TW201343802A - Photoelectric conversion element, metal complex dye, dye adsorption solution composition for dye-sensitized solar cell, dye adsorption electrode for dye-sensitized solar cell, dye sensitized solar cell and method of manufacturing the same - Google Patents

Abstract

A photoelectric conversion element having a semiconductor and a dye represented by formula (1) or formula (2), a dye-sensitized solar cell, dye adsorption solution composition for the cell and a method of manufacturing the cell. M(L1)(L2)(L3)mL1(X)mX.(Y)mY formula (1) M(L1)(L3)mL2(X)mX.(Y)mY formula (2) [Wherein, M represents Fe2+, Ru2+ or Os2+; L1 represents a bidentate, tridentate or tetradentate ligand having an acidic group and a nitrogen-containing aromatic heterocyclic skeleton; L2 represents a coordination atom which is a bidentate or tridentate ligand of silicon or phosphorus having no unsaturated bond; L3 represents a coordination atom which is a monodentate ligand of silicon, phosphorus or sulfur having no unsaturated bond; X represents a monodentate or bidentate ligand; Y represents a counterion for charge neutral; mL1 represents 0 to 2; mL2 represents 2 to 4; mX represents 0 to 3; and mY represents 0 to 2.]

Description

Photoelectric conversion element, metal complex dye, dye-sensitized liquid composition for dye-sensitized solar cell, dye-sensitized solar cell, and manufacturing method thereof

The present invention relates to a photoelectric conversion element, a metal complex dye, a dye adsorption liquid composition for a dye-sensitized solar cell, a dye-sensitized solar cell, and a method for producing the same.

The photoelectric conversion element is used in various photo sensors, photocopiers, solar cells, etc., and various methods are studied and put into practical use. For example, the photoelectric conversion material includes a photoelectric conversion material using a metal, a photoelectric conversion material using a semiconductor, a photoelectric conversion material using an organic pigment or a pigment, and the like. The background can be exemplified by the fact that solar cells that are expected to utilize non-exhaustive solar energy use endless clean energy without fossil fuel. Among them, the lanthanide solar cells have been researched and developed since very early. Countries also have policy considerations to promote their popularity. However, niobium is an inorganic material and naturally has limitations in terms of throughput and molecular modification.

Therefore, research on dye-sensitized solar cells is being carried out as much as possible. In particular, the research results of Graetzel et al. at the University of EPFL (École Polytechnique Fédérale de Lausanne) in Switzerland became an opportunity. They use a structure in which a pigment containing a ruthenium complex is fixed on the surface of a porous titanium oxide film to achieve the same conversion efficiency as that of amorphous ruthenium. Therefore, the dye-sensitized solar cell has attracted the attention of researchers all over the world.

A ligand containing a specific nitrogen-containing aromatic heterocyclic compound such as a terpyridyl compound is known as a ligand which can be used as a metal complex of the above-mentioned sensitizing dye (see, for example, Patent Document 1). In addition, recently, a phosphorus-coordination ruthenium metal complex of a single tooth has been developed and reported in the society (see Non-Patent Document 1 and Non-Patent Document 2). As a result, attempts have been made to increase the photoelectric conversion efficiency (η).

On the other hand, in particular, solar cells have recently increased their attention and expectations as an energy source for replacing atomic power generation, and are required to be further improved as a solar cell.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent No. 4298799

[Non-patent literature]

[Non-Patent Document 1] Summary of the 2011 Electrochemical Autumn Conference (Chemical Society of Corporate Legal Person), lecture number 2N08

[Non-Patent Document 2] Summary of the 2011 Electrochemical Autumn Conference (Chemical Society of Corporate Legal Person), speech number 2N09

The performance level required for the solar cell is increasing year by year. On the other hand, the metal complex described in Non-Patent Document 1 and Non-Patent Document 2 can achieve long-wavelength of the dye, but it is not necessarily satisfactory.

Therefore, an object of the present invention is to provide a novel metal complex as a sensitizing dye, which aims to improve short-circuit current density and charge injection efficiency of a photoelectric conversion element or a dye-sensitized solar cell by using the metal complex. Further, the durability of the component is improved.

In addition, it is an object of the invention to provide a metal complex dye, a dye adsorption liquid composition, and a method for producing a dye-sensitized solar cell using the same, which are suitably used in the above-described photoelectric conversion element and dye-sensitized solar cell.

In the case of a dye-sensitized solar cell using an anthraquinone pigment, electrons excited by the electron transfer from the center of the europium to the polypyridyl-based receptor ligand (MLCT migration; Metal to Ligand Charge Transfer) are injected into the titanium oxide. The transmission thus functions as a battery.

The previous sensitizing dye of the bipyridyl ligand does not only use polypyridyl type ligands in the receptor ligand, but also often uses polypyridyl type coordination in the donor ligand. body. Therefore, it is estimated that MLCT migration from the metal center to the donor ligand occurs in a ratio that cannot be ignored, and the absorbed light cannot be effectively used for power generation.

In this regard, the present inventors believe that by using a ligand that inhibits MLCT migration as a donor ligand, or permitting the absorbed light to be effectively used for power generation, Intensive research was carried out. As a result, the short-circuit current density (Jsc) is successfully improved by coordinating a relatively soft ligand having a specific coordinating atom in a specific form. Further, it has been found that by using such a ligand, the reduction rate of the metal complex dye reduced by iodine can be improved.

Further, it is estimated that the stabilizing effect by the chelation of the multidentate ligand or the three-dimensional volume of the donor ligand of the two or more specific coordinating atoms is large, thereby causing water to be caused The performance degradation is suppressed and the durability is improved.

That is, the subject of the present invention can be achieved by the following technical means.

(1) A photoelectric conversion element comprising at least a photoreceptor layer containing a semiconductor and a metal complex dye represented by the following formula (1) or (2): M(L1)(L2) (L3) ) _mL1 (X) _mX . (Y) _mY type (1)

M(L1)(L3) _mL2 (X) _mX . (Y) _mY type (2)

[wherein, M represents Fe ²⁺ , Ru ²⁺ or Os ²⁺ ; L1 represents a ligand of a bidentate to tetradentate having an acidic group and a nitrogen-containing aromatic heterocyclic skeleton; and L2 represents a non-unsaturated bond. a ruthenium atom, a phosphorus atom, or a sulfur atom as a ligand of a didentate or a tridentate of a coordinating atom; L3 represents a monodentate coordination having a deuterium atom, a phosphorus atom, or a sulfur atom having no unsaturated bond as a coordinating atom Body; mL1 represents an integer from 0 to 2; mL2 represents an integer from 2 to 4; X represents a single or two-dentate ligand; mX represents an integer from 0 to 3; Y represents a relative ion in the case where the charge must be neutralized (counterion); mY is an integer from 0 to 2].

(2) The photoelectric conversion element according to (1), wherein the L2 is a ligand represented by any one of the following formulas (4) to (6):

Wherein D1 is selected from the group consisting of -Si(R ⁷ ) ₂ , -P(R ⁷ ) ₂ , -P(R ⁷ ), -S(R ⁷ ) and -S, and the ruthenium atom, phosphorus atom and sulfur atom are coordinated. Located on the metal; R ⁷ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; D2 is an atom coordinated to the metal, and is selected from the group consisting of a nitrogen atom, a carbon atom, a germanium atom, and a phosphorus atom. And a sulfur atom; Za represents a group of atoms forming a ring; E represents -O-, -N(R ⁸ )-, -C(R ⁸ ) ₂ -, -C(=R ⁸ ')-, -C(=O )- or -C(=NR ⁸ )-; R ⁸ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; and R ⁸ ' represents an alkylene group, an alkenylene group or a subring Alkyl; here, R ⁸ or R ⁸ ' may also bond with Za to form a ring]

Wherein d represents 0 or 1; Zb represents a group of atoms forming a ring; D3 is selected from the group consisting of -Si(R ⁹ ) ₂ , -P(R ⁹ ) ₂ , -P(R ⁹ ), -S(R ⁹ ) And -S, the germanium atom, the phosphorus atom and the sulfur atom are coordinated to the metal; D4 is selected from the group consisting of -O-, -N-, -N(R ⁹ )-, -Si(R ⁹ )-, -P(R ⁹ )-, -P- and -S-, the oxygen atom, the nitrogen atom, the halogen atom, the phosphorus atom and the sulfur atom are coordinated to the metal; R ⁹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aryloxy group. Or a heteroaryl group; here, Zb may also be bonded to each other to form a ring]

Wherein D5 is selected from the group consisting of -Si(R ¹⁰ ) ₂ , -P(R ¹⁰ ) ₂ , -P(R ¹⁰ ), -S(R ¹⁰ ) and -S, and the ruthenium atom, phosphorus atom and sulfur atom are coordinated. Located on the metal; R ¹⁰ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; D6 is an atom coordinated to a metal selected from a nitrogen atom, a carbon atom, a halogen atom, a phosphorus atom. And a sulfur atom; Zc represents a group of atoms forming a ring; E represents -O-, -N(R ¹¹ )-, -C(R ¹¹ ) ₂ -, -C(=R ¹¹ ')-, -C(=O )- or -C(=NR ¹¹ )-; R ¹¹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; and R ¹¹ ' represents an alkylene group, an alkenylene group or a subring Alkyl; here, R ¹¹ or R ¹¹ ' may also bond with Zc to form a ring].

