the content of the metal complex dye represented by the general formula (6) is 0.5 to 5% in terms of the area detected at 254 nm of HPLC (high performance liquid chromatography).

_{^{M 1 (LL 1) m1 (}} LL 2) m2 (Z 1) 2 · (CI 1) m3 formula (1)

[In the formula (1), M ¹ represents a metal atom, LL ¹ is a two-coordinate ligand represented by the following formula (2), and LL ² is a two-coordinate ligand represented by the following formula (3).

m1 and m2 are both 1s. m3 is an integer of 0 or more.

Z ¹ represents a ligand and is at least one selected from an isothiocyanato group, an isocyanato group and an isoselenocyanato group. Z ^{1 s} may be the same or different, but they are preferably the same.

CI ¹ represents a counter ion when a counter ion is required to neutralize the charge.

[Chemical Formula 14]

In the general formula (2), R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ independently represent an acidic group or a salt or a hydrogen atom, and R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ may be the same or different, do. Provided that at least one of R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ is an acidic group or a salt thereof]

[Chemical Formula 15]

[, N1 in the general formula (3), n2 is independently an integer of ^{0 ~ 3, Y 1, Y} 2 are respectively independently a heteroaryl group represented by formula (4) or a hydrogen atom. Ar ¹ and Ar ² independently represent a heteroaryl group represented by the following formula (4):

[Chemical Formula 16]

[In the general formula (4), R ³¹ to R ³³ independently represent a hydrogen atom, an alkyl group, an alkoxy group or an alkynyl group, and at least one of R ³¹ to R ³³ is an alkyl group, an alkoxy group or an alkynyl group. X is a sulfur atom, an oxygen atom, a selenium atom or NR ⁴ , and R ⁴ is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

_{^{M 1 (LL 1) m1 (}} LL 2) m2 (Z 1) (CN) · (CI 1) m3 general formula (5)

(In the general formula (5), M ¹ , LL ¹ , LL ² , Z ¹ , CI ¹ , m1, m2 and m3 have the same meanings as in formula (1)

_{^{M 1 (LL 1) m1 (}} LL 2) m2 (CN) 2 · (CI 1) m3 general formula (6)

(In the general formula (6), M ¹ , LL ¹ , LL ² , Z ¹ , CI ¹ , m1, m2 and m3 have the same meanings as in formula (1)

(A) a metal complex dye represented by the general formula (1)

(A1) metal atom M ¹

M ¹ represents a metal atom. M ¹ is preferably a metal capable of coordinating four or more times in coordination and more preferably Ru, Fe, Os, Cu, W, Cr, Mo, Ni, Pd, Pt, Co, Ir, Rh, Zn. Particularly preferably Ru, Os, Fe or Cu, and most preferably Ru. Ru of bivalent Ru is preferable.

(A2) Ligand LL ¹

The ligand LL ¹ is the 2-position represented by the following general formula (2). M1 representing the number of ligands LL ¹ is 1.

[Chemical Formula 17]

R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ in the general formula (2) independently represent an acidic group or a salt or a hydrogen atom, and R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ may be the same or different. Examples of R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ include a hydrogen atom, an acid group (for example, a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group (preferably having 1 to 20 carbon atoms trioxide of the hydroxyl group, for example, -CONHOH, -CONCH ₃ OH and the like), phosphonium group-(e.g., -OP (O) (OH) _2, etc.) or a phosphonyl group (for example, -P (O) (OH) ₂ ), etc.) or salts thereof. The acidic group may be bonded via a linking group, and an acidic group in which an acidic group such as a carboxyl group, a sulfonic acid group, a hydroxyl group or a hydroxyl group is bonded via a linking group is also included. At least one of R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ is an acid group or a salt thereof. When R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ represent an acidic group, the acidic group is preferably an acidic group such as a carboxyl group, a sulfonic acid group or a phosphonyl group, or a salt thereof, A carboxyl group or a phosphonyl group or a salt thereof, more preferably a carboxyl group or a salt thereof. R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ are an acid group, a salt thereof, or a hydrogen atom, the metal complex dye can be effectively adsorbed on the semiconductor fine particles.

(A3) Ligand LL ²

The ligand LL ² is a ^two -terminal ligand represented by the following general formula (3). M2 represents the number of ligand of the ligand LL LL ^{2 2} represents the 1. The double bond may be E-form or Z-form.

[Chemical Formula 18]

In the general formula (3), n1 and n2 independently represent an integer of 0 to 3. n1 and n2 are preferably 0 to 3, more preferably 0 to 1. Y ¹ and Y ² independently represent a hydrogen atom or a heteroaryl group represented by the following general formula (4). Ar ¹ and Ar ² independently represent a heteroaryl group represented by the following formula (4).

In the formula (4), R ³¹ to R ³³ independently represent a hydrogen atom, an alkyl group, an alkoxy group or an alkynyl group, at least one of R ³¹ to R ³³ is an alkyl group, an alkoxy group or an alkynyl group, , An alkyl group or an alkynyl group, and particularly preferably an alkynyl group. These may be linear or branched and preferably have 2 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, and particularly preferably 4 to 8 carbon atoms. By adsorbing the dye in the dye composition to the semiconductor fine particles using the metal complex dye composition having such a hydrophobic substituent, access of water present in the electrolyte in the charge transporting layer is inhibited, and desorption of the dye from the semiconductor fine particles can be suppressed . If the number of carbon atoms of the hydrophobic substituent is excessively large, not only the approach of water but also the approach of, for example, iodine and the like in the electrolyte is interrupted, so that the reduction from the redox system is not smoothly performed.

When Y ¹ or Y ² is represented by the general formula (4), it is preferable that Y ¹ or Y ² is conjugated with the pyridine ring and Ar ¹ and Ar ² are conjugated with the pyridine ring. The HOMO level for the metal atom M ¹ in the metal complex dye is improved by the conjugation of Y ¹ or Y ² represented by the general formula (4) so that the light in the long wavelength region is absorbed ) can do. In the general formula (4), X is a sulfur atom, an oxygen atom, a selenium atom or NR ⁴ , and R ⁴ is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. X in the general formula (4) is preferably a sulfur atom or a selenium atom, more preferably a sulfur atom, from the viewpoints of stability against nucleophilic species, difficulty in oxidation and difficulty in synthesis. When the ligand LL ² has such a structure, it is possible to suppress deterioration of performance as a cell due to dye desorption and to exhibit the effect of prolonging the wavelength.

[Chemical Formula 19]

It is preferable that the ligand LL ² is represented by the following general formula (7). In the general formula (7), R ⁴¹ to R ⁴³ and R ⁵¹ to R ⁵³ independently represent a hydrogen atom, an alkyl group, an alkoxy group or an alkynyl group. At least one of R ⁴¹ to R ⁴³ is an alkyl group, an alkoxy group or an alkynyl group. At least one of R ⁵¹ to R ⁵³ is an alkyl group, an alkoxy group or an alkynyl group. X ¹ and X ² are each independently a sulfur atom, an oxygen atom, a selenium atom or NR ⁷ , and R ⁷ is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. The double bond may be E-form or Z-form. R ⁴¹ to R ⁴³ are preferably an alkyl group or an alkynyl group. R ⁵¹ to R ⁵³ are preferably an alkyl group or an alkynyl group. X ¹ and X ² in the general formula (7) are preferably a sulfur atom or a selenium atom, and more preferably a sulfur atom. Since the ligand LL ² has such a structure, n1 and n2 in the general formula (3) are 1, so that it is possible to exhibit the effect of being stable and not oxidized well as compared with the case of two or more.

[Chemical Formula 20]

The metal complex dye represented by the above general formula (1) is preferably represented by the following general formula (8). In the general formula (8), R ⁶¹ and R ⁶² independently represent an alkyl group, an alkoxy group or an alkynyl group, and A ¹ and A ² independently represent a carboxyl group or a salt thereof. R ⁶¹ and R ⁶² are preferably an alkyl group or an alkynyl group. The metal complex dye represented by the general formula (1) can absorb light in the long wavelength region due to the high electron donating property of thiophene with this structure. Further, by removing the approach of water by the substituent bonding to vinylthiophene and thiophene which bind to the bipyridine ring, detachment of the dye from the semiconductor fine particles can be suppressed. In addition, electrons are efficiently injected electronically by a carboxyl group or a salt thereof, and light of a long wavelength region can be absorbed by an isothiocyanato group of a high electron donor.

In the metal complex coloring matter represented by the general formula (1), by having LL ¹ and LL ² one by one, the dye is adsorbed to the surface of the semiconductor fine particle at the acidic group portion of LL ¹ , and the coloring matters such as alkyl group, alkoxy group or alkynyl group By disposing LL ² having a hydrophobic group on the side opposite to the semiconductor particulate layer on the opposite side, the accessibility of water can be effectively suppressed, and detachment of the dye can be suppressed.

[Chemical Formula 21]

(A4) Ligand Z ¹

The ligand Z ¹ is at least one selected from an isothiocyanato group, an isocyanato group and an isoselenocyanato group. These groups are high in electron donors and contribute to long-term pigmentation. The ligand Z ¹ is preferably an isothiocyanato group or an isoselenocyanato group.

(A5) Counter ion CI ¹

CI ¹ in the general formula (1) represents a counter ion when a counter ion is required to neutralize the charge. Generally, whether a dye is a cation or an anion or has a well-defined ionic charge depends on the metals, ligands and substituents in the dye. The number m3 of the counter ions CI ¹ is an integer of 0 or more.

The dye of the general formula (1) may dissociate and have a negative charge due to the substituent having a dissociable group. In this case, the electric charge of the whole dye of the general formula (1) becomes electrically neutral by the counter ion CI ¹ .

For example, when the counter ion CI ¹ is a positive counter ion, for example, the counter ion CI ¹ may be an inorganic or organic ammonium ion (for example, a tetraalkylammonium ion, a pyridinium ion, etc.) to be.

When the counter ion CI ¹ is a negative counter ion, for example, the counter ion CI ¹ may be an inorganic anion or an organic anion. (E.g., a fluoride ion, a chloride ion, a bromide ion, an iodide ion, etc.), a substituted arylsulfonate ion (such as a p-toluenesulfonic acid ion or a p-chlorobenzenesulfonic acid ion) (E.g., 1,3-benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion and the like), alkylsulfuric acid ion (e.g. methylsulfate ion) Sulfuric acid ion, thiocyanic acid ion, perchloric acid ion, tetrafluoroboric acid ion, hexafluorophosphate ion, picric acid ion, acetic acid ion, trifluoromethanesulfonic acid ion and the like. As the charge balance counter ion, an ionic polymer or another dye having a reversed charge to the dye may be used, or a metal complex ion (for example, bisbenzene-1,2-dithiolato nickel (III)) may be used Do.