(3) The photoelectric conversion element according to (1) or (2), wherein the L2 is a ligand represented by any one of the formulae (7) to (12):

Wherein D1 is selected from the group consisting of -Si(R ⁷ ) ₂ , -P(R ⁷ ) ₂ , -P(R ⁷ ), -S(R ⁷ ) and -S, and the ruthenium atom, phosphorus atom and sulfur atom are coordinated. Located on the metal; R ⁷ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; D2 is an atom coordinated to the metal, and is selected from the group consisting of a nitrogen atom, a carbon atom, a germanium atom, and a phosphorus atom. And a sulfur atom; R ¹² each independently represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; n12 represents an integer of 0 to 4; and E represents -O-, -N(R ⁸ )-, -C(R ⁸ ) ₂ -, -C(=R ⁸ ')-, -C(=O)- or -C(=NR ⁸ )-; R ⁸ represents a hydrogen atom, an alkyl group, an alkoxy group, an aromatic group a group, an aryloxy group or a heteroaryl group; R ⁸ ' represents an alkylene group, an alkenylene group or a cycloalkylene group; here, R ⁸ or R ⁸ ' may also bond with R ¹² to form a ring]

Wherein D1 is selected from the group consisting of -Si(R ⁷ ) ₂ , -P(R ⁷ ) ₂ , -P(R ⁷ ), -S(R ⁷ ) and -S, and the ruthenium atom, phosphorus atom and sulfur atom are coordinated. Located on the metal; R ⁷ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; D2a is an atom coordinated to the metal, selected from a nitrogen atom, a phosphorus atom and a sulfur atom; R ¹³ Represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; n13 represents an integer from 0 to 3; and E represents -O-, -N(R ⁸ )-, -C(R ⁸ ) ₂ -, -C(=R ⁸ ')-, -C(=O)- or -C(=NR ⁸ )-; R ⁸ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group R ⁸ ' represents an alkylene group, an alkenylene group or a cycloalkylene group; here, R ⁸ or R ⁸ ' may also bond with R ¹³ to form a ring]

Wherein R ¹⁴ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; n14 represents an integer of 0 to 4; and D3 is selected from -Si(R ⁹ ) ₂ , -P(R ⁹ ) ₂ , -P(R ⁹ ), -S(R ⁹ ) and -S, the deuterium atom, the phosphorus atom and the sulfur atom are coordinated to the metal; R ⁹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aromatic group Oxy or heteroaryl]

Wherein R ¹⁵ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; n15 represents an integer of 0 to 4; and D3 is selected from -Si(R ⁹ ) ₂ , -P(R ⁹ ) ₂ , -P(R ⁹ ), -S(R ⁹ ) and -S, the germanium atom, the phosphorus atom and the sulfur atom are coordinated to the metal; D4 is selected from -O-, -N-, -N(R ⁹ ) -, -Si(R ⁹ )-, -P(R ⁹ )-, -P- and -S-, the oxygen atom, nitrogen atom, germanium atom, phosphorus atom and sulfur atom are coordinated to the metal; R ⁹ represents hydrogen An atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; here, each of the R ¹⁵ groups present on the two benzene rings may be bonded to each other to form a ring]

Wherein D5 is selected from the group consisting of -Si(R ¹⁰ ) ₂ , -P(R ¹⁰ ) ₂ , -P(R ¹⁰ ), -S(R ¹⁰ ) and -S, and the ruthenium atom, phosphorus atom and sulfur atom are coordinated. Located on the metal; R ¹⁰ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; D6 is an atom coordinated to a metal selected from a nitrogen atom, a carbon atom, a halogen atom, a phosphorus atom. And a sulfur atom; R ¹⁶ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; n16 represents an integer of 0 to 3; and E represents -O-, -N(R ¹¹ )-, -C( R ¹¹ ) ₂ -, -C(=R ¹¹ ')-, -C(=O)- or -C(=NR ¹¹ )-; R ¹¹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aromatic group An oxy or heteroaryl group; R ¹¹ ' represents an alkylene group, an alkenylene group or a cycloalkylene group; here, R ¹¹ or R ¹¹ ' may also bond with R ¹⁶ to form a ring]

Wherein D5 is selected from the group consisting of -Si(R ¹⁰ ) ₂ , -P(R ¹⁰ ) ₂ , -P(R ¹⁰ ), -S(R ¹⁰ ) and -S, and the ruthenium atom, phosphorus atom and sulfur atom are coordinated. Located on the metal; R ¹⁰ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; D6 is an atom coordinated to a metal selected from a nitrogen atom, a carbon atom, a halogen atom, a phosphorus atom. And a sulfur atom; R ¹⁷ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; n17 represents an integer of 0 to 3; and E represents -O-, -N(R ¹¹ )-, -C( R ¹¹ ) ₂ -, -C(=R ¹¹ ')-, -C(=O)- or -C(=NR ¹¹ )-; R ¹¹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aromatic group An oxy or heteroaryl group; R ¹¹ ' represents an alkylene group, an alkenylene group or a cycloalkylene group; here, R ¹¹ or R ¹¹ ' may also bond with R ¹⁷ to form a ring].

The photoelectric conversion element according to any one of (1) to (3), wherein L3 in the formula (1) or (2) is selected from Si(R ⁹ ) ₃ , P(R) ⁹ ) ₃ , P(R ⁹ ) ₂ , S(R ⁹ ) ₂ , S(R ⁹ ) [R ⁹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group].

(5) The photoelectric conversion element according to any one of (1), wherein the L1 is a ligand represented by the following formula (3):

[wherein, c represents 0 or 1; R ¹ to R ³ represent an acidic group, and R ⁴ to R ⁶ represent a substituent; and b1 to b3 and c1 to c3 represent an integer of 0 or more and 4 or less].

(6) The photoelectric conversion element according to any one of (1) to (5), wherein X in the formula (1) or (2) is NCS ^- , Cl ^- , Br ^- , I ^- , CN ^- , NCO ^- , H ₂ O or NCN ₂ ^- .

The photoelectric conversion element according to any one of (1) to (6), wherein Y in the formula (1) or (2) is a halide ion, an arylsulfonate ion, Aryl disulfonic acid ion, alkyl sulfate ion, sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroboric acid ion, hexafluorophosphate ion, acetate ion, trifluoromethanesulfonate ion, ammonium ion, alkali metal Ion or hydrogen ion.

The photoelectric conversion element according to any one of (1), wherein the redox-based compound contained in the electrolyte is a cobalt complex.

(9) A dye-sensitized solar cell comprising the photoelectric conversion element according to any one of the above (1) to (8).

(10) A metal complex dye represented by the following formula (1) or formula (2): M(L1)(L2)(L3) _mL1 (X) _mX . (Y) _mY type (1)

M(L1)(L3) _mL2 (X) _mX . (Y) _mY type (2)

[wherein, M represents Fe ²⁺ , Ru ²⁺ or OS ²⁺ ; L1 represents a ligand of a bidentate to tetradentate having an acidic group and a nitrogen-containing aromatic heterocyclic skeleton; and L2 represents a non-unsaturated bond. a ruthenium atom, a phosphorus atom, or a sulfur atom as a ligand of a didentate or a tridentate of a coordinating atom; L3 represents a monodentate coordination having a deuterium atom, a phosphorus atom, or a sulfur atom having no unsaturated bond as a coordinating atom Body; mL1 represents an integer from 0 to 2; mL2 represents an integer from 2 to 4; X represents a single or two-dentate ligand; mX represents an integer from 0 to 3; Y represents a relative ion in the case where the charge must be neutralized ;mY is an integer from 0 to 2].

(11) The metal complex dye according to (10), wherein the L2 is a ligand represented by any one of the following formulas (4) to (6):

Wherein D1 is selected from the group consisting of -Si(R ⁷ ) ₂ , -P(R ⁷ ) ₂ , -P(R ⁷ ), -S(R ⁷ ) and -S, and the ruthenium atom, phosphorus atom and sulfur atom are coordinated. Located on the metal; R ⁷ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; D2 is an atom coordinated to the metal, and is selected from the group consisting of a nitrogen atom, a carbon atom, a germanium atom, and a phosphorus atom. And a sulfur atom; Za represents a group of atoms forming a ring; E represents -O-, -N(R ⁸ )-, -C(R ⁸ ) ₂ -, -C(=R ⁸ ')-, -C(=O )- or -C(=NR ⁸ )-; R ⁸ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; and R ⁸ ' represents an alkylene group, an alkenylene group or a subring Alkyl; here, R ⁸ or R ⁸ ' may also bond with Za to form a ring]

Wherein d represents 0 or 1; Zb represents a group of atoms forming a ring; D3 is selected from the group consisting of -Si(R ⁹ ) ₂ , -P(R ⁹ ) ₂ , -P(R ⁹ ), -S(R ⁹ ) And -S, the germanium atom, the phosphorus atom and the sulfur atom are coordinated to the metal; D4 is selected from the group consisting of -O-, -N-, -N(R ⁹ )-, -Si(R ⁹ )-, -P(R ⁹ )-, -P- and -S-, the oxygen atom, the nitrogen atom, the halogen atom, the phosphorus atom and the sulfur atom are coordinated to the metal; R ⁹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aryloxy group. Or a heteroaryl group; Zb may also be bonded to each other to form a ring]

Wherein D5 is selected from the group consisting of -Si(R ¹⁰ ) ₂ , -P(R ¹⁰ ) ₂ , -P(R ¹⁰ ), -S(R ¹⁰ ) and -S, and the ruthenium atom, phosphorus atom and sulfur atom are coordinated. Located on the metal; R ¹⁰ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; D6 is an atom coordinated to a metal selected from a nitrogen atom, a carbon atom, a halogen atom, a phosphorus atom. And a sulfur atom; Zc represents a group of atoms forming a ring; E represents -O-, -N(R ¹¹ )-, -C(R ¹¹ ) ₂ -, -C(=R ¹¹ ')-, -C(=O )- or -C(=NR ¹¹ )-; R ¹¹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; and R ¹¹ ' represents an alkylene group, an alkenylene group or a subring Alkyl; here, R ¹¹ or R ¹¹ ' may also bond with Zc to form a ring].