(B) a metal complex dye of the general formula (5) or the general formula (6)

The metal complex colorant composition of the present invention is characterized in that, in addition to the metal complex coloring matter represented by the general formula (1), at least one of the metal complex coloring matter represented by the following general formula (5) and the metal complex coloring matter represented by the following general formula (6) . The compounding ratio of the metal complex dye represented by the general formula (5) and the content of the metal complex dye represented by the general formula (6) in the area% detected at 254 nm of HPLC (high performance liquid chromatography) 0.5 to 5% in the pigment composition.

The metal complex dye of the general formula (5) has one cyano group as a ligand, and the metal complex dye of the general formula (6) has two cyano groups as a ligand. In the general formula (5) of, M ^1, LL ^1, LL ^2, Z ^1, CI ^1, m1, m2 and m3 are as defined as in the general formula (1), Formula (6), M ¹ , LL ¹ , LL ² , Z ¹ , CI ¹ , m ¹ , m 2 and m 3 have the same meanings as those in the general formula (1) and are omitted because they are duplicated. M ¹ , LL ¹ , LL ² , Z ¹ , CI ¹ , m ¹ , m 2 and m 3 in the general formulas (5) and (6) are preferably the same as those in the general formula (1) Do.

_{^{M 1 (LL 1) m1 (}} LL 2) m2 (Z 1) (CN) · (CI 1) m3 general formula (5)

_{^{M 1 (LL 1) m1 (}} LL 2) m2 (CN) 2 · (CI 1) m3 general formula (6)

Compared with the isothiocyanato group mentioned above, cyano group is low in electron donating group. For this reason, the metal complex dye represented by the general formula (5) having one cyano group and the metal complex dye represented by the general formula (6) having two cyano groups has a low HOMO level and shortens the absorption, When it is adsorbed on fine particles and used as a sensitizing dye, light on the longwave side can not be effectively used, and the conversion efficiency tends to be lowered.

However, when the content of the metal complex dye represented by the general formula (5) and the content of the metal complex dye represented by the general formula (6) in the metal complex dye composition is within the range of 0.5 - 5%, the solubility of the dye in the solution can be dramatically improved without causing deterioration of the conversion efficiency, and the amount of dye adsorbed to the semiconductor fine particles can be improved and a high photoelectric conversion efficiency can be obtained. Further, the dye solution can be prepared in a short time, and the productivity of manufacturing the photoelectric conversion element is improved. The reason for the improvement of the solubility in the solution of the coloring matter is not clear. However, the metal complex coloring matter represented by the general formula (1) is mixed with the metal complex coloring matter having a basic skeleton but chemically different in nature from 0.5 to 5% , It is believed that the reason for this is that the crystal arrangement of the metal complex pigment is different between when the purity is as high as 0.5% or less.

The area of the metal complex dye represented by the general formula (5) and the metal complex dye represented by the general formula (6) detected at 254 nm of HPLC (high performance liquid chromatography) is 0.5 to 5% Water = 63/37 (containing 0.1% trifluoroacetic acid buffer), measuring time 50 [deg.] C, eluent composition YMC-Pack ODS-AM312 150 mm x 6.0 mm ID, flow rate 0.75 ml / Min, respectively.

Wherein the metal complex dye represented by the general formula (5) is represented by the following general formula (9), the metal complex dye represented by the general formula (6) is represented by the following general formula (10) It is preferable that the sum of the content of the complex dye and the content of the metal complex dye represented by the general formula (10) is 0.5 to 5% in an area detected at 254 nm of HPLC (high performance liquid chromatography). In the general formula (9), R ⁷¹ and R ⁷² independently represent an alkyl group, an alkoxy group or an alkynyl group, and A ⁵ and A ⁶ independently represent a carboxyl group or a salt thereof. In the general formula (10), R ⁷³ and R ⁷⁴ independently represent an alkyl group, an alkoxy group or an alkynyl group, and A ⁷ and A ⁸ independently represent a carboxyl group or a salt thereof. R ⁷¹ and R ⁷² are preferably an alkyl group or an alkynyl group. R ⁷³ and R ⁷⁴ are preferably an alkyl group or an alkynyl group. The metal complex dye represented by the general formula (5) and the metal complex dye represented by the general formula (6) have such a structure and the sum of the content ratios of these metal complex dyes is detected at 254 nm of HPLC (high performance liquid chromatography) , The absorption of the dye is prolonged by the electron donor of the thiophene ring and the cyano group is present. Therefore, the conversion efficiency is not remarkably lowered due to short-wavelength irradiation, Effect can be exerted. The sum of the content of the metal complex dye represented by the general formula (5) and the content of the metal complex dye represented by the general formula (6) is preferably 0.5 to 4.5% in terms of the area detected at 254 nm of HPLC (high performance liquid chromatography) , More preferably 0.5 to 4%, and particularly preferably 0.5 to 3.5%.

[Chemical Formula 22]

The metal complex dye represented by the general formula (5) is represented by the following general formula (11), and the metal complex dye represented by the general formula (6) is preferably represented by the following general formula (12). In formulas (11) and (12), R ⁸¹ to R ⁸⁴ independently represent an alkynyl group, and A ¹³ to A ¹⁶ independently represent a carboxyl group or a salt thereof. Since the metal complex coloring matter of this structure has an alkynyl group as R ⁸¹ to R ⁸⁴ , it is possible to exhibit the effect of the long-wavelength excitation and the improvement of? Resulting from the? -Π * transition of LL ² due to conjugated system stretching. Further, since R ⁸¹ to R ⁸⁴ are alkynyl groups, the metal complex coloring matter of this structure is improved in planarity of R ⁸¹ to R ⁸⁴ with respect to the thiophene ring, or the dye is adsorbed on the surface of the semiconductor fine particles It is expected that it is likely that a desired association which contributes to the long-term polarization among the molecules is likely to occur. R ⁸¹ to R ⁸⁴ are preferably a linear or branched alkynyl group having 3 to 13 carbon atoms, more preferably a linear or branched alkynyl group having 3 to 8 carbon atoms, particularly preferably a linear chain having 4 to 7 carbon atoms Or branched alkynyl group.

(23)

The metal complex dye composition is preferably dissolved in the organic solvent in the metal complex dye of the general formula (1), the metal complex dye represented by the general formula (5) and / or the metal complex dye represented by the general formula (6). Examples of such organic solvents include alcohols (methanol, ethanol, isopropanol, etc.), nitrile solvents (acetonitrile, propionitrile, methoxypropionitrile and valeronitrile), ester solvents (ethyl acetate, (Dichloromethane, dichloroethane, chlorobenzene, chloroform, etc.), benzene, toluene, xylene and the like can be given as examples of the solvent , And is not particularly limited. Or a mixed solvent composed of a plurality of solvents.

(C) Method for producing metal complex dye

The metal complex dye of the general formula (1) of the present invention is a step of raising the temperature of the mixed solution by external heating of a mixed solution containing the metal complex dye of the following general formula (13) and the compound of the general formula (14) And the like.

_{^{M 1 (LL 1) m1 (}} LL 2) m2 (Z 2) m4 · (CI 1) m5 general formula (13)

In the general formula (13), M ¹ , LL ¹ , LL ² , CI ¹ , m ¹ and m 2 have the same meanings as in formula (1). Z ² is a 1-left or 2-left ligand. Z ² is preferably a halogen atom (F, Cl, Br, I), water, a dimethylformamide group, -OC (═O) - (CH ₂ ) _p -C (═O) Preferably 0 to 6, more preferably 0 to 4, and particularly preferably 0 to 2). More preferably a chlorine atom, water, a dimethylformamide group, and particularly preferably a chlorine atom. m4 is when an integer of 1 ~ ^2, Z 2 is L 1 ligand m4 represents a 2, Z ² is L 2 represents a ligand days when m4 is 1. When m4 is 2, Z &lt; ² &gt; may be the same or different, but the same is preferable. m5 is an integer of 0 or more.

The compound of formula (14) is represented by the following formula.

M ¹¹ QCN In general formula (14)

Wherein M ¹¹ represents an inorganic or organic ammonium ion, a proton or an alkali metal ion, and Q represents a sulfur atom, an oxygen atom or a selenium atom,

M ¹¹ is preferably an inorganic or organic ammonium ion (for example, NH ₄ ⁺ , NBu ₄ ⁺ or NEt ₃ H ⁺ ) or an alkali metal ion (for example Na ⁺ , K ⁺ or Li ⁺ NH ₄ ⁺ , NBu ₄ ⁺ , K ⁺ , particularly preferably NH ₄ ⁺ , K ⁺ . Q is preferably a sulfur atom or a selenium atom in view of the absorption wavelength of the metal complex dye of the general formula (1), that is, the electron donor of QCN as a ligand, more preferably a sulfur atom.

The metal complex dye represented by the general formula (1) is represented by the following formula as described above.

_{^{M 1 (LL 1) m1 (}} LL 2) m2 (Z 1) 2 · (CI 1) m3 formula (1)

In the general formula (1), M ¹ represents a metal atom, LL ¹ is a 2-position ligand represented by the following general formula (2), and LL ² is a ^2-position ligand represented by the following general formula (3). m1 and m2 are both 1s. Z ¹ represents a ligand and is at least one selected from an isothiocyanato group, an isocyanato group and an isoselenocyanato group. Z ^{1 s} may be the same or different, but they are preferably the same. CI ¹ represents a counter ion when a counter ion is required to neutralize the charge. m3 is an integer of 0 or more.

&Lt; EMI ID =

In the general formula (2), R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ independently represent an acidic group or a salt or a hydrogen atom, and R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ may be the same or different, do. Provided that at least one of R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ is an acidic group or a salt thereof]

(25)

[, N1 in the general formula (3), n2 is independently an integer of ^{0 ~ 3, Y 1, Y} 2 are respectively independently a heteroaryl group represented by formula (4) or a hydrogen atom. Ar ¹ and Ar ² independently represent a heteroaryl group represented by the following formula (4):

(26)

[In the general formula (4), R ³¹ to R ³³ independently represent a hydrogen atom, an alkyl group, an alkoxy group or an alkynyl group, and at least one of R ³¹ to R ³³ is an alkyl group, an alkoxy group or an alkynyl group. X is a sulfur atom, an oxygen atom, a selenium atom or NR ⁴ , and R ⁴ is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

The descriptions of the above-mentioned general formulas (1) to (4) are the same as those described above, and are omitted because they are duplicated.