(12) A dye-sensitizing liquid composition for a dye-sensitized solar cell, comprising 0.001% by mass to 0.1% by mass of the metal complex dye according to (10) or (11) in an organic solvent, and water The inhibition is 0.1% by mass or less.

(13) A dye-adsorbing electrode for a dye-sensitized solar cell, which comprises applying the dye-adsorbing liquid composition according to (12) to a conductive support provided with a semiconductor, and curing the dye-adsorbing liquid composition A photoreceptor layer is formed.

(14) A method for producing a dye-sensitized solar cell, which is prepared by using the materials of the dye-adsorbing electrode, the electrolyte, and the counter electrode according to (13) above, and using these materials.

In the present specification, unless otherwise specified, the carbon-carbon double bond may be any of the E-type and the Z-type in the molecule, and may be a mixture of these. When a plurality of substituents, a linking group, a ligand, or the like (hereinafter referred to as a substituent or the like) represented by a specific symbol are present, or when a plurality of substituents or the like are specified at the same time or the like, each substituent or the like may be used. They are the same or different. The same applies to the number of substituents and the like. Further, when a plurality of substituents or the like are in close contact (for example, adjacent), the substituents may be bonded to each other to form a ring. Further, a ring (for example, an alicyclic ring, an aromatic ring or a heterocyclic ring) may be further condensed to form a condensed ring.

In the present invention, each substituent may be substituted unless otherwise specified. Replaced.

Therefore, the photoelectric conversion element or the dye-sensitized solar cell of the present invention can improve the short-circuit current density and the charge injection efficiency by applying a novel metal complex as a sensitizing dye, and further improve the durability of the element.

Further, the metal complex dye of the present invention has a novel structure and can be used as a sensitizing dye for the above-mentioned photoelectric conversion element and dye-sensitized solar cell.

In addition, the photoelectric conversion element and the dye-sensitized solar cell which exhibit the above-described excellent performance can be suitably produced by the method for producing a dye-sensitized solar cell of the present invention, the dye-adsorbing liquid composition for a dye-sensitized solar cell, and the like.

The above and other features and advantages of the present invention will become more apparent from the description and appended claims.

1‧‧‧Electrical support

2‧‧‧Photoreceptor layer

3‧‧‧ electrolyte layer

4‧‧‧relative electrode

5‧‧‧Photoelectrode

6‧‧‧ Circuitry

10‧‧‧ photoelectric conversion components

20‧‧‧Pigment sensitized solar cells

21‧‧‧Metal complex pigment

22‧‧‧Semiconductor particles

23‧‧‧CdSe Quantum Dots

24‧‧‧Co-adsorbent

40‧‧‧Photoelectrode

41‧‧‧Transparent electrode

42‧‧‧Semiconductor electrodes

43‧‧‧Transparent conductive film

44‧‧‧Substrate

45‧‧‧Semiconductor layer

46‧‧‧Light scattering layer

100‧‧‧System for the use of pigment-sensitized solar cells

CE‧‧‧relative electrode

E‧‧‧ Electrolytes

M‧‧‧Action Agency

S‧‧‧ spacers

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view schematically showing an embodiment of a photoelectric conversion element of the present invention, including an enlarged view of a circular portion in a layer.

Fig. 2 is a cross-sectional view schematically showing a dye-sensitized solar cell produced in Example 1.

3 is a dye-sensitized solar cell produced in Example 2 using a cobalt complex in an electrolytic solution, and schematically shows a modified example of the photoelectric conversion element shown in FIG. 1 in an enlarged portion (circle) thereof. Sectional view.

Hereinafter, the present invention will be described in detail.

First, the metal complex dye of the present invention will be described in detail.

[metal complex pigment]

The metal complex dye of the present invention is a metal complex dye represented by the following formula (1) or formula (2).

M(L1)(L2)(L3) _mL1 (X) _mX . (Y) _mY type (1)

M(L1)(L3) _mL2 (X) _mX . (Y) _mY type (2)

In the formulae (1) and (2), M represents Fe ²⁺ , Ru ²⁺ or Os ²⁺ . L1 represents a ligand of a bidentate to tetradentate having an acidic group and a nitrogen-containing aromatic heterocyclic skeleton, and L2 represents a bipartite having at least one coordinating atom selected from the group consisting of a halogen atom having no unsaturated bond, a phosphorus atom and a sulfur atom. Or a ligand of a tridentate, L3 represents a monodentate ligand of a coordinating atom selected from the group consisting of a deuterium atom having no unsaturated bond, a phosphorus atom and a sulfur atom. mL1 represents an integer from 0 to 2, and mL2 represents an integer from 2 to 4. X represents a single or bidentate ligand different from L1, L2 and L3, and mX represents an integer of 0 to 3. Y represents a relative ion in the case where the charge must be neutralized, and mY is selected from an integer ranging from 0 to 2 in such a manner that the charge of the entire metal complex of the formula (1) or the formula (2) becomes zero. Here, when there are a plurality of cases in which L3, X, and Y respectively exist, the numbers may be the same or different.

M is preferably Ru ²⁺ .

The heterocyclic ring of the nitrogen-containing aromatic heterocyclic skeleton of L1 has at least a nitrogen atom The ring-constituting atomic aromatic hetero ring, the ring-constituting atom may contain an oxygen atom or a sulfur atom in addition to nitrogen, preferably a 5-membered ring or a 6-membered ring, and the ring may also be an aromatic ring or an aromatic heterocyclic ring. , heterocyclic or alicyclic and condensed ring. Further, the ring-constituting atom may have one or two or more nitrogen atoms. Examples of the nitrogen-containing aromatic heterocyclic ring include a pyridine ring, a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a tetrazole ring, an anthracene ring, an indazole ring, an anthracene ring, and a quinoline. a ring, an isoquinoline ring, a quinazoline ring, a thiazole ring, an isothiazole ring, an oxazole ring, an isoxazole ring, etc., in the present invention, a pyridine ring is preferred, preferably in the ortho position. Bipyridine or terpyridine.

Moreover, the ligand of L1 is a ligand of two teeth to four teeth, preferably two teeth or three teeth, and particularly preferably three teeth.

The nitrogen-containing aromatic heterocyclic skeleton of L1 has at least one acidic group. Further, it may have a substituent, and examples of the substituent include a substituent T to be described later.

Here, the acidic group means a substituent having a dissociative proton, and examples thereof include a carboxyl group, a phosphonyl group, a phosphoryl group, a sulfo group, a boric acid group, etc., or any of these groups. The group is preferably a carboxyl group or a group having a carboxyl group. Further, the acidic group may be in a form of dissociating by releasing protons, or may be a salt. The acidic group is preferably a carboxyl group, a sulfonic acid group, a phosphonium group, or a phosphonium group, or any of these salts. The acidic group may be a group bonded via a linking group, and examples thereof include a carboxyl group-extended vinyl group, a dicarboxy-vinyl group, a cyanocarboxy group-extended vinyl group, and a carboxyphenyl group.

Further, as described above, the acidic group may be a group having a group exhibiting an acidity, and in other words, an acid group may be introduced through a predetermined linking group. In addition, The acidic group may also exist as a salt thereof. The counter ion which is a salt is not particularly limited, and examples thereof include the following positive ions in the counter ion Y. Examples of the linking group include an alkylene group having 1 to 4 carbon atoms, an extended alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, a carbonyl group, and a carbonyloxy group.

In the present invention, from the viewpoint of electron transport, it is preferred not to pass through an acidic group of a linking group, and particularly preferably a carboxyl group.

Further, it is preferable to have a plurality of (two or more) acidic groups, more preferably three or more, and particularly preferably three. It is preferred to have an acidic group at the para position with respect to the nitrogen atom of the pyridine ring.

In the present invention, L1 is preferably a ligand of a second or three teeth represented by the following formula (3).

In the formula (3), c represents 0 or 1. R ¹ to R ³ each independently represent an acidic group, and R ⁴ to R ⁶ each independently represent a substituent. B1 to b3 and c1 to c3 each independently represent an integer of 0 or more and 4 or less. Among them, b1~b3 do not all become 0. When b1 to b3 and c1 to c3 are 2 or more, a plurality of R ¹ to R ³ and R ⁴ to R ⁶ may be the same or different, and when c1 to c3 are 2 or more, R ^{4 is} mutually Between R ⁵ and R ⁶ and R ⁴ and R ⁵ or R ⁵ and R ⁶ may be bonded to each other to form a ring. Here, when there are a plurality of cases where R ¹ to R ⁶ are respectively present, the ones may be the same or different from each other.

c is preferably 1, preferably any two of b1 to b3 is 1, and particularly preferably b1 to b3 are all 1.

The substituent in R ⁴ to R ⁶ may, for example, be a substituent T described later.

In the present invention, it is particularly preferred that all of c1 to c3 are 0, and it is preferred that R ¹ to R ³ are substituted in the para position with respect to the nitrogen atom of the pyridine.

L2 in the formula (1) represents a ligand of at least one coordinating atom selected from a didentate or a tridentate having no antimony atom, a phosphorus atom and a sulfur atom. Here, the non-unsaturated bond means a bond which does not have sp2 or sp as a bond, and preferably has only sp3 or a lone pair.