The metal complex coloring matter of the present invention is obtained by heating a mixture liquid containing the metal complex dye of the above general formula (13) and the compound of the general formula (14) by external heating, as shown in the following synthesis scheme, And a step of raising the temperature of the reaction mixture. As the mixed solution containing the metal complex dye of the general formula (13) and the compound of the general formula (14), an organic solvent may preferably be used, and for example, an alcohol solvent (methanol, ethanol, propanol, isopropanol , Butanol), nitrile solvents (acetonitrile, propionitrile, methoxypropionitrile, valeronitrile, etc.), ester solvents (ethyl acetate,? -Butyrolactone and the like), amide solvents (dimethylformamide, dimethyl Acetone, NMP), a halogen-based solvent (dichloromethane, dichloroethane, chlorobenzene, chloroform, etc.), benzene, toluene, xylene and the like. It may be a mixed solvent comprising a plurality of solvents or a mixed solvent with water. The organic solvent is preferably an alcohol solvent, a nitrile solvent or an amide solvent, more preferably an alcohol solvent or an amide solvent, particularly preferably an amide solvent.

As a method for heating the mixed liquid containing the metal complex dye of the general formula (13) and the compound of the general formula (14) to increase the temperature of the mixed liquid, it is necessary to heat the mixed liquid from the outside. The method of heating from the outside means a method of heating by heat transfer from an external heat source. As a heat source, there is no particular limitation, but a heat source for converting electrical energy into heat and a heat source by burning can be mentioned. The mixed liquid may be heated via heat medium obtained from the heat source. Examples of the medium include oil, water (water vapor), and the like. A method of irradiating a microwave or the like is heating from the inside by heating the microwave absorbed by the material and converting the energy of the microwave into heat, and is not included in the external heating. (14) contained in the mixture and the metal complex dye of the general formula (14) contained in the mixture are mixed with each other, Or the decomposition of the metal complex dye of the general formula (1) occurs. Therefore, it is not preferable to prepare the metal complex dye of the present invention. As a method by external heating, a method of heating the mixture with an oil bath or steam is preferable. The heating temperature and the reaction time can be appropriately selected depending on the metal complex dye to be reacted or the solvent used. The temperature for heating is preferably 90 to 170 占 폚, more preferably 90 to 160 占 폚, particularly preferably 100 to 150 占 폚, and most preferably 100 to 140 占 폚. The reaction time is preferably 30 minutes to 12 hours, more preferably 1 to 8 hours, further preferably 2 to 6 hours.

The metal complex dye of the general formula (13) can be obtained by introducing LL ¹ and LL ² into a compound having Ru as shown in the following scheme. The Ru source is not particularly limited, and examples thereof include ruthenium chloride and its hydrate, and d-1-6 described later. And preferably d-1-6 which will be described below, wherein the valence of Ru is divalent. The introduction order of LL ¹ and LL ² is not particularly limited, but is preferably introduced from LL ² . Z ² is usually determined by a Ru source, but additives such as potassium iodide, potassium bromide, KO-C (═O) - (CH ₂ ) _p -C (═O) -OK (p is an integer of 0 or more) ), Z ² can be changed. Further, the solvent can be coordinated to Z ² . Thereafter, the compound (14) is put into a solution containing the metal complex coloring matter of the obtained general formula (13) and heated from the outside as described above to obtain the metal complex coloring matter of the general formula (1).

(27)

In the above general formula (13), the ligand LL ² is preferably represented by the following general formula (7). In the general formula (7), R ⁴¹ to R ⁴³ and R ⁵¹ to R ⁵³ independently represent a hydrogen atom, an alkyl group, an alkoxy group or an alkynyl group. At least one of R ⁴¹ to R ⁴³ is an alkyl group, an alkoxy group or an alkynyl group. At least one of R ⁵¹ to R ⁵³ is an alkyl group, an alkoxy group or an alkynyl group. X ¹ and X ² are a sulfur atom, an oxygen atom, a selenium atom or NR ⁷ , and R ⁷ is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ⁴¹ to R ⁴³ are preferably an alkyl group or an alkynyl group. R ⁵¹ to R ⁵³ are preferably an alkyl group or an alkynyl group. X ¹ and X ² in the general formula (7) are preferably a sulfur atom or a selenium atom, and more preferably a sulfur atom.

(28)

The metal complex dye of the general formula (13) is represented by the following general formula (15) and the compound of the general formula (14) is represented by the following general formula (16) Is preferable. In formulas (8) and (15), R ⁶¹ , R ⁶² , R ⁹¹ and R ⁹² independently represent a hydrogen atom, an alkyl group, an alkoxy group or an alkynyl group, A ¹ to A ⁴ independently represent a carboxyl group or It represents the salt. In the general formula (16), M ¹² represents an inorganic or organic ammonium ion, a proton or an alkali metal ion. R ⁶¹ , R ⁶² , R ⁹¹ and R ⁹² are preferably an alkyl group or an alkynyl group. Since the metal complex dye (13) and the compound of the general formula (14) have these structures, the metal complex dye (13) has a stable thiophene ring to the nucleophilic compound (14) Cl is a leaving group having a high elimination capability and a low nucleophilicity, so that a metal complex dye of the general formula (8) in which an -NCS group is selectively coordinated to a Ru atom can be efficiently produced.

[Chemical Formula 29]

The metal complex dye of the general formula (13) is represented by the following general formula (18) and the compound of the general formula (14) is represented by the following general formula (19) Is preferable. In formulas (17) and (18), R ¹⁰¹ , R ¹⁰² , R ¹¹¹ and R ¹¹² independently represent an alkynyl group, and A ⁹ to A ¹² independently represent a carboxyl group or a salt thereof. In the general formula (19), M ¹³ represents an inorganic or organic ammonium ion, a proton or an alkali metal ion. R ¹⁰¹ , R ¹⁰² , R ¹¹¹ and R ¹¹² are preferably a linear or branched alkynyl group having 3 to 13 carbon atoms, more preferably a linear or branched alkynyl group having 3 to 8 carbon atoms, Or a linear or branched alkynyl group having 4 to 7 carbon atoms.

(30)

The dye represented by the general formula (1) has a maximum absorption wavelength in a solution in a range of 500 to 700 nm, more preferably in a range of 500 to 650 nm.

Specific examples of the dye having the structure represented by the general formula (1) used in the present invention are shown below, but the present invention is not limited thereto. When the dye in the following specific examples includes a ligand having a proton-dissociable group, the ligand may be dissociated as necessary to form a counterion and a salt. There are isomers based on double bond sites, isomers based on the positions of ligands of the complex, and the like, but either of them may be used or a mixture thereof may be used.

(31)

(32)

(33)

(D)

The electrolyte composition used for the photoelectric conversion element 10 of the present invention may contain, as the redox pair, for example, a combination of iodine and iodide (for example, lithium iodide, tetrabutylammonium iodide, tetramethylammonium iodide, etc.) A combination of a biologen (for example, methylviologen chloride, hexylbiologen bromide, benzyl birogen tetrafluoroborate) and a reducing body thereof, a combination of polyhydroxybenzenes (for example, hydroquinone, naphtho Hydroquinone, etc.) and its oxidized form, a combination of a divalent and trivalent iron complex (e.g., a red blood salt and a sulfur black salt), and the like. The combination of iodine and iodide in these is preferred.

The cation of the iodide salt is preferably a nitrogen-containing aromatic cation of a five-membered ring or a six-membered ring. Particularly, when the compound represented by the general formula (1) is not an iodide salt, the compound represented by the general formula (1) 1997), and the like are preferably used in combination with iodine salts such as pyridinium salts, imidazolium salts, and triazolium salts.

The electrolyte composition used in the photoelectric conversion element 10 of the present invention preferably contains iodine in combination with a heterocyclic quaternary salt compound. The content of iodine in the electrolyte composition is preferably 0.1 to 20 mass%, more preferably 0.5 to 5 mass%.

The electrolyte composition used in the photoelectric conversion element 10 of the present invention may contain a solvent. The content of the solvent in the electrolyte composition is preferably 50 mass% or less, more preferably 30 mass% or less, and particularly preferably 10 mass% or less.

It is preferable that the solvent is capable of exhibiting excellent ion conductivity because of low viscosity, high ion mobility, high dielectric constant and effective carrier concentration, or both. Such solvents include, but are not limited to, carbonate compounds such as ethylene carbonate and propylene carbonate, heterocyclic compounds such as 3-methyl-2-oxazolidinone, ether compounds such as dioxane and diethyl ether, (Ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, polypropylene glycol dialkyl ether, polypropylene glycol dialkyl ether, etc.) (Ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin and the like), nitrile compounds (acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile and the like), polyhydric alcohols Benzonitrile, bis-cyanoethyl ether, etc.), esters (such as carboxylic acid (Dimethylsulfoxide (DMSO), sulfolane, etc.), water, a functional electrolytic solution described in Japanese Patent Application Laid-Open No. 2002-110262, Japanese Patent Application Laid- 36332, Japanese Unexamined Patent Application Publication No. 2000-243134, and the electrolyte solvent described in the re-publication WO / 00-54361. These solvents may be used in a mixture of two or more kinds.

As the electrolyte solvent, an electrochemically inert salt having a melting point at room temperature and lower than room temperature may be used. For example, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, and the like, imidazolium salts such as imidazolium salts and pyridinium salts, A quaternary quaternary salt compound, or a tetraalkylammonium salt.

The electrolyte composition used in the photoelectric conversion element of the present invention may be gelled (solidified) by adding a polymer or an oil gelling agent, or by a method such as polymerization of multifunctional monomers or crosslinking reaction of a polymer.

When the electrolyte composition is gelled by adding a polymer, compounds described in Polymer Electrolyte Reviews-1 and 2 (published by J. R. MacCallum and C. A. Vincent, ELSEVIER APPLIED SCIENCE) can be added. In this case, it is preferable to use polyacrylonitrile or polyvinylidene fluoride.

When an electrolyte composition is gelled by adding an oil gelling agent, it is preferable to use an oil gelling agent as described in J. Chem. Soc. Japan, Ind. Chem. Soc., 46779 (1943), J. Am. Chem. Soc., 111, 5542 (1989), J. Chem. Soc., Chem. Coimun., 390 (1993), Angew. Chem. Int. Ed. Engl., 35, 1949 (1996), Chem. Lett., 885, (1996), J. Chem. Soc., Chem. Coilun., 545, (1997), etc., and it is preferable to use a compound having an amide structure.

In the case of gelation of an electrolyte composition by polymerization of multifunctional monomers, a solution is prepared from polyfunctional monomers, a polymerization initiator, an electrolyte and a solvent, and the solution is prepared by a casting method, a coating method, a dipping method, A method of forming an electrolyte layer on a sol-like electrode on the electrode carrying thereon a conductive polymer and then gelling it by radical polymerization of the polyfunctional monomer is preferable. The multifunctional monomers are preferably compounds having two or more ethylenic unsaturated groups, and examples thereof include divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate , Triethylene glycol diacrylate, triethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, and the like.

The gel electrolyte may be formed by polymerization of a mixture containing a monofunctional monomer in addition to the multifunctional monomers. Examples of monofunctional monomers include acrylic acid or? -Alkylacrylic acid (acrylic acid, methacrylic acid, itaconic acid, etc.), esters or amides thereof, vinyl esters (such as vinyl acetate), maleic acid or fumaric acid or esters Methacrylonitrile, dienes (butadiene, cyclopentadiene, isoprene, etc.), aromatic vinyl compounds (such as styrene, butadiene, isoprene and the like) methylstyrene, sodium styrenesulfonate, etc.), N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl- (Meth) acrylates such as acetamide, vinylsulfonic acid, sodium vinylsulfonate, sodium allylsulfonate, sodium methacrylate sulfonate, vinylidene fluoride, vinylidene chloride, vinyl alkyl ethers Butylene, propylene, butene, isobutene, etc., N- phenyl maleimide can be used.

The blending amount of the multifunctional monomer is preferably 0.5 to 70 mass%, more preferably 1.0 to 50 mass%, based on the whole monomer. The above-mentioned monomers can be obtained by radical polymerization, which is a general polymer synthesis method described in Takayuki Otsu, Masayoshi Kiyoshi, "Experimental Method of Polymer Synthesis" (Chemical Drivers) or Takayuki Otsu "Lecture Polymerization Theory 1 Radical Polymerization (I)" Can be polymerized. The monomer for gel electrolyte used in the present invention can be radically polymerized by heating, light or electron beam or electrochemically, but it is particularly preferable to perform radical polymerization by heating. In this case, polymerization initiators that can be preferably used include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis 2-methylpropionate) and dimethyl 2,2'-azobisisobutylate; peroxide initiators such as lauryl peroxide, benzoyl peroxide, and t-butyl peroctoate; and the like. The amount of the polymerization initiator to be added is preferably from 0.01 to 20% by mass, more preferably from 0.1 to 10% by mass, based on the total amount of monomers.

The weight composition range of the monomer in the gel electrolyte is preferably 0.5 to 70% by mass. And more preferably 1.0 to 50 mass%. When the electrolyte composition is gelled by the crosslinking reaction of the polymer, it is preferable to add a polymer having a crosslinkable reactive group and a crosslinking agent to the composition. Preferred reactive groups are nitrogenous heterocycle such as pyridine rings, imidazole rings, thiazole rings, oxazole rings, triazole rings, morpholine rings, piperidine rings, piperazine rings, etc. Preferred crosslinking agents are those in which the nitrogen atom attacks nucleophilic A halogenated alkylaryl, a halogenated aralkyl, a sulfonic acid ester, an acid anhydride, an acid chloride, an isocyanate, and the like, which have two or more functional groups.

Examples of the electrolyte composition of the present invention include metal iodide (LiI, NaI, KI, CsI, CaI ₂ ), metal bromide (LiBr, NaBr, KBr, CsBr, CaBr ₂ ), quaternary ammonium bromide Metal complexes (such as ferrocenate-ferricyanide and ferrocene-ferricinium ions), sulfur compounds (such as sodium polysulfide and alkylthiol-alkyl disulfide), biologen pigments, hydroquinone -Quinone may be added. They may be mixed and used.

In the present invention, Ceram. Butylpyridine described in Soc., 80, (12), 3157-3171 (1997), or a basic compound such as 2-picoline or 2,6-lutidine. When a basic compound is added, the preferable concentration range is 0.05 to 2 M.

As the electrolyte of the present invention, a charge transport layer containing a hole conductor material may be used. As the hole conductor material, 9,9'-spirobifluorene derivatives and the like can be used.

In addition, an electrode layer, a photoconductor layer (photoelectric conversion layer), a charge carrier layer (hole transport layer), a conductive layer, and a counter electrode layer can be sequentially laminated. a hole transporting material functioning as a p-type semiconductor can be used as the hole transporting layer. As the preferable hole transporting layer, for example, an inorganic or organic hole transporting material can be used. Examples of the inorganic hole transporting material include CuI, CuO, NiO and the like. Examples of the organic-based hole transporting material include high-molecular-weight and low-molecular-weight organic-based transporting materials, and examples of the polymer-based ones include polyvinylcarbazole, polyamine and organic polysilane. Examples of low-molecular-based compounds include triphenylamine derivatives, stilbene derivatives, hydrazone derivatives, and phenamine derivatives. Of these, organic polysilanes are preferred because σ electrons, which are unstimulated along Si of the main chain, contribute to light conduction and have a high hole mobility, unlike conventional carbon-based polymers (Phys. Rev. B, 35 , 2818 (1987)).

The conductive layer is not particularly limited as long as it has good conductivity, and examples thereof include an inorganic conductive material, an organic conductive material, a conductive polymer, and an intermolecular charge transfer complex. Among them, an intermolecular charge transfer complex formed from a donor material and an acceptor material is preferable. Of these, those formed from an organic donor and an organic acceptor can be preferably used.

The thickness of the conductive layer is not particularly limited, but is preferably such that the porous body can be completely embedded.

The donor material preferably has a rich electron in the molecular structure. Examples of the organic donor material include those having an amine group, a hydroxyl group, an ether group, a selenium, or a sulfur atom in a pi-electron system of a molecule. Specific examples thereof include phenylamine, triphenylmethane, Based, phenol-based, and tetrathiafulvalene-based materials. As the acceptor material, it is preferable to be electron deficient in the molecular structure. Examples of the organic acceptor material include fullerene, those having a substituent such as a nitro group, a cyano group, a carboxyl group, or a halogen group in the pi electron system of the molecule, and specifically, those having substituents such as PCBM, benzoquinone, naphthoquinone , Fluorenone-based compounds, chlororanil-based compounds, boranyl-based compounds, tetracyanoquinodimethane-based compounds, tetracyanoethylene-based compounds and the like.

(E) a conductive support

As shown in Fig. 1, in the photoelectric conversion element of the present invention, a photoconductor layer 2 on which a sensitizing dye 21 is adsorbed is formed on a porous semiconductor fine particle 22 on a conductive support 1. As described later, the photoconductor layer 2 can be produced, for example, by applying a dispersion of semiconductor fine particles to an electrically conductive substrate and drying the same, followed by immersion in the dye solution of the present invention.

As the conductive support 1, it is possible to use a conductive material such as a metal itself or a glass or polymer material having a conductive film layer on its surface. The conductive support 1 is preferably substantially transparent. The substantially transparent means that the light transmittance is 10% or more, preferably 50% or more, and particularly preferably 80% or more. As the conductive support 1, glass or a polymer material coated with a conductive metal oxide may be used. The amount of the conductive metal oxide to be applied at this time is preferably 0.1 to 100 g per 1 m &lt; 2 &gt; of glass or a support of a polymeric material. When a transparent conductive support is used, it is preferable that light is incident from the support side. Preferable examples of the polymer material include tetraacetylcellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate ), Polyarylate (PAR), polysulfone (PSF), polyester sulfone (PES), polyetherimide (PEI), cyclic polyolefin, and phenoxy bromide. On the surface of the conductive support 1, a light management function may be applied to the surface. For example, an antireflection film prepared by alternately laminating a high-refraction film and a low-refractive-index oxide film described in Japanese Patent Application Laid-Open No. 2003-123859, -260746. &Lt; / RTI &gt;

In addition, a metal support may be preferably used. Examples thereof include titanium, aluminum, nickel, iron, stainless steel, and copper. These metals may be alloys. More preferably, titanium, aluminum and copper are preferable, and titanium and aluminum are particularly preferable.

It is preferable that the conductive support 1 has a function of blocking ultraviolet light. For example, a method of allowing a fluorescent material capable of converting ultraviolet light to visible light to exist on the surface of the transparent support or on the surface of the transparent support, or a method of using an ultraviolet absorber.

On the conductive support 1, the functions described in JP-A-11-250944 and the like may be additionally provided.

Preferable examples of the conductive film include metal (for example, platinum, gold, silver, copper, aluminum, rhodium, indium, etc.), carbon, or metal oxides (for example, indium- .

The thickness of the conductive film is preferably 0.01 to 30 占 퐉, more preferably 0.03 to 25 占 퐉, and particularly preferably 0.05 to 20 占 퐉.

The lower the surface resistance of the conductive support 1 is, the better. The preferable range of the surface resistance is 50 Ω / cm 2 or less, and more preferably 10 Ω / cm 2 or less. There is no particular limitation on the lower limit, but it is usually about 0.1? / Cm 2.

Since the resistance value of the conductive film increases as the cell area increases, the current collecting electrode may be disposed. Either or both of a gas barrier film and an ion diffusion preventing film may be disposed between the conductive support 1 and the transparent conductive film. As the gas barrier layer, a resin film or an inorganic film can be used.

Further, the transparent electrode and the porous semiconductor electrode photocatalyst-containing layer may be formed. The transparent conductive film may have a laminated structure, and FTO may be laminated on ITO, for example, by a preferable method.

(F) Semiconductor fine particles

As shown in Fig. 1, in the photoelectric conversion element 10 of the present invention, a photoconductor layer 2 on which a sensitizing dye 21 is adsorbed is formed on a porous semiconductor fine particle 22 on a conductive support 1. As described later, the photoconductor layer 2 can be produced, for example, by applying a dispersion liquid of the semiconductor fine particles 22 to the conductive support 1, drying it, and immersing it in the above-described dye solution.

As the semiconductor fine particles 22, metal chalcogenides (for example, oxides, sulfides, selenides, etc.) or fine particles of perovskite are preferably used. The metal chalcogenide is preferably an oxide of titanium, tin, zinc, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium or tantalum, cadmium sulfide, cadmium selenide . The perovskite is preferably strontium titanate, calcium titanate, or the like. Of these, titanium oxide, zinc oxide, tin oxide and tungsten oxide are particularly preferable.

In semiconductors, there are n-type carriers in which electrons are related to conduction and p-type carriers in which carriers are holes. However, in the device of the present invention, it is preferable to use n-type carriers in view of conversion efficiency. In the n-type semiconductor, an n-type semiconductor (for example, an intrinsic semiconductor) having no impurity level and having a carrier concentration equal to that of the conduction band electrons and the valence band of the valence band Lt; / RTI &gt; The n-type inorganic semiconductor preferably used in the present invention is at least one selected from the group consisting of TiO ₂ , TiSrO ₃ , ZnO, Nb ₂ O ₃ , SnO ₂ , WO ₃ , Si, CdS, CdSe, V ₂ O ₅ , ZnS, ZnSe, SnSe, KTaO ₃ , FeS ₂ , PbS, InP, GaAs, CuInS ₂ , and CuInSe ₂ . Of these, the most preferred n-type semiconductors are TiO ₂ , ZnO, SnO ₂ , WO ₃ , and Nb ₂ O ₃ . A semiconductor material in which a plurality of these semiconductors are combined is also preferably used.