L2 in the formula (1) is preferably a ligand of a second or three teeth represented by any one of the following formulas (4) to (6).

In the formula (4), D1 is selected from the group consisting of -Si(R ⁷ ) ₂ , -P(R ⁷ ) ₂ , -P(R ⁷ ), -S(R ⁷ ) and -S, the germanium atom, the phosphorus atom and The sulfur atom is coordinated to the metal. D1 is preferably selected from the group consisting of -Si(R ⁷ ) ₂ and -P(R ⁷ ) ₂ , and particularly preferably -P(R ⁷ ) ₂ . R ⁷ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group. In the case where there are two R ⁷ , two R ⁷ may be bonded to each other to form a ring. D2 is an atom which is bonded to a metal and is selected from a nitrogen atom, a carbon atom, a halogen atom, a phosphorus atom and a sulfur atom, and is preferably selected from a nitrogen atom and a carbon atom, and particularly preferably a nitrogen atom. Za denotes a group of atoms forming a ring which may be further substituted by a substituent. E represents -O-, -N(R ⁸ )-, -C(R ⁸ ) ₂ -, -C(=R ⁸ ')-, -C(=O)- or -C(=NR ⁸ )-, Preferred is -O- or -C(R ⁸ ) ₂ -, particularly preferably -C(R ⁸ ) ₂ -. R ⁸ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group. R ⁸ ' represents an alkylene group, an alkenylene group or a cycloalkylene group. R ⁸ or R ⁸ ' and Za may also be bonded to form a ring. Here, when there are a plurality of cases where R ⁷ and R ⁸ are respectively present, the ones may be the same or different.

Further, R ⁸ or R ⁸ ' may be bonded to Za to form a ring, and the ring is preferably 5 or 6 members, more preferably an aromatic ring, and particularly preferably a 6-membered aromatic ring. The ring formed may also have a substituent, and the substituent may be a substituent T.

Here, in the case where R ⁸ or R ⁸ ' is bonded to Za to form a ring, a compound represented by the following formula (4') is more preferable.

In the formula (4'), D1 and D2 are synonymous with D1 and D2 of the formula (4), and the preferred range is also the same. Za' denotes a group of atoms forming a ring, and the ring formed is preferably the same as Za shown below. Zy represents a group of atoms forming a ring, and the ring formed is preferably an aromatic ring or an aromatic hetero ring, more preferably an aromatic ring, further preferably a benzene ring. E' represents >C(R ⁸ )- or -C(=)-.

Za represents a group of atoms forming a ring, and a ring formed of Za is preferably an aromatic ring or an aromatic heterocyclic ring, preferably a 5-membered ring or a 6-membered ring, and the rings may also be through an aromatic ring, a heterocyclic ring or It is alicyclic and condensed, and may have a substituent. Examples of the substituents include a substituent T to be described later. Moreover, the substituent may be D1. Further, an atom coordinated to the metal may be present on the substituent.

Examples of the ring include a benzene ring, a naphthalene ring, a pyridine ring, a pyrrole ring, an anthracene ring, a quinoline ring, an imidazole ring, a pyrazole ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a tetrazole ring, and a carbazole. Ring, anthracene ring, quinoline ring, isoquinoline ring, quinazoline ring, thiazole ring, isothiazole ring, oxazole ring, isoxazole ring, furan ring, benzo[b]furan ring, thiophene ring, benzene And [b] thiophene ring, preferably benzene ring, pyridine ring, pyrrole ring, anthracene ring, quinoline ring, imidazole ring, pyrazole ring, pyrimidine ring, triazole ring, more preferably benzene ring, pyridine Ring, pyrrole ring.

The alkyl group in R ⁷ and R ⁸ is preferably an alkyl group having 1 to 20 carbon atoms, and examples thereof include methyl group, ethyl group, isopropyl group, n-butyl group, tert-butyl group, n-hexyl group, and n-octyl group. a group, n-dodecyl group, n-octadecyl group; alkoxy group is preferably an alkoxy group having 1 to 20 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, an isopropoxy group, and a n-butyl group. Oxyl, n-hexyloxy, n-octyloxy, n-dodecyloxy, n-octadecyloxy; aryl is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. The aryloxy group is preferably an aryloxy group having 6 to 20 carbon atoms, and examples thereof include a phenoxy group and a naphthyloxy group; and the heteroaryl group preferably has a carbon number of 1 to 20 and at least a ring-constituting atom The heteroaryl group of a nitrogen atom, an oxygen atom or a sulfur atom is preferably a 5-membered ring or a 6-membered ring, and the ring may have a condensed ring or a substituent, and examples thereof include a pyridine ring, a pyrrole ring, a thiophene ring, and a fluorene ring. Anthracycline, quinoline ring, benzo[b]thiophene ring.

Here, it is particularly preferable that two R ^{7 are} bonded to each other to form a ring, and D1 forming such a ring is preferably a formula (S1) or a formula (S2) having the following structure.

Here, Da represents -Si< or -P<. Rx represents a substituent. d represents an integer from 0 to 4. The substituent in Rx can be exemplified by the substituent T described later. d is preferably 0 to 2, more preferably 0 or 1.

The alkylene group in R ⁸ ' is preferably an alkylene group having 1 to 20 carbon atoms, and examples thereof include a methine group, an ethylene group, an isopropylidene group, and an octylene group; and an alkenylene group is preferably Examples of the alkenylene group having 2 to 20 carbon atoms include a vinylidene group, a propenylene group, and a hexylene group; and the cycloalkylene group is preferably a cycloalkylene group having 5 to 20 carbon atoms, and examples thereof include Cyclopentylene, cyclohexylene.

In the formula (5), d represents 0 or 1, and is preferably 1. Zb each independently represents a group of atoms forming a ring, and the ring may be further substituted with a substituent. D3 is selected from the group consisting of -Si(R ⁹ ) ₂ , -P(R ⁹ ) ₂ , -P(R ⁹ ), -S(R ⁹ ) and -S, and the germanium atom, the phosphorus atom and the sulfur atom are coordinated to the metal. D3 is preferably selected from the group consisting of -Si(R ⁹ ) ₂ and -P(R ⁹ ) ₂ , and particularly preferably -P(R ⁹ ) ₂ . D4 is selected from the group consisting of -O-, -N-, -N(R ⁹ )-, -Si(R ⁹ )-, -P(R ⁹ )-, -P- and -S-, the oxygen atom, the nitrogen atom, The ruthenium atom, the phosphorus atom and the sulfur atom are coordinated to the metal. D4 is preferably selected from the group consisting of -N-, -N(R ⁹ )-, and -Si(R ⁹ )-, and particularly preferably selected from the group consisting of -N- and -N(R ⁹ )-. R ⁹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group. In the case where there are two R ⁹ , two R ⁹ may be bonded to each other to form a ring. Moreover, R ⁹ may also bond with Zb to form a ring. Here, the presence of the plurality of D3 or Zb, D4, R ⁹ there are a plurality of circumstances, these may be mutually the same or different.

Moreover, Zbs may be bonded to each other to form a ring. The ring is preferably a 5-membered ring or a 6-membered ring. Such a ring is preferably a heterocyclic ring of 5 or 6 members, and examples thereof include a furan ring, a thiophene ring, a 4H-pyran ring, a 1,4-dihydropyridine ring, a pyrazine ring, and a tetrahydrohydromorpholine ring. , tetradehydrothiomorpholine ring. The ring formed may also have a substituent. The substituent T can be exemplified as the substituent.

Zb represents a group of atoms forming a ring, and the ring formed is preferably a 5-membered ring to a 7-membered ring (preferably a 5-membered ring or a 6-membered ring), and the ring may be an alicyclic ring or an aromatic ring. It can also be a heterocyclic ring. These rings may also have a substituent in the condensed ring, and examples of the substituent include a substituent T to be described later. Moreover, the substituent may also be D3.

The alicyclic ring may, for example, be a cyclopentane ring, a cyclohexane ring or a cyclohexene ring; and the heteroaryl ring as a part of the aromatic ring or the heterocyclic ring may be a ring formed of Za in the formula (4); a heteroaryl ring; Examples of the heterocyclic ring include a pyrrolidine ring, a piperidine ring, a morpholine ring, a piperazine ring, a tetrahydrofuran ring, and a tetrahydropyran ring. The ring formed of Zb is preferably an aromatic ring or an aromatic heterocyclic ring, more preferably an aromatic ring, of which a benzene ring is preferred.

R ⁹ is synonymous with R ⁷ and the preferred range is also the same. Among them, it is preferred that two R ⁹ are bonded to each other to form a ring, and D3 forming such a ring is preferably a formula (S1) or a formula (S2) of the structure.

In the formula (6), D5 is selected from the group consisting of -Si(R ¹⁰ ) ₂ , -P(R ¹⁰ ) ₂ , -P(R ¹⁰ ), -S(R ¹⁰ ) and -S, the germanium atom, the phosphorus atom and The sulfur atom is coordinated to the metal. D5 is preferably selected from the group consisting of -Si(R ¹⁰ ) ₂ and -P(R ¹⁰ ) ₂ , and particularly preferably -P(R ¹⁰ ) ₂ . R ¹⁰ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group. In the case where there are two R ¹⁰ , two R ¹⁰ may be bonded to each other to form a ring. D6 is an atom coordinated to a metal selected from a nitrogen atom, a carbon atom, a halogen atom, a phosphorus atom and a sulfur atom, preferably selected from a nitrogen atom and a carbon atom, and particularly preferably a carbon atom. Zc represents a group of atoms forming a ring, and the ring may be further substituted with a substituent. E represents -O-, -N(R ¹¹ )-, -C(R ¹¹ ) ₂ -, -C(=R ¹¹ ')-, -C(=O)- or -C(=NR ¹¹ )-, Preferred is -O- or -C(R ⁸ ) ₂ -, particularly preferably -C(R ⁸ ) ₂ -. R ¹¹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group. R ¹¹ ' represents an alkylene group, an alkenylene group or a cycloalkylene group. R ¹¹ or R ¹¹ ' may also bond with Zc to form a ring. Here, when a plurality of D5, E, or R ¹⁰ and R ¹¹ are present in a plurality of cases, each of them may be the same or different from each other.

Further, R ¹¹ or R ¹¹ ' may also be bonded to Za to form a ring, and the ring is preferably 5 or 6 members, more preferably an aromatic ring, and particularly preferably a 6-member aromatic ring. The ring formed may also have a substituent, and the substituent may be a substituent T.

Zc represents a group of atoms forming a ring, and the ring formed therefrom is preferably an aromatic ring or an aromatic heterocyclic ring, preferably a 5-membered ring or a 6-membered ring, and the rings may also be through an aromatic ring or a heterocyclic ring. The ring is condensed and may also have a substituent. Examples of the substituents include a substituent T to be described later. Moreover, the substituent may also be D5.

Examples of the ring include a benzene ring, a naphthalene ring, a pyridine ring, a pyrrole ring, an anthracene ring, a quinoline ring, an imidazole ring, a pyrazole ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a tetrazole ring, and a carbazole. Ring, anthracene ring, quinoline ring, isoquinoline ring, quinazoline ring, thiazole ring, isothiazole ring, oxazole ring, isoxazole ring, furan ring, benzo[b]furan ring, thiophene ring, benzene And [b] thiophene ring, preferably benzene ring, pyridine ring, pyrrole ring, anthracene ring, quinoline The ring, the imidazole ring, the pyrazole ring, the pyrimidine ring, and the triazole ring are more preferably a benzene ring, a pyridine ring or a pyrrole ring.

R ¹⁰ is synonymous with R ⁷ , R ¹¹ is synonymous with R ⁸ , and R ¹¹ 'is synonymous with R ⁸ ', and the preferred ranges are also the same in each.

R ^{10 is} preferably one in which two R ^{10 are} bonded to each other to form a ring, and D5 forming such a ring is preferably a formula (S1) or a formula (S2) of the structure.

When L2 in the formula (1) is a ligand of a second or three teeth represented by the formula (4), preferred ones of the following formula (7) or (8) The case of the indicated two or three tooth ligands.

In the formula (7), D1 is selected from the group consisting of -Si(R ⁷ ) ₂ , -P(R ⁷ ) ₂ , -P(R ⁷ ), -S(R ⁷ ) and -S, the germanium atom, the phosphorus atom and The sulfur atom is coordinated to the metal. D1 is preferably selected from the group consisting of -Si(R ⁷ ) ₂ and -P(R ⁷ ) ₂ , and particularly preferably -P(R ⁷ ) ₂ . R ⁷ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group. In the case where there are two R ⁷ , two R ⁷ may be bonded to each other to form a ring. D2 is an atom which is bonded to a metal and is selected from a nitrogen atom, a carbon atom, a halogen atom, a phosphorus atom and a sulfur atom, and is preferably selected from a nitrogen atom and a carbon atom, and particularly preferably a nitrogen atom. R ¹² each independently represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group. N12 represents an integer of 0 to 4. When n is 2 or more, a plurality of R ¹² may be bonded to each other to form a ring. E represents -O-, -N(R ⁸ )-, -C(R ⁸ ) ₂ -, -C(=R ⁸ ')-, -C(=O)- or -C(=NR ⁸ )-, Preferred is -O- or -C(R ⁸ ) ₂ -, particularly preferably -C(R ⁸ ) ₂ -. R ⁸ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group. R ⁸ ' represents an alkylene group, an alkenylene group or a cycloalkylene group. R ⁸ or R ⁸ ' may also be bonded to R ¹² to form a ring. Here, when there are a plurality of cases where R ¹² , R ⁷ , and R ⁸ are respectively present, the ones may be the same or different from each other.

In the formula (8), D1 is selected from the group consisting of -Si(R ⁷ ) ₂ , -P(R ⁷ ) ₂ , -P(R ⁷ ), -S(R ⁷ ) and -S, the germanium atom, the phosphorus atom and The sulfur atom is coordinated to the metal. D1 is preferably selected from the group consisting of -Si(R ⁷ ) ₂ and -P(R ⁷ ) ₂ , and particularly preferably -P(R ⁷ ) ₂ . R ⁷ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group. In the case where there are two R ⁷ , two R ⁷ may be bonded to each other to form a ring. D2a is an atom coordinated to a metal selected from a nitrogen atom, a phosphorus atom and a sulfur atom, preferably selected from a nitrogen atom or a sulfur atom, and more preferably a nitrogen atom. R ¹³ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group. N13 represents an integer of 0 to 3. When n is 2 or more, a plurality of R ¹³ may be bonded to each other to form a ring. E represents -O-, -N(R ⁸ )-, -C(R ⁸ ) ₂ -, -C(=R ⁸ ')-, -C(=O)- or -C(=NR ⁸ )-, Preferred is -O- or -C(R ⁸ ) ₂ -, particularly preferably -C(R ⁸ ) ₂ -. R ⁸ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group. R ⁸ ' represents an alkylene group, an alkenylene group or a cycloalkylene group. R ⁸ or R ⁸ ' may also be bonded to R ¹³ to form a ring. Here, when there are a plurality of R ¹³ , R ⁷ , and R ⁸ , respectively, the ones may be the same or different.

In the formula (7) and the formula (8), R ⁸ or R ⁸ ' may be bonded to R ¹² or R ¹³ to form a ring, and the ring is preferably 5 or 6 members, more preferably aromatic. Ring, especially good is the aromatic ring of 6 members. The ring formed may also have a substituent, and the substituent may be a substituent T.

Here, in the case where R ⁸ or R ⁸ ' and R ¹² or R ¹³ are bonded to each other to form a ring, a compound represented by the following formula (7') or formula (8') is preferred.

In the formula (7 '), Formula (8'), D1 D1, D2, and R ¹² in the formula (7) of, D2 and R ¹² are synonymous, and preferred scope are also the same. D2a and R ¹³ in the formula (8) of D2a and R ¹³ are synonymous and preferred scope are also the same. Zx represents a group of atoms forming a ring, and the ring formed is preferably an aromatic ring or an aromatic heterocyclic ring, more preferably an aromatic ring, still more preferably a benzene ring. E' represents >C(R ⁸ )- or -C(=)-, preferably -C(=)-. N12a represents an integer from 0 to 3, and n13a represents an integer from 0 to 2.

The substituent of R ¹² in the formula (7) and R ¹³ in the formula (8) is exemplified by the substituent T described later. Moreover, the substituent may also be D1.

In the case where L2 in the formula (1) is a ligand of a second or three teeth represented by the formula (5), preferred ones of the following formulas (9) or (10) The case of the indicated two or three tooth ligands.

In the formula (9), R ¹⁴ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group. N14 represents an integer of 0 to 4. When n is 2 or more, a plurality of R ¹⁴ may be bonded to each other to form a ring. D3 is selected from the group consisting of -Si(R ⁹ ) ₂ , -P(R ⁹ ) ₂ , -P(R ⁹ ), -S(R ⁹ ) and -S, and the germanium atom, the phosphorus atom and the sulfur atom are coordinated to the metal. D3 is preferably selected from the group consisting of -Si(R ⁹ ) ₂ and -P(R ⁹ ) ₂ , and particularly preferably -P(R ⁹ ) ₂ . R ⁹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group. In the case where there are two R ⁹ , a plurality of R ⁹ may be bonded to each other to form a ring. Moreover, R ⁹ may also form a ring with R ¹⁴ . Here, when there are a plurality of two D3 or R ¹⁴ and R ⁹ respectively, the two may be the same or different.

In the formula (10), R ¹⁵ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group. N15 represents an integer of 0 to 4. When n is 2 or more, a plurality of R ¹⁵ may be bonded to each other to form a ring. D3 is selected from the group consisting of -Si(R ⁹ ) ₂ , -P(R ⁹ ) ₂ , -P(R ⁹ ), -S(R ⁹ ) and -S, and the germanium atom, the phosphorus atom and the sulfur atom are coordinated to the metal. D3 is preferably selected from the group consisting of -Si(R ⁹ ) ₂ and -P(R ⁹ ) ₂ , and particularly preferably -P(R ⁹ ) ₂ . D4 is selected from the group consisting of -O-, -N-, -N(R ⁹ )-, -Si(R ⁹ )-, -P(R ⁹ )-, -P- and -S-, the oxygen atom, the nitrogen atom, The ruthenium atom, the phosphorus atom and the sulfur atom are coordinated to the metal. D4 is preferably selected from the group consisting of -N-, -N(R ⁹ )-, and -Si(R ⁹ )-, and particularly preferably selected from the group consisting of -N- and -N(R ⁹ )-. R ⁹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group. In the case where there are two R ⁹ , a plurality of R ⁹ may be bonded to each other to form a ring. Further, R ⁹ may be bonded to R ¹⁵ to form a ring. Here, when there are a plurality of two D3 or R ¹⁵ and R ⁹ respectively, the ones may be the same or different.

Moreover, each of the R ¹⁵ present on the two benzene rings may be bonded to each other to form a ring. The ring is preferably a heterocyclic ring of 5 or 6 members, and examples thereof include a furan ring, a thiophene ring, a 4H-pyran ring, a 1,4-dihydropyridine ring, a pyrazine ring, and a tetrahydrohydromorpholine ring. Tetrahydrothiomorpholine ring.