As the method for producing the semiconductor fine particles 22, the gel-sol method described in "Science of Sol-Gel Method" by Agatsu-Shio, Agneshoffa (1998) is preferable. Also, a method of producing an oxide by high temperature hydrolysis of a chloride developed by Degussa in an acid salt is also preferable. When the semiconductor fine particles 22 are titanium oxide, the sol-gel method, the gel-sol method, and the high-temperature hydrolysis method of the chloride in an acid salt of sodium chloride are all preferable, but the "titanium oxide property and application technology" (1997) can also be used. As a sol-gel method, a method described in Journal of American Ceramic Society, Vol. 80, No. 12, pp. 3157 to 3171 (1997) by Balbe et al., And a method described in Chemistry of Materials, , 10, 9, 2419-2425 are also preferable.

In addition, as a method of producing semiconductor fine particles, for example, a method of producing titania nanoparticles, preferably, a method by flame hydrolysis of titanium tetrachloride, a titanium tetrachloride combustion method, a hydrolysis of a stable chalcogenide complex, Hydrolysis of titanic acid, dissolution and removal of soluble portion after formation of semiconductor fine particles from soluble portion and insoluble portion, hydrothermal synthesis of aqueous solution of peroxide, or production of core / shell structure titanium oxide fine particles by sol / gel method .

Examples of the crystal structure of titania include anatase type, brookite type, and rutile type, and anatase type and brookite type are preferable.

Titania nanotubes, nanowires, and nanorods may be mixed with titania fine particles.

The titania may be doped with a non-metallic element or the like. In addition to the dopant as an additive to titania, a binder for improving necking or an additive for the surface may be used for preventing reverse electron transfer. Preferred examples of the additive include charge transporting molecules such as ITO, SnO 2 particles, whiskers, fibrous graphite and carbon nanotubes, zinc oxide-zinc oxide binders, fibrous materials such as cellulose, metals, organic silicon, dodecylbenzenesulfonic acid, , And a dislocation-type dendrimer.

For the purpose of removing surface defects on the titania, etc., the titania may be treated with an acid base or a redox treatment before the adsorption of the dye. Etching, oxidation treatment, hydrogen peroxide treatment, dehydrogenation treatment, UV-ozone, oxygen plasma, or the like.

(G) Semiconductor fine particle dispersion

In the present invention, a semiconductor fine particle dispersion in which the content of solids other than the semiconductor fine particles is 10% by mass or less based on the total amount of the semiconductor fine particle dispersion is applied to the conductive support 1 and heated appropriately to obtain the porous semiconductor fine particle coating layer .

As a method for producing the semiconductor fine particle dispersion, besides the above-mentioned sol-gel method, there is a method in which a semiconductor is precipitated as a fine particle in a solvent to be used as it is, a method in which fine particles are irradiated with ultrasonic waves to be pulverized with ultrafine particles, And a method of grinding and grinding using mechanical grinding. As the dispersion solvent, one or more of water and various organic solvents may be used. Examples of the organic solvent include alcohols such as methanol, ethanol, isopropyl alcohol, citronellol and terpineol, ketones such as acetone, esters such as ethyl acetate, dichloromethane and acetonitrile.

When dispersed, a small amount of a polymer such as polyethylene glycol, hydroxyethylcellulose, carboxymethylcellulose, a surfactant, an acid, or a chelating agent may be used as a dispersion aid, if necessary. However, it is preferable that most of these dispersion auxiliaries are removed by a filtration method, a separation membrane method, or a centrifugal separation method before the step of producing a film on the conductive support. The solid content of the semiconductor fine particle dispersion other than the semiconductor fine particles may be 10 mass% or less of the total dispersion. This concentration is preferably 5% or less, more preferably 3% or less, particularly preferably 1% or less. , More preferably 0.5% or less, and particularly preferably 0.2%. That is, the solids other than the solvent and the semiconductor fine particles in the semiconductor fine particle dispersion can be made up to 10 mass% or less of the whole semiconductor micro dispersion. It is preferable that it is composed substantially only of the semiconductor fine particles and the dispersion solvent.

If the viscosity of the semiconductor microparticle dispersion is too high, the dispersion may aggregate to form a film. Conversely, if the viscosity of the semiconductor microparticle dispersion is too low, the liquid may flow and the film may not be produced. Therefore, the viscosity of the dispersion is preferably 10 to 300 N · s / m 2 at 25 ° C. And more preferably 50 to 200 N · s / m 2 at 25 ° C.

As a method of applying the semiconductor fine particle dispersion, a roller method, a dipping method, or the like can be used as an application system method. As the metering method, an air knife method, a blade method, or the like can be used. In addition, the method of the application system and the method of the metering system can be carried out in the same way. The wire bar method disclosed in Japanese Patent Publication No. 58-4589, the slide hopper method described in the specification of US Patent No. 2681294, extrusion method, Method and the like are preferable. It is also preferable to use a general-purpose machine for application by a spin method or a spray method. The wet printing method is preferably a concave plate, a rubber plate, a screen printing, or the like, including three printing methods of relief, offset and gravure. Among them, a preferable film production method is selected according to the liquid viscosity or the wet thickness. In addition, since the dispersion of the semiconductor fine particles of the present invention has high viscosity and viscosity, the cohesive force may be strong, and may not be well fused with the support at the time of coating. In such a case, the surface is cleaned and hydrophilized by the UV ozone treatment, whereby the bonding strength between the applied semiconductor fine particle dispersion and the surface of the conductive support 1 is increased, and the application of the semiconductor fine particle dispersion becomes easy.

A preferable thickness of the entire semiconductor fine particle layer is 0.1 mu m to 100 mu m. The thickness of the semiconductor fine particle layer is also preferably 1 mu m to 30 mu m, more preferably 2 mu m to 25 mu m. The supported amount of the semiconductor fine particles per 1 m 2 of the support is preferably 0.5 g to 400 g, more preferably 5 g to 100 g.

In order to enhance the electrical contact between the semiconductor fine particles and improve the adhesion with the support, the layer of the coated semiconductor fine particles is subjected to heat treatment in order to dry the coated fine semiconductor particle dispersion. The porous semiconductor fine particle layer can be formed by this heat treatment.

In addition to the heat treatment, the energy of light may also be used. For example, when titanium oxide is used as the semiconductor fine particles 22, the surface may be activated by giving light absorbed by the semiconductor fine particles 22 such as ultraviolet light, and only the surface of the semiconductor fine particles 22 Can be activated. By irradiating the semiconductor fine particles 22 with light absorbed by the fine particles, impurities adsorbed on the surface of the particles are decomposed by the activation of the surface of the particles, so that a desired state can be obtained for the above purpose. In the case of combining the heat treatment and the ultraviolet light, the semiconductor fine particles 22 are heated at 100 ° C to 250 ° C, or preferably 100 ° C to 150 ° C, while irradiating the light absorbed by the fine particles desirable. By photo-exciting the semiconductor fine particles 22 in this way, the impurities incorporated into the fine particle layer can be cleaned by photo decomposition and the physical bonding between the fine particles can be strengthened.

Further, the semiconductor fine particle dispersion may be applied to the conductive support 1 and subjected to other treatment than heating or light irradiation. Preferable methods include, for example, energization, chemical treatment, and the like.

Pressure may be applied after application, and as a method of applying pressure, JP-A-2003-500857 and the like can be mentioned. Examples of the light irradiation include JP-A-2001-357896 and the like. Examples of the plasma, microwave, and energization include JP-A-2002-353453 and the like. As a chemical treatment, for example, JP-A-2001-357896 can be mentioned.

The method of forming the above-described semiconductor fine particles 22 on the electrically conductive substrate 1 may be a method of applying the above-described semiconductor fine particle dispersion onto the electrically conductive substrate 1, as well as the method of coating the semiconductor fine particles 22 described in Japanese Patent No. 2664194 A method in which a precursor of the conductive fine particles 22 is coated on the conductive support 1 and hydrolyzed by moisture in the air to obtain a semiconductor fine particle film can be used.

Examples of the precursor include (NH ₄ ) ₂ TiF ₆ , titanium peroxide, metal alkoxide metal complexes, metal organic acid salts and the like.

Further, a method of applying a slurry in which a metal organic oxide (alkoxide or the like) coexists and forming a semiconductor film by heat treatment, light treatment, or the like, a slurry in which an inorganic precursor is mixed, and a slurry, . A small amount of the binder may be added to these slurries, and examples of the binder include cellulose, fluoropolymer, crosslinked rubber, polybutyl titanate, and carboxymethyl cellulose.

Examples of techniques for forming the semiconductor fine particles 22 or the precursor layer thereof include a method of hydrophilizing by a physical method such as corona discharge, plasma or UV, a chemical treatment using alkali, polyethylene dioxythiophene and polystyrenesulfonic acid, And the like.

As the method of forming the semiconductor fine particles 22 on the conductive support 1, the dry method (2), (3) other methods may be used in combination with the above-described (1) wet method. (2) As the dry method, JP-A-2000-231943 is preferably used. (3) As another method, JP-A-2002-134435 is preferably used.

Examples of the dry method include vapor deposition, sputtering, aerosol deposition, and the like. In addition, an electrophoresis method or an electrophoresis method may be used.

Alternatively, a method may be used in which a coating film is once formed on a heat-resistant substrate and then transferred to a film such as a plastic film. Preferably, a method of transferring via EVA described in Japanese Patent Application Laid-Open No. 2002-184475, a method in which a semiconductor layer is formed on a sacrificial substrate containing an inorganic salt removable by ultraviolet rays and an aqueous solvent described in JP-A No. 2003-98977, A method of removing the sacrificial substrate after transfer of the conductive layer to the organic substrate after forming the conductive layer, and the like.

It is preferable that the semiconductor fine particles 22 have a large surface area so as to adsorb a large number of the increasing and decreasing dye 21. The surface area of the semiconductor fine particles 22 is preferably 10 times or more and more preferably 100 times or more of the projected area in a state where the semiconductor fine particles 22 are coated on the conductive support 1. The upper limit is not particularly limited, but is usually about 5000 times. As the structure of the preferable semiconductor fine particle 22, JP-A-2001-93591 and the like can be mentioned.

Generally, as the thickness of the semiconductor fine particle layer is larger, the amount of the sensitizing dye 21 that can be supported per unit area increases, so that the absorption efficiency of light increases, but the diffusion distance of generated electrons increases, . The preferred thickness of the semiconductor particulate layer varies depending on the use of the device, but is typically 0.1 mu m to 100 mu m. In the case of being used as a photoelectrochemical cell, it is preferably 1 mu m to 50 mu m, more preferably 3 mu m to 30 mu m. The semiconductor fine particles may be heated at a temperature of 100 ° C to 800 ° C for 10 minutes to 10 hours in order to bring the particles into close contact with each other after they are applied to a support. When glass is used as the support, the film-forming temperature is preferably 400 ° C to 600 ° C.

When a polymer material is used as the support, it is preferable to heat the film after the film formation at 250 DEG C or lower. The membrane manufacturing method in this case may be any of (1) a wet method, (2) a dry method, and (3) an electrophoresis method (including an electrostatic method) , And more preferably (1) wet method.

The application amount of the semiconductor fine particles 22 per 1 m 2 of the support is preferably 0.5 g to 500 g, more preferably 5 g to 100 g.

In order to adsorb the sensitizing dye 21 to the semiconductor fine particles 22, it is preferable to immerse the fine semiconductor particles 22 dried for a long time in the dye and the coloring matter solution for dye adsorption comprising the dye according to the present invention. The solvent used for the coloring matter adsorbing dye solution may be any solvent as long as it can dissolve the sensitizing dye 21 according to the present invention. The solvent for dissolving the metal complex colorant composition in the present invention is an organic solvent, and examples thereof include a nonpolar solvent, a polar aprotic solvent, a polar protic solvent and an ionic liquid. Preferably, the solvent is a nonpolar solvent, A protonic solvent or a polar protic solvent can be used as a preferable example of the solvent. Examples of the solvent include ethanol, methanol, isopropanol, toluene, t-butanol, acetonitrile, acetone, n-butanol, N, , N-dimethylacetamide, and the like. Among them, ethanol and toluene can be preferably used.

In the present invention, the solubility of the metal complex dye composition in the solvent is preferably 100 mg / L or more, more preferably 105 mg / L or more, and particularly preferably 110 mg / L or more, at 25 占 폚.

The coloring matter solution for dye adsorption comprising the solvent and the dye of the present invention may be heated to 50 to 100 캜, if necessary. The adsorption of the sensitizing dye 21 may be carried out before or after the application of the semiconductor fine particles 22. Further, the semiconductor fine particles 22 and the sensitizing dye 21 may be simultaneously applied and adsorbed. Unsorbed sensitizing dye (21) is removed by washing. When the coating film is baked, the adsorption of the sensitizing dye 21 is preferably carried out after baking. It is particularly preferable to quickly adsorb the sensitizing dye 21 before the water is adsorbed onto the surface of the coating film after firing. The sensitizing dyes 21 to be adsorbed may be one kind of the dye A1 or may be mixed with other dyes. The dye to be mixed is selected so as to make the wavelength region of the photoelectric conversion as wide as possible. When the dyes are mixed, it is preferable that all of the dyes are dissolved so as to form a dye solution for dye adsorption.

The amount of the sensitizing dyes 21 to be used is preferably from 0.01 to 100 moles, more preferably from 0.1 to 50 moles, and particularly preferably from 0.1 to 10 moles per 1 m 2 of the support. In this case, the use amount of the sensitizing dye 21 according to the present invention is preferably 5 mol% or more.

The adsorption amount of the sensitizing dye 21 to the semiconductor fine particles 22 is preferably from 0.001 millimole to 1 millimole, more preferably from 0.1 to 0.5 millimole, per gram of the semiconductor fine particles.

By using such a small amount of color, the effect of increasing or decreasing in the semiconductor can be sufficiently obtained. On the other hand, if the amount of dye is small, the effect of increase and decrease becomes insufficient, and if the amount of dye is excessively large, the dye not adhered to the semiconductor floats to cause a decrease or decrease effect.

In addition, a colorless compound may be co-adsorbed for the purpose of reducing the interaction between the coloring matters such as association. Examples of the hydrophobic compound that adsorbs a coenzyme include a steroid compound having a carboxyl group (e.g., cholic acid, pivaloylic acid).

After the sensitizing dyes 21 are adsorbed, the surfaces of the semiconductor fine particles 22 may be treated with amines. Preferred amines include 4-tert-butylpyridine, polyvinylpyridine, and the like. They may be used as they are in the case of a liquid or dissolved in an organic solvent.

The counter electrode 4 acts as a positive electrode of a photoelectrochemical cell. The counter electrode 4 generally has the same meaning as the above-described conductive support 1, but a counter electrode support is not necessarily required in such a configuration that the strength is sufficiently maintained. However, the side having the support is advantageous in terms of hermeticity. Examples of the material of the counter electrode 4 include platinum, carbon, and a conductive polymer. Preferred examples include platinum, carbon, and conductive polymers.

As the structure of the counter electrode 4, a structure having a high current collecting effect is preferable. A preferable example is JP-A-10-505192 and the like.

The light-receiving electrode 5 may be a composite electrode made of titanium oxide and tin oxide (TiO ₂ / SnO ₂ ) or the like, for example, JP-A-2000-113913 and the like as a mixed electrode of titania. As mixed electrodes other than titania, for example, JP-A-2001-185243 and JP-A-2003-282164 can be cited.

The structure of the photoelectric conversion element may have a structure in which the first electrode layer, the first photoelectric conversion layer, the conductive layer, the second photoelectric conversion layer, and the second electrode layer are sequentially laminated. In this case, the dyes used in the first photoelectric conversion layer and the second photoelectric conversion layer may be the same or different, and when different, it is preferable that the absorption spectrum is different.

The light receiving electrode 5 may be of a tandem type in order to increase the utilization ratio of the incident light. Examples of preferable configurations of the tandem type include the examples described in JP-A-2000-90989, JP-A-2002-90989, and the like.

The light management function for efficiently performing light scattering and reflection within the layer of the light receiving electrode 5 may be formed. Preferably, those described in JP-A-2002-93476 can be mentioned.

It is preferable to form a short-circuit prevention layer between the conductive support 1 and the porous semiconductor fine particle layer in order to prevent a reverse current caused by direct contact between the electrolyte and the electrode. A preferable example is JP-A-06-507999.

It is preferable to use a spacer or a separator in order to prevent contact between the light-receiving electrode 5 and the counter electrode 4. A preferable example is JP-A-2001-283941.

Examples of the sealing method of the cell and the module include a method of using an aluminum alkoxide in a polyisobutylene thermosetting resin, a novolac resin, a photocurable (meth) acrylate resin, an epoxy resin, an ionomer resin, a glass frit, And a method of laser melting the melting point glass paste. In the case of using glass frit, powder glass may be mixed with an acrylic resin to be a binder.

Example

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.

1. Preparation of unpurified metal complex pigment

(1) a method of external heating, and (2) a method of heating by microwave to prepare an unpurified metal complex, which was then purified in step 2.

(1) preparation of undefined metal complex pigment by external heating

(a) Preparation of unpurified metal complex dye D-20

Of the metal complex dyes of the general formula (1) shown in the above specific examples, the crude D-20 was prepared by the following method.

(34)

(35)

<Ligand Synthesis>

(i) Preparation of compound d-1-2

25 g of d-1-1, 3.8 g of Pd ₂ (dba) ₃ , triphenylphosphine 8.6 g, copper iodide 2.5 g and 1-heptyn 25 g were added to 70 ml of triethylamine and 50 ml of tetrahydrofuran at room temperature , And the mixture was stirred at 80 占 폚 for 4.5 hours. Concentrated, and then purified by column chromatography to obtain 26.4 g of a compound d-1-2.

(ii) Preparation of d-1-4

6.7 g of d-1-3 was dissolved in 200 ml of THF (tetrahydrofuran) at -15 캜 under a nitrogen atmosphere, LDA (lithium diisopropylamide) adjusted separately was added to 2.5 And the mixture was stirred for 75 minutes. Thereafter, a solution prepared by dissolving 15 g of d-1-2 in 30 ml of THF was added dropwise, and the mixture was stirred at 0 ° C for 1 hour and then at room temperature overnight. After concentration, 150 ml of water was added, and the mixture was separated and extracted with 150 ml of methylene chloride. The organic layer was washed with brine, and the organic layer was concentrated. The obtained crystals were recrystallized from methanol to obtain 18.9 g of d-1-4.

(iii) Preparation of compound d-1-5

13.2 g of d-1-4 and 1.7 g of PPTS (pyridinium para-toluenesulfonic acid) were added to 1000 ml of toluene, and the mixture was heated under reflux for 5 hours under a nitrogen atmosphere. After concentration, the mixture was partitioned between saturated aqueous sodium hydrogencarbonate and methylene chloride, and the organic layer was concentrated. The obtained crystals were recrystallized from methanol and methylene chloride to obtain 11.7 g of d-1-5.

<Complexation>

And external heating furnace complexation was carried out to prepare a metal complex dye D-20. 3.0 g of d-1-5 and 1.64 g of d-1-6 synthesized above were added to 35 ml of DMF, and the mixture was stirred in a dark place at 70 DEG C for 90 minutes. At that time, the oil bath was heated from the outside. 1.3 g of d-1-7 was then added, 270 ml of DMF was added, and the mixture was heated and stirred at 160 占 폚 for 150 minutes. At that time, the oil bath was heated from the outside. Thereafter, 14.25 g of ammonium thiocyanate was added, and the mixture was stirred at 130 캜 for 5 hours. At that time, the oil bath was heated from the outside. After concentration, 300 ml of water was added thereto, followed by filtration and washing with diethyl ether to obtain crude D-20.

(b) Preparation of unpurified metal complex dye D-10

Of the metal complex dyes of the general formula (1) shown in the above specific examples, the crude D-10 was prepared by the following method.

<Ligand Synthesis>

Compound d-2-5 was prepared by the following method.

(i) Preparation of compound d-2-2

25 g of d-2-1 was dissolved in 500 ml of tetrahydrofuran, and 1.05 equivalent of n-butyllithium (1.6 mol / l hexane solution) was added dropwise. Then, 1.5 equivalents of dimethylformamide was added dropwise, and the mixture was stirred at room temperature for 1 hour. Saturated ammonium chloride aqueous solution was added dropwise, separated and extracted, concentrated, and then purified by vacuum distillation to obtain 25.6 g of compound d-2-2.

(ii) Preparation of d-2-4

d-2-2 used in the preparation of d-1-4 was changed to d-2-2 in the preparation of the metal complex dye D-20 of (a) To prepare d-2-4.