The substituent of R ¹⁴ in the formula (9) and R ¹⁵ in the formula (10) may be a substituent T to be described later. Moreover, the substituent may also be D3.

In the case where L2 in the formula (1) is a ligand of a second or three teeth represented by the formula (6), preferred ones of the following formula (11) or formula (12) The case of the two or three teeth ligands indicated.

In the formula (11), D5 is selected from the group consisting of -Si(R ¹⁰ ) ₂ , -P(R ¹⁰ ) ₂ , -P(R ¹⁰ ), -S(R ¹⁰ ) and -S, the germanium atom, the phosphorus atom and The sulfur atom is coordinated to the metal. D5 is preferably selected from the group consisting of -Si(R ¹⁰ ) ₂ and -P(R ¹⁰ ) ₂ , and particularly preferably -P(R ¹⁰ ) ₂ . R ¹⁰ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group. In the case where there are two R ¹⁰ , a plurality of R ¹⁰ may be bonded to each other to form a ring. D6 is an atom coordinated to a metal selected from a nitrogen atom, a carbon atom, a halogen atom, a phosphorus atom and a sulfur atom, preferably selected from a nitrogen atom and a carbon atom, and particularly preferably a carbon atom. R ¹⁶ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group. N16 represents an integer of 0 to 3. When n is 2 or more, a plurality of R ¹⁶ may be bonded to each other to form a ring. E represents -O-, -N(R ¹¹ )-, -C(R ¹¹ ) ₂ -, -C(=R ¹¹ ')-, -C(=O)- or -C(=NR ¹¹ )-, Preferred is -O- or -C(R ⁸ ) ₂ -, particularly preferably -C(R ⁸ ) ₂ -. R ¹¹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group. R ¹¹ ' represents an alkylene group, an alkenylene group or a cycloalkylene group. R ¹¹ or R ¹¹ ' may also be bonded to R ¹⁶ to form a ring. Here, when there are a plurality of two D5, E, or R ¹⁶ , R ¹⁰ , and R ¹¹ , respectively, the two may be the same or different.

In the formula (12), D5 is selected from the group consisting of -Si(R ¹⁰ ) ₂ , -P(R ¹⁰ ) ₂ , -P(R ¹⁰ ), -S(R ¹⁰ ) and -S, the germanium atom, the phosphorus atom and The sulfur atom is coordinated to the metal. D5 is preferably selected from the group consisting of -Si(R ¹⁰ ) ₂ and -P(R ¹⁰ ) ₂ , and particularly preferably -P(R ¹⁰ ) ₂ . R ¹⁰ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group. In the case where there are two R ¹⁰ , a plurality of R ¹⁰ may be bonded to each other to form a ring. D6 is an atom coordinated to a metal selected from a nitrogen atom, a carbon atom, a halogen atom, a phosphorus atom and a sulfur atom, preferably selected from a nitrogen atom and a carbon atom, and particularly preferably a carbon atom. R ¹⁷ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group. N17 represents an integer of 0 to 3. When n is 2 or more, a plurality of R ¹⁷ may be bonded to each other to form a ring. E represents -O-, -N(R ¹¹ )-, -C(R ¹¹ ) ₂ -, -C(=R ¹¹ ')-, -C(=O)- or -C(=NR ¹¹ )-, Preferred is -O- or -C(R ⁸ ) ₂ -, particularly preferably -C(R ⁸ ) ₂ -. R ¹¹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group. R ¹¹ ' represents an alkylene group, an alkenylene group or a cycloalkylene group. R ¹¹ or R ¹¹ ' may also be bonded to R ¹⁷ to form a ring. Here, when there are a plurality of two D5, E, or R ¹⁷ , R ¹⁰ , and R ¹¹ , respectively, the two may be the same or different.

In the formulae (11) and (12), R ¹¹ or R ¹¹ ' may also be bonded to R ¹⁶ or R ¹⁷ to form a ring, and the ring is preferably 5 or 6 members, more preferably aromatic. Ring, especially good is a 6-member aromatic ring. The ring formed may also have a substituent, and the substituent may be a substituent T.

¹⁷ of the said T. The substituent group include the substituent group R (11) in the formula ^16, the formula R (12) in the Moreover, the substituent may also be D5.

The L3 in the formula (1) or the formula (2) represents a monodentate ligand in which the coordinating atom is selected from the group consisting of a halogen atom having no unsaturated bond, a phosphorus atom and a sulfur atom, preferably Si(R ⁹ ) _{3 .} , P(R ⁹ ) ₃ , P(R ⁹ ) ₂ , S(R ⁹ ) ₂ , S(R ⁹ ). Here, R ⁹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group. Further, in the case where there are two R ⁹ , a plurality of R ⁹ may be bonded to each other to form a ring.

R ⁹ is synonymous with R ⁷ and the preferred range is also the same.

In the present invention, L3 is preferably a monodentate ligand having a coordinating atom which is a phosphorus atom having no unsaturated bond, more preferably P(R ⁹ ) ₃ or P(R ⁹ ) ₂ , further preferably Is P(R ⁹ ) ₃ .

Here, R ^{9 is} preferably an alkyl group, an alkoxy group, an aryl group or an aryloxy group, more preferably an alkoxy group or an aryloxy group, still more preferably an aryloxy group.

X in the formula (1) or (2) represents a single or bidentate ligand different from L1, L2 and L3, mX represents an integer of 0 to 3, and mX is preferably 1 to 3. More preferably 1 or 2. When X is a single tooth ligand, it is preferred that mX is 2; When X is a bidentate ligand, it is preferred that mX is 1. When mX is 2 or more, X may be the same or different, and X may be connected to each other.

As X, for example, a monodentate ligand may be selected from the group consisting of a decyloxy anion, a sulfonium anion, a thiodecyloxy anion, a thiosulfonium anion, a mercaptoamino anion, a thioamine group. Formate anion, dithiocarbamate anion, thiocarbonate anion, dithiocarbonate anion, trithiocarbonate anion, mercapto anion, thiocyanate anion, isothiocyanate Or an anion of a group consisting of an anion, a cyanate anion, an isocyanate anion, a cyano anion, an alkylthio anion, an arylthio anion, an alkoxy anion, and an aryloxy anion, or coordinated by the groups Monodentate ligand, or an anion, atom or compound containing a halogen atom, a cyano group, a carbonyl group, a dialkyl ketone, a carbonamide, a thiocarbamide, and a thiourea (including a hydrogen atom substituted by an anion) Compound). Further, when the ligand X contains an alkyl group, an alkenyl group, an alkynyl group or an alkylene group, these may be linear or branched, and may be substituted or unsubstituted. Further, in the case of containing an aryl group, a heterocyclic group, a cycloalkyl group or the like, these may be substituted or unsubstituted, and may be monocyclic or condensed.

Examples of the bidentate ligand include a decyloxy anion, a sulfonium anion, a thiodecyloxy anion, a thiosulfonium anion, a mercaptoamino anion, a thiourethane anion, and a second. Thiocarbamate anion, thiocarbonate anion, dithiocarbonate anion, trithiocarbonate anion, sulfhydryl anion, alkylthio anion, arylthio anion, alkoxy anion, and aryloxy a base anion or a bidentate ligand having a partial structure selected from the group consisting of the groups, specifically Examples thereof include a 1,3-diketone and the like.

In the present invention, X is preferably a monodentate ligand, more preferably NCS ^- , Cl ^- , Br ^- , I ^- , CN ^- , NCO ^- , H ₂ O or NCN ₂ ^- .

Y represents the relative ion in the case where the charge must be neutralized. In general, the metal complex dye is a cation or an anion, or whether it has a net ionic charge depending on the metal, ligand and substituent in the metal complex dye.

The metal complex dye represented by the formula (1) or the formula (2) may be dissociated by a substituent having a dissociable group or the like to have a negative charge. In this case, the charge of the entire metal complex dye represented by the formula (1) or the formula (2) becomes electrically neutral due to Y.

In the case where the relative ion Y is a positive relative ion, the relative ion Y is, for example, an inorganic or organic ammonium ion (for example, a tetraalkylammonium ion, a pyridinium ion, etc.), a phosphonium ion (for example, a tetraalkylphosphonium ion, an alkyl group). Triphenylphosphonium ion, etc.), alkali metal ion or proton.

In the case where the relative ion Y is a negative relative ion, for example, the relative ion Y may be an inorganic anion or an organic anion. For example, a halogen anion (for example, a fluoride ion, a chloride ion, a bromide ion, an iodide ion, or the like), a substituted arylsulfonate ion (for example, a p-toluenesulfonate ion, a p-chlorobenzenesulfonate ion, etc.), An aryl disulfonic acid ion (eg, 1,3-benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalene disulfonic acid ion, etc.), alkyl sulfate ion (eg, methyl sulfate ion) Etc.), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroboric acid ion, hexafluorophosphate ion, picric acid ion, acetate ion, trifluoromethanesulfonate ion, and the like. Further, As the charge-balanced counter ion, another dye having a charge opposite to that of the ionic polymer or the dye may be used, and a metal counter ion (for example, bis-benzene-1,2-dithiol nickel (III) or the like) may be used.

In the present invention, Y is preferably a halide ion, an arylsulfonic acid ion, an aryl disulfonic acid ion, an alkyl sulfate ion, a sulfate ion, a thiocyanate ion, a perchloric acid ion, a tetrafluoroborate ion, or a sixth Fluorophosphate ion, acetate ion, trifluoromethanesulfonate ion, ammonium ion, alkali metal ion or hydrogen ion.

Specific examples of the metal complex dye of the present invention are shown below, but the present invention is not limited to these specific examples.

Here, Ph represents a phenyl group, and Me represents a methyl group.

The ligand represented by L2 and L3 of the metal complex dye of the present invention can be easily synthesized by a usual method.

The metal complex dye of the present invention can be easily synthesized by a method based on the method described in JP-A-2009-051999.

The maximum absorption wavelength of the metal complex pigment of the present invention in the solution is preferably in the range of 300 nm to 1000 nm, more preferably in the range of 350 nm to 950 nm, and particularly preferably in the range of 370 nm to 900 nm. .

Here, the effect of the metal complex dye of the preferred embodiment of the present invention can be estimated as follows.

The soft ligand can form a very stable complex with Ru ²⁺ or the like as a soft acid. Moreover, the soft acid-base is more covalently bonded than the hard acid-base pair, and it is difficult to generate an anion exchange reaction as a decomposition path of the dye, and it is difficult to produce a complex not only in a non-polar solvent. The dissociation of the ligand is also difficult to produce dissociation of the ligand in a polar solvent.

Soft ligands can be roughly classified into the following (1) and (2).

(1) A ligand in which a coordination atom forms a π-conjugated system and has a π ^* orbital

For example: pyridine, phenyl, morpholine, CO, CN, etc.

(2) Heavy atomic ligands with low energy levels of σ ^* orbitals

For example, a bipyridyl ligand, a phosphine ligand, a thiolate ligand, or the like, which has been previously used, is classified as (1), and a halogen atom having no unsaturated bond of L2 or L3 in the present invention, Phosphorus atoms and sulfur atoms are mainly classified as (2).

Therefore, in consideration of the above, the mechanism for improving the electron injection efficiency, improving the durability, and improving the reduction rate by iodine reduction can be estimated as follows.

- Inferred mechanism for improving electron injection efficiency -

In contrast to the above-described group of ligands (1) showing absorption of MLCT migration, the type of (2) without π ^* orbit does not exhibit absorption of MLCT migration in principle. Therefore, the MLCT generated by absorbing visible light is limited to the electron movement from the metal center to the acceptor side ligand, and in principle does not produce MLCT migration to the donor side ligand which does not contribute to power generation. According to this principle, it is considered that the electron injection efficiency to TiO ₂ is greatly improved as compared with the conventional dye. In the case where L2 of the present invention is of a type in which at least one of the coordinating atoms is (2), the other coordinating atoms may be of the type of (1). In this case, strictly speaking, L2 is a complex showing absorption of MLCT migration. Body. However, L2 contains a soft and highly enthalpy atom, a phosphorus atom or a sulfur atom, and thus the π inverse supply of L1 as its trans position becomes strong. By making the π inverse supply from the metal center to L1 strong, the orbital overlap between the metal center and L1 becomes good, and it becomes easier to generate the MLCT to L1.

- Inferred mechanism for durability improvement -

The type of the above (1) has a planar structure such as pyridine or a rod-like structure such as NCS, and cannot widely cover the center of a metal atom such as Ru ²⁺ . On the other hand, the type of the above (2) has a large atomic radius and a plurality of substituents in the three-dimensional direction, so that the volume of the solid is large, and the center of the metal atom can be effectively covered. However, in order to obtain sufficient durability, it is important to increase the stabilizing effect of chelation or to introduce two or more of the above (2) by setting it as a multidentate ligand as in each embodiment of the present invention. A type of ligand that increases the volume of the solid volume.

- Inferred mechanism for increasing the rate of reduction of iodine -

Unexpected effects, the detailed mechanism has not been confirmed. As a speculative mechanism, it is considered that since the coordination atom uses a soft heavy atom, the affinity with the iodine of the same soft heavy atom is improved. That is, when electrons are moved from the iodine to the dye, the alignment of the tracks becomes good, and the efficiency of electron transfer is improved.

[Photoelectric conversion element and dye-sensitized solar cell]

The photoelectric conversion element of the present invention comprises a substrate, a transparent electrode, and a semiconductor (half a conductor microparticle), a metal complex dye having an adsorption group, an electrolyte, and a counter electrode, and a member that holds the electrolyte to insulate the transparent electrode from the counter electrode. For example, as shown in FIG. 1, the photoelectric conversion element 10 includes a conductive support 1 including a substrate and a transparent electrode, and a photoreceptor layer 2 sensitized by a dye (metal complex dye) 21 provided thereon. An electrolyte layer (electrolyte) 3 and an opposite electrode 4. Here, in the present invention, it is preferred that the dye (metal complex dye) 21 and the co-adsorbent 24 are adsorbed on the photoreceptor layer 2. The conductive support 1 provided with the photoreceptor layer 2 functions as a working electrode in the photoelectric conversion element 10. In the present embodiment, the photoelectric conversion element 10 is shown as a system 100 using a dye-sensitized solar cell, which can be used in a battery application in which the operation mechanism M is operated by the external circuit 6.

In the present embodiment, the light receiving electrode (dye adsorption electrode) 5 includes a guide The electric support 1 and the photoreceptor layer 2 coated thereon with the semiconductor fine particles 22 to which the dye (metal complex dye) 21 is adsorbed are applied. In the present embodiment, for the sake of convenience of illustration, the electrolyte may be contained in the light-receiving electrode (dye-adsorbing electrode) 5, and it may be considered that the electrolyte is not contained. The photoreceptor layer 2 is designed according to the purpose, and may be a single layer structure or a multilayer structure. The pigment (metal complex pigment) 21 in one layer of the photoreceptor layer may be one type or a mixture of a plurality of types. The light incident on the photoreceptor layer 2 excites the dye (metal complex dye) 21. The excited dye has an electron with high energy, and the electron is transferred from the dye (metal complex dye) 21 to the conduction band of the semiconductor fine particle 22, and further reaches the conductive support 1 by diffusion. At this time, the dye (metal complex dye) 21 becomes an oxidized body. The electron side of the electrode The external circuit 6 operates to return to the photoreceptor layer 2 in which the oxidant of the dye (metal complex dye) 21 is present via the counter electrode 4, thereby functioning as a solar cell.

Regarding the photoelectric conversion element and the dye-sensitized solar cell of the present invention The materials to be used and the method of producing the members can be made by using such materials and the usual manufacturing methods of the members. For example, reference is made to the specification of U.S. Patent No. 4,927,721, the specification of U.S. Patent No. 4,684,537, and U.S. Patent No. 5,084,365. The specification, the specification of the U.S. Patent No. 5,350,644, the specification of the U.S. Patent No. 5,463,057, the specification of the U.S. Patent No. 5,525,440, the Japanese Patent Laid-Open No. Hei 7-249790, the Japanese Patent Publication No. 2004-220974, and the Japanese Patent Laid-Open No. 2008- Bulletin No. 135197. Hereinafter, the main components will be briefly described.

(electrolyte composition)

Electrolyte composition usable in the photoelectric conversion element of the present invention The redox pair may, for example, be a combination of iodine and an iodide (for example, lithium iodide, tetrabutylammonium iodide, tetrapropylammonium iodide, etc.), an alkyl viologen (for example, methyl viologen). Combination of chloride, hexyl viologen bromide, benzyl viologen tetrafluoroborate) and its reducing body, polyhydroxybenzene (such as hydroquinone, naphthohydroquinone, etc.) and its oxidant, 2 A combination of a valence with a trivalent iron complex (for example, red blood salt and yellow blood salt), a combination of a divalent and trivalent cobalt complex, and the like. Preferred among these are combinations of iodine and iodide, and combinations of divalent and trivalent cobalt complexes.

-cobalt complex -

The cobalt complex is preferably a cobalt complex represented by the following formula (A).

Co(LL3)ma(X1)mb. CI type (A)

In the formula (A), LL3 represents a ligand of a second or third tooth. X1 represents a ligand for a single tooth. Ma represents an integer from 0 to 3. Mb represents an integer from 0 to 6. CI denotes a relative ion in the case where a relative ion is necessary in order to neutralize the charge.

The monodentate ligand in X1 may be a monodentate ligand represented by x in the formula (1) or the formula (2), and CI may be Y.

LL3 is preferably a compound represented by the following formula (B).

In the formula (B), Zd, Ze, and Zf are each independently represented to form 5 A ring of atoms or a ring of 6 members. Zd, Ze and Zf may also have a substituent, and may also be closed to the adjacent ring via a substituent. h means 0 or 1. The substituent T which will be described later can be mentioned as this substituent.

X1 is preferably a halide ion.

More preferably, the compound represented by the above formula (B) is represented by the following formula (B-1). ~ is expressed by the formula (B-3).

R'a~R'i represents a substituent. Na~nb represents an integer from 0 to 4. Nc and ne represent integers from 0 to 3. Nd represents an integer from 0 to 2. Nf and nj represent integers from 0 to 4.

In the formula (B-1) to the formula (B-3), examples of the substituent of R'a to R'i include an aliphatic group, an aromatic group, and a heterocyclic group. Specific examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, and a heterocyclic ring. Preferred examples thereof include an alkyl group (e.g., methyl, ethyl, n-butyl, n-hexyl, isobutyl, t-butyl, t-butyl, n-dodecyl, cyclohexyl, benzyl, etc.), Substituted aryl (e.g., phenyl, tolyl, naphthyl, etc.), alkoxy (e.g., methoxy, ethoxy, isopropoxy, butoxy, etc.).