(iii) Preparation of compound d-2-5

2-5 was prepared in the same manner as d-2-4 except that d-1-4 used in the preparation of d-1-5 was changed to d-2-4 in preparing the metal complex dye D-20 of (a) .

<Complexation>

And an external heating furnace complexation was carried out to prepare a crude metal salt D-10.

(D-10) was prepared in the same manner as in (a) except that d-2-5 was changed to d-2-5.

(36)

(2) Preparation of undefined pigments of metal complex pigments by microwave heating

(a) Preparation of unpurified metal complex dye D-20

3.0 g of compound d-1-5 and 1.64 g of d-1-6 were added to 35 ml of DMF, stirred in a dark place at 70 占 폚 for 10 minutes under irradiation of microwave (frequency: 2.45 GHz). Thereafter, 1.3 g of d-1-7 was added, DMF (270 ml) was added, and the mixture was heated and stirred at 160 캜 for 10 minutes using the microwave. Thereafter, 14.25 g of ammonium thiocyanate was added, and the mixture was stirred at 130 캜 for 10 minutes using the microwave. After concentration, 300 ml of water was added, followed by filtration and washing with diethyl ether to obtain crude D-20.

(b) Preparation of unpurified metal complex dye D-10

2.5 g of the crude product of D-10 was obtained in the same manner except that the external heating of (1) (b) was changed to microwave heating (the same condition as (2) (a)).

2. Preparation of a metal complex coloring composition containing a metal complex coloring matter of the general formula (5) and / or a metal complex coloring matter of the general formula (6) and a metal complex coloring matter

(1) Preparation of metal complex coloring composition by external heating

1. (1) The crude product of the metal complex dye D-20 obtained in (a) was dissolved in a methanol solution together with TBAOH (tetrabutylammonium hydroxide) and purified by a column of Sephadex LH-20 (trade name, GE Healthcare) . The main fraction was collected, concentrated, and then 0.2 M nitric acid was added to obtain a precipitate. Filtered and washed with water and diethyl ether to obtain a metal complex coloring composition comprising at least one of the metal complex dye of the general formula (5) and the metal complex dye of the general formula (6) containing D-17 as a main component . In the column purification, 50 g of the carrier was used per 200 mg of the crude product, and the number of times of column purification was changed from 1 to 4 times to obtain the metal complex dye of the general formula (5) and the metal of the general formula (6) (Examples 1 to 4) containing at least one kind of complex dye were obtained.

(1) The crude product of the metal complex dye D-10 obtained in (b) was purified and the metal complex dye of general formula (5) containing D-11 as a main component and the metal complex of general formula (6) To obtain metal complex coloring compositions (Examples 5 to 8) containing at least one of the pigments. Further, the metal complex color composition thus obtained was further dissolved in a methanol solution together with TBAOH (tetrabutylammonium hydroxide), and a 0.1 N nitric acid methanol solution was dropped to a pH of 0 to obtain a metal complex dye composition of the general formula (5) containing D-10 as a main component A metal complex coloring composition containing at least one of a metal complex dye and a metal complex dye of the general formula (6) (Examples 9 to 12) was obtained.

(2) Preparation of metal complex coloring composition by microwave heating

(1), the crude product of the metal complex dye D-20 prepared by the microwave heating obtained in (1) (2) (a) was purified in the same manner as in (1) A metal complex coloring composition containing at least one of a metal complex dye of the general formula (5) and a metal complex dye of the general formula (6) as main components was obtained (Comparative Examples 1 to 3). The metal complex dye of the general formula (5) containing D-11 as a main component and the dye of the general formula (6) were obtained by purifying the crude product of the metal complex dye D-10 obtained in 1. (2) ) Were obtained (Comparative Examples 5 to 7). Further, the obtained metal complex coloring composition was dissolved in a methanol solution together with TBAOH (tetrabutylammonium hydroxide), and a 0.1 N nitric acid methanol solution was dropped to a pH of 0 to obtain a metal of the general formula (5) containing D-10 as a main component A complex dye composition containing at least one of a complex dye and a metal complex dye of the general formula (6) (Comparative Examples 9 to 11) was obtained.

(3) Preparation of metal complex pigments by HPLC fractionation

1. (1) The crude product obtained in (a) was purified by HPLC (high performance liquid chromatography). At that time, the crude product was dissolved in a methanol solution of TBAOH (tetrabutylammonium hydroxide), and the composition of the eluent was changed to methanol / water = 85/100 by using CAPCELL PAK UG120 manufactured by Shiseido, 15 to 95/5. The main fraction was collected, concentrated, and then 0.2 M nitric acid was added to obtain a precipitate. After filtration, the mixture was washed with water and diethyl ether to obtain 3.2 g of a metal complex dye D-17 (Comparative Example 4) represented by the general formula (1).

The structure of the obtained metal complex dye D-17 was confirmed by NMR measurement and LC-MS.

The resulting metal complex dye D-17 (Comparative Example 8) was dissolved in tetrahydrofuran: water = 63: 37 (0.1% trifluoroacetic acid) to prepare a solution having a concentration of 8.5 mu mol / Manufactured by Hitachi, Ltd.), and the result showed that the maximum absorption wavelength was 568 nm.

In the same manner, the metal complex dye D-11 (Comparative Example 8) was also obtained by purifying by HPLC using the crude product obtained in (1) and (b).

MS-ESI m / z: 1003.2 (M + H) &lt; ^{+ &}

Thereafter, the solution was dissolved in tetrahydrofuran: water = 63: 37 (0.1% trifluoroacetic acid) to prepare a solution having a concentration of 8.5 mu mol / l. Spectrophotometry was performed using a U-4100 spectrophotometer (manufactured by Hitachi, Ltd.) As a result, the maximum absorption wavelength was 566 nm.

The resulting metal complex dye D-11 was dissolved in a methanol solution together with TBAOH (tetrabutylammonium hydroxide), and a 0.1 N nitric acid methanol solution was dropped to a pH of 0 to obtain D-10 (Comparative Example 12).

MS-ESI m / z: 1003.2 (M + H) &lt; ^{+ &}

Thereafter, the solution was dissolved in tetrahydrofuran: water = 63: 37 (0.1% trifluoroacetic acid) to prepare a solution having a concentration of 8.5 mu mol / l. Spectrophotometry was performed using a U-4100 spectrophotometer (manufactured by Hitachi, Ltd.) As a result, the maximum absorption wavelength was 571 nm.

3. Measurement of the content of the metal complex dye of the general formula (5) and / or the metal complex dye of the general formula (6) in the metal complex composition

Identification and content of metal complex pigments contained in the metal complex pigment composition obtained in 2. were determined by the following (a) to (b). The values are shown in Table 1.

(a) Measurement of high performance liquid chromatography

The metal complex dye composition obtained in 2. was subjected to high performance liquid chromatography under the following conditions. The content of the metal complex colorant of the general formula (5) and / or the metal complex colorant of the general formula (6) was determined by identifying the metal complex having the CN ligand together with the measurement result of LC-MS described later.

(Measurement conditions of high performance liquid chromatography (HPLC)

Equipment used: System controller SCL-10AVP

Column oven CTO-10ASVP

Detector SPD-10AVVP

DGU-14AM

Pumping unit LC-10ADVP

(Trade name, manufactured by Shimadzu Corporation)

Column: YMC-Pack ODS-AM, Model No. AM-312,

Size 150 x 6.0 mm ID. (Manufactured by YMC Co., Ltd. Japan)

Flow rate: 0.75 ml / min

Eluent: THF / water = 63/37 0.1% Trifluoroacetic acid containing

Temperature: 40 ° C

Detection wavelength: 254 nm

(b) Identification of the metal complex pigment in the metal complex dye composition

The LC-MS of the metal complex dye composition was measured to identify the structure of the metal complex dye contained in the metal complex dye composition. LC-MS was performed by the following method.

(Measurement conditions of LC-MS)

Apparatus: Applied Biosystems QSTAR pulser (trade name), manufactured by Applied Biosystems

Ionization method: ESI-posi

Detection method: TOF-MS

Column: YMC-Pack ODS-AM, Model No. AM-312,

Size 150 x 6.0 mm ID. (Manufactured by YMC Co., Ltd. Japan)

Flow rate: 0.75 ml / min

Eluent: THF / water = 63/37 0.1% Trifluoroacetic acid containing

Temperature: 40 ° C

The metal complex dye of the general formula (5) and the metal complex dye of the general formula (6) contained in the metal complex dye composition containing D-17 as a main component were detected as the following structures. The counter ion of the acidic group is detected as a proton because it contains trifluoroacetic acid in the eluent, but in the metal complex composition, the counter ion may be proton or tetrabutylammonium.

(37)

The absorption maximum wavelength is 542 nm

(38)

The absorption maximum wavelength is 515 nm

The metal complex coloring matter of the general formula (5) and the metal complex coloring matter of the general formula (6) contained in the metal complex coloring composition containing D-11 as a main component and the metal complex coloring composition containing D- . The counter ion of the acidic group is detected as a proton because it contains trifluoroacetic acid in the eluent, but in the metal complex composition, the counter ion is proton or tetrabutylammonium.

[Chemical Formula 39]

The absorption maximum wavelength is 540 nm

(40)

The absorption maximum wavelength is 513 nm

4. Evaluation of Solubility of Dye in Solution

12 mg of each metal complex coloring composition shown in Table 1 was dissolved in a mixed solvent of 50 ml of toluene and 50 ml of methanol in a dark place and stirred with a stirring blade at 25 캜 for 15 minutes to obtain a dye solution. The dissolution amount of the metal complex dye represented by the general formula (1) in this solution was quantified by using the HPLC apparatus used in the above-mentioned 3. method. The dissolution amount was more than 11.0 ㎎, A not less than 10.0 ㎎, less than 11.0 ㎎ B, not less than 9.0 ㎎, less than 10.0 ㎎ C, less than 9.0 ㎎ D, and A and B were passed.

5. Evaluation of adsorption of pigments to semiconductor particulate electrodes

(Fabrication of Semiconductor Fine Particle Electrode)

On the glass substrate, tin oxide doped with fluorine was formed as a transparent conductive film by sputtering, and this was scribed with a laser to divide the transparent conductive film into two parts.

Subsequently, 32 g of anatase-type titanium oxide (P-25 (trade name), manufactured by Nippon Aerosil Co., Ltd.) was mixed with 100 ml of a mixed solvent of water and acetonitrile in a volume ratio of 4: 1, Using a conditioner, they were uniformly dispersed and mixed to obtain a dispersion of semiconductor fine particles. The dispersion was applied to a transparent conductive film and heated at 500 캜 to produce a semiconductor fine particle electrode.