Specific examples of the cobalt complex represented by the formula (A) include the following compounds.

The cation of the iodide salt is preferably a nitrogen-containing aromatic cation of a 5-membered ring or a 6-membered ring. In particular, when the compound represented by the formula (A) is not an iodide salt, it is preferred to use the re-issued publication No. WO95/18456, Japanese Patent Laid-Open No. Hei 8-259543, and Electrochemistry (Vol. 65, No. Iodine salts such as pyridinium salts, imidazolium salts, and triazolium salts described in No. 11, p. 923 (1997).

It is preferable that the electrolyte composition used in the photoelectric conversion element of the present invention contains a heterocyclic quaternary salt compound together with iodine. The content of iodine is preferably 0.1% by mass to 20% by mass, and more preferably 0.5% by mass to 5% by mass based on the entire electrolyte composition.

-Co-adsorbent -

In the photoelectric conversion element of the present invention, it is preferred to use a co-adsorbent together with the metal complex dye of the present invention or a pigment which is used in combination as needed. Such a co-adsorbent is preferably a co-adsorbent having a carboxyl group or a salt thereof, and the co-adsorbent may be a fatty acid or a compound having a steroid skeleton. The fatty acid may be a saturated fatty acid or an unsaturated fatty acid, and examples thereof include butyric acid, caproic acid, caprylic acid, capric acid, and hexadecanoic acid. Dodecanoic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linoleic acid, and the like.

Examples of the compound having a steroid skeleton include cholic acid, glycocholic acid, chenodeoxycholic acid, porcine cholic acid, deoxycholic acid, lithocholic acid, and ursodeoxycholic acid. Preferred are cholic acid, deoxycholic acid, chenodeoxycholic acid, and more preferably chenodeoxycholic acid.

A preferred co-adsorbent is a compound represented by the following formula (CA).

In the formula (CA), R ^a represents a substituent having an acidic group. R ^g represents a substituent. Na represents an integer of 0 or more.

The acidic group is synonymous with the acidic group shown above. Further, examples of the substituent in R ^a and R ^g include a substituent T to be described later.

n is preferably 2 to 4.

Specific examples of such a compound include the compounds exemplified above as the compound having a steroid skeleton.

The co-adsorbent of the present invention has an effect of suppressing the ineffective association of the dye and preventing the reverse electron transfer from the surface of the semiconductor fine particles to the redox system in the electrolyte by being adsorbed on the semiconductor fine particles. The amount of the co-adsorbent used is not particularly limited, and from the viewpoint of effectively exhibiting the above effects, it is preferred to The metal complex pigment 1 mole is preferably 1 mole to 200 moles, more preferably 10 moles to 150 moles, and particularly preferably 20 moles to 50 moles.

In addition, in this specification, regarding a compound (including a complex, a pigment) It is used in the following sense: in addition to the compound itself, it also includes a salt, a complex thereof, and an ion thereof. Further, in the present specification, the substituent which is not substituted or unsubstituted (the same applies to the linking group and the ligand) is that the group may have any substituent. Compounds that are not labeled as substituted or unsubstituted are also synonymous with this. Preferred substituents include the following substituents T.

The substituent T can be exemplified by the following substituents.

The alkyl group (preferably an alkyl group having 1 to 20 carbon atoms) is exemplified. Such as methyl, ethyl, isopropyl, tert-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc., alkenyl (preferably an alkenyl group having 2 to 20 carbon atoms, such as a vinyl group, an allyl group or an oleyl group), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms, such as acetylene). a base, a butadiynyl group, a phenylethynyl group, etc., a cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a 4-methyl group) Cyclohexyl, etc., aryl (preferably an aryl group having 6 to 26 carbon atoms, such as phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methyl a phenyl group or the like, a heterocyclic group (preferably a heterocyclic group having 2 to 20 carbon atoms, more preferably a 5-membered ring or a 6-membered ring having at least one oxygen atom, a sulfur atom, a nitrogen atom) Heterocyclic group, such as 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl, etc., alkoxy (preferably carbon atom) Alkoxy groups of 1 to 20, such as methoxy, ethoxy, isopropoxy, benzyloxy, etc., aryloxy a group (preferably an aryloxy group having 6 to 26 carbon atoms, such as a phenoxy group, a 1-naphthyloxy group, a 3-methylphenoxy group, a 4-methoxyphenoxy group, etc.), an alkoxy group a carbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as an ethoxycarbonyl group, a 2-ethylhexyloxycarbonyl group, etc.) or an amine group (preferably having a carbon number of 0~) Amino group of 20, comprising an alkylamino group, an arylamine group, such as an amine group, N,N-dimethylamino group, N,N-diethylamino group, N-ethylamino group, anilino group, etc. ), amidoxime (preferably a sulfonylamino group having 0 to 20 carbon atoms, such as N,N-dimethylaminesulfonyl, N-phenylaminesulfonyl, etc.), anthracene oxygen a base (preferably an oxirane having 1 to 20 carbon atoms, such as an ethoxylated methoxy group, a benzhydryloxy group, etc.), an amine formazan group (preferably an amine having 1 to 20 carbon atoms) a mercapto group, for example, N,N-dimethylaminecarbamyl, N-phenylaminecarbamyl, etc.), a mercaptoamine group (preferably a mercaptoamine group having 1 to 20 carbon atoms, For example, an ethyl sulfhydryl group, a benzhydrylamino group, etc., a sulfonylamino group (preferably an amine sulfonyl group having a carbon number of 0 to 20, such as methotrexate, benzenesulfonamide, N -methylmethanesulfonate Amine, N-ethylbenzenesulfonamide, etc.), alkylthio (preferably an alkylthio group having 1 to 20 carbon atoms, such as methylthio, ethylthio, isopropylthio, benzylthio) And arylthio (preferably an arylthio group having 6 to 26 carbon atoms, such as phenylthio, 1-naphthylthio, 3-methylphenylthio, 4-methoxyphenylthio) Or an alkylsulfonyl or arylsulfonyl group (preferably an alkylsulfonyl or arylsulfonyl group having 1 to 20 carbon atoms, such as methylsulfonyl or ethylsulfonyl) a base, a benzenesulfonyl group, a hydroxyl group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like), more preferably an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. An alkoxy group, an aryloxy group, an alkoxycarbonyl group, an amine group, a mercaptoamine group, a cyano group or a halogen atom, particularly preferably an alkyl group, an alkenyl group, a heterocyclic group, an alkoxy group or an alkoxycarbonyl group. Amine, Mercaptoamine or cyano group.

When a compound, a substituent or the like contains an alkyl group, an alkenyl group or the like, the groups may be The linear form may also be branched, and may be substituted or unsubstituted. Further, when an aryl group, a heterocyclic group or the like is contained, the groups may be monocyclic or condensed, and may be substituted or unsubstituted.

Regarding the photoelectric conversion element and the dye-sensitized solar cell of the present invention The materials to be used and the method of producing the members can be made by using such materials and the usual manufacturing methods of the members. For example, reference is made to the specification of U.S. Patent No. 4,927,721, the specification of U.S. Patent No. 4,684,537, and U.S. Patent No. 5,084,365. The specification, the specification of the U.S. Patent No. 5,350,644, the specification of the U.S. Patent No. 5,463,057, the specification of the U.S. Patent No. 5,525,440, the Japanese Patent Laid-Open No. Hei 7-249790, the Japanese Patent Publication No. 2004-220974, and the Japanese Patent Laid-Open No. 2008- Bulletin No. 135197. Hereinafter, the main components will be briefly described.

The conductive support is such that the support itself is electrically conductive Or a glass or plastic support having a conductive film layer on the surface. In addition to the glass and the plastic, a ceramic (Japanese Patent Laid-Open Publication No. 2005-135902) and a conductive resin (Japanese Patent Laid-Open Publication No. 2001-160425) can be used. The surface of the support may be subjected to a light management function, and for example, an antireflection film in which an alternating film having a high refractive film and a low refractive index oxide film is laminated as described in Japanese Laid-Open Patent Publication No. 2003-123859, The light guide function described in Japanese Laid-Open Patent Publication No. 2002-260746.

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

The conductive support is preferably substantially transparent. The term "substantially transparent" means that the transmittance of light is 10% or more, preferably 50% or more, and particularly preferably 80% or more. The transparent conductive support is preferably a support in which a conductive metal oxide (preferably, semiconductor fine particles) is coated on glass or plastic. The amount of the conductive metal oxide applied at this time is preferably from 0.1 g to 100 g per 1 m ^{2 of the} glass or plastic support. In the case of using a transparent conductive support, it is preferred that light is incident from the side of the support.

The semiconductor microparticles are preferably metal chalcogenides (chalcogenide) (eg oxides, sulfides, selenides, etc.) or perovskite microparticles. The metal chalcogenide is preferably an oxide of titanium, tin, zinc, tungsten, zirconium, hafnium, yttrium, indium, lanthanum, cerium, lanthanum, vanadium, niobium or tantalum, cadmium sulfide, cadmium selenide or the like. The perovskite is preferably exemplified by barium titanate, calcium titanate or the like. Particularly preferred among these are titanium oxide, zinc oxide, tin oxide, and tungsten oxide.

The crystal structure of titanium dioxide may be anatase type, brookite type, or gold. The red stone type is preferably an anatase type or a brookite type. A titanium dioxide nanotube, a nanowire, or a nanorod may be mixed in the titanium dioxide fine particles or used as a semiconductor electrode.

Moreover, in the present invention, CdSe quantum dot processing can also be implemented. Semiconductor microparticles are used as photoelectrodes.

The particle size of the semiconductor fine particles