Thereafter, similarly, a dispersion liquid containing silica particles and rutile titanium oxide in a ratio of 40: 60 (mass ratio) was prepared. The dispersion liquid was applied to the light receiving electrode and heated at 500 ° C to form an insulating porous body. Subsequently, a carbon electrode was formed as a counter electrode.

Next, the glass substrate on which the insulating porous body was formed was immersed in an ethanol solution of the metal complex coloring composition of Table 1 for 12 hours. The glass in which the sensitizing dye was dissolved was immersed in a 10% ethanol solution of 4-tert-butylpyridine for 30 minutes, washed with ethanol, and naturally dried. The thickness of the photosensitive layer thus obtained was 10 占 퐉, and the application amount of the semiconductor fine particles was 20 g / m2.

(Evaluation of Adsorption Property)

Of the semiconductor fine particle electrodes prepared by the above method, 2.3 cm 2 was immersed in each dye solution in a dark place at 40 ° C for 30 minutes. The dye-adsorbed semiconductor fine particle electrode was desorbed with a 10% TBAOH methanol solution, and the initial adsorption amount of each dye was determined by HPLC. The dissolution amount in this solution was determined by the same method as HPLC used in the above-mentioned 3. method. B, 0.7 mg or more, C: less than 0.9 mg, D: less than 0.7 mg, and A and B were determined to be 1.0 mg or more.

6. Evaluation of photoelectric conversion efficiency of photoelectric conversion element

(Fabrication of Semiconductor Fine Particle Electrode)

On the glass substrate, tin oxide doped with fluorine was formed as a transparent conductive film by sputtering, and this was scribed with a laser to divide the transparent conductive film into two parts.

Subsequently, 32 g of anatase-type titanium oxide (P-25 (trade name), manufactured by Nippon Aerosil Co., Ltd.) was added to 100 ml of a mixed solvent of water and acetonitrile in a volume ratio of 4: 1, Using a mixing conditioner, they were uniformly dispersed and mixed to obtain a dispersion of semiconductor fine particles. The dispersion was applied to a transparent conductive film and heated at 500 캜 to produce a semiconductor fine particle electrode.

Thereafter, a dispersion liquid containing silica particles and rutile titanium oxide in a weight ratio of 40:60 (mass ratio) was prepared. The dispersion liquid was applied to the light receiving electrode and heated at 500 ° C to form an insulating porous body. Subsequently, a carbon electrode was formed as a counter electrode.

Next, the glass substrate on which the above-described insulating porous body was formed was immersed in the dye solution shown in Table 1, prepared in 4, for 12 hours. The glass in which the sensitizing dye was dissolved was immersed in a 10% ethanol solution of 4-tert-butylpyridine for 30 minutes, washed with ethanol, and naturally dried. The thickness of the photosensitive layer thus obtained was 10 占 퐉, and the application amount of the semiconductor fine particles was 20 g / m2.

Thereafter, the semiconductor fine particle electrode was disposed opposite to the platinum sputter FTO substrate through a thermoplastic polyolefin resin sheet having a thickness of 50 mu m, and the resin sheet portion was thermally melted to fix the cathode plate.

An electrolyte solution was poured in advance from the nipple of the electrolytic solution opened in advance on the platinum sputter electrode side to fill the space between the electrodes. In addition, the peripheral portion and the electrolyte main liquid port were sealed with an epoxy sealing resin, and silver paste was applied to the current collecting terminal portion to form a photoelectric conversion element.

As the electrolytic solution, a methoxypropionitrile solution of dimethylpropylimidazolium iodide (0.5 mol / l) and iodine (0.1 mol / l) was used.

(Evaluation of Photoelectric Conversion Element)

Light of a 500 W xenon lamp (manufactured by Ushio Inc.) was passed through an AM 1.5 filter (manufactured by Oriel) and a sharp cut filter (Kenko L-42) to produce a simulated sunlight not containing ultraviolet rays. The light intensity was 89 mW / cm 2.

Alligator clips were connected to a conductive glass plate and a platinum-deposited glass plate of the photoelectrochemical cell, and the alligator clips were connected to a current-voltage measuring device (Keithley SMU238 type (trade name)). Simulated sunlight was irradiated from the side of the conductive glass plate, and the generated electricity was measured by a current voltage measuring apparatus. A conversion efficiency of the photoelectrochemical cell thus obtained was defined as A, 8.0% to 9.0% B, 7.0% to less than 8.0% C, and less than 7.0% D as A, B, .

As can be seen from Table 1, when the metal complex coloring matter represented by the general formula (5) or the general formula (6) is excessively large, there is a problem in the photoelectric conversion efficiency, and when these metal complex coloring matters are excessively small, It was found that there was a problem in both the dissolution amount, the adsorption amount, and the photoelectric conversion efficiency.

On the contrary, the metal complex coloring composition of the present invention was satisfactory in all properties.

When the content of the metal complex dye represented by the general formula (5) or the general formula (6) is high, the solubility tends to be improved. However, the amount of the metal complex tends to decrease when the content of the metal complex is more than 5.0% It is expected that the metal complex coloring matter represented by the formula (5) or (6) is preferentially adsorbed, and the conversion efficiency is lowered accordingly.

While the invention has been described in conjunction with the embodiments thereof, it is to be understood that the invention is not to be limited to any details of the description, unless explicitly specified otherwise, and is not to be construed as limited to the spirit and scope of the invention as set forth in the appended claims. .

The present application claims priority based on Japanese Patent Application No. 2011-054802 filed on March 11, 2011, and Japanese Patent Application No. 2012-044602 filed on February 29, 2012, which is hereby incorporated by reference herein in its entirety The contents of which are incorporated herein by reference.

One ; Conductive support
2 ; The photoconductor layer
21; A sensitizing dye
22; Semiconductor particulate
3; The charge-
4 ; Counter electrode
5; Receiving electrode
6; External circuit
10; Photoelectric conversion element
100; Photoelectrochemical cell

Claims (14)

(1), a metal complex coloring matter represented by the following general formula (5) and / or a metal complex coloring matter represented by the following general formula (6)
The content of the metal complex dye represented by the general formula (5) and the content of the metal complex dye represented by the general formula (6) is 0.5 to 5% in terms of the area detected at 254 nm of HPLC (high performance liquid chromatography) A metal complex coloring composition.
_{^{M 1 (LL 1) m1 (}} LL 2) m2 (Z 1) 2 · (CI 1) m3 formula (1)
[Formula (1) of, M ¹ represents a metal atom, LL ¹ is to a 2 L ligand represented by formula (2), LL ² is a ligand of the two left and represented by the following formula (3). m1 represents 1. m2 represents 1. Z ¹ represents a ligand and is at least one selected from an isothiocyanato group, an isocyanato group and an isoselenocyanato group. CI ¹ represents a counter ion when a counter ion is required to neutralize the charge, and m 3 is an integer of 0 or more.
[Chemical Formula 1]

In the general formula (2), R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ independently represent an acidic group or a salt or a hydrogen atom, and R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ may be the same or different, do. Provided that at least one of R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ is an acid group or a salt thereof]
(2)

[, N1 in the general formula (3), n2 is independently an integer of ^{0 ~ 3, Y 1, Y} 2 are respectively independently a heteroaryl group represented by formula (4) or a hydrogen atom. Provided that Ar ¹ and Ar ² independently represent a heteroaryl group represented by the following general formula (4):
(3)

[In the general formula (4), R ³¹ to R ³³ independently represent a hydrogen atom, an alkyl group, an alkoxy group or an alkynyl group, and at least one of R ³¹ to R ³³ is an alkyl group, an alkoxy group or an alkynyl group. X is a sulfur atom, an oxygen atom, a selenium atom or NR ⁴ , and R ⁴ is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
_{^{M 1 (LL 1) m1 (}} LL 2) m2 (Z 1) (CN) · (CI 1) m3 general formula (5)
(In the general formula (5), M ¹ , LL ¹ , LL ² , Z ¹ , CI ¹ , m1, m2 and m3 have the same meanings as in formula (1)
_{^{M 1 (LL 1) m1 (}} LL 2) m2 (CN) 2 · (CI 1) m3 general formula (6)
(In the general formula (6), M ¹ , LL ¹ , LL ² , Z ¹ , CI ¹ , m1, m2 and m3 have the same meanings as in formula (1) The method according to claim 1,
The metal complex dye composition according to the above-mentioned (1), wherein LL ² is represented by the following general formula (7).
[Chemical Formula 4]

[In the general formula (7), R ⁴¹ to R ⁴³ and R ⁵¹ to R ⁵³ independently represent a hydrogen atom, an alkyl group, an alkoxy group or an alkynyl group. At least one of R ⁴¹ to R ⁴³ is an alkyl group, an alkoxy group or an alkynyl group. At least one of R ⁵¹ to R ⁵³ is an alkyl group, an alkoxy group or an alkynyl group. X ¹ and X ² are each independently a sulfur atom, an oxygen atom, a selenium atom or NR ⁷ , and R ⁷ is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. 3. The method of claim 2,
Wherein X ¹ and X ² in the general formula (7) are sulfur atoms. 4. The method according to any one of claims 1 to 3,
Wherein the metal complex dye represented by the general formula (1) is represented by the following general formula (8).
[Chemical Formula 5]

[Wherein R ⁶¹ and R ⁶² independently represent an alkyl group, an alkoxy group or an alkynyl group, and A ¹ and A ² independently represent a carboxyl group or a salt thereof]. 4. The method according to any one of claims 1 to 3,
Wherein the metal complex dye represented by the general formula (5) is represented by the following general formula (9) and the metal complex dye represented by the general formula (6) is represented by the general formula (10)
[Chemical Formula 6]

[In the formula (9), R ⁷¹ and R ⁷² independently represent an alkyl group, an alkoxy group or an alkynyl group, and A ⁵ and A ⁶ independently represent a carboxyl group or a salt thereof.
In the general formula (10), R ⁷³ and R ⁷⁴ independently represent an alkyl group, an alkoxy group or an alkynyl group, and A ⁷ and A ⁸ independently represent a carboxyl group or a salt thereof. 4. The method according to any one of claims 1 to 3,
Wherein the metal complex dye represented by the general formula (5) is represented by the following general formula (11) and the metal complex dye represented by the general formula (6) is represented by the general formula (12)
(7)

[In formulas (11) and (12), R ⁸¹ to R ⁸⁴ independently represent an alkynyl group. A ¹³ to A ¹⁶ independently represent a carboxyl group or a salt thereof. delete delete delete delete delete A photoelectric conversion element characterized by using the metal complex coloring composition according to any one of claims 1 to 3 as a sensitizing dye. delete A photoelectrochemical cell comprising the photoelectric conversion element according to claim 12.

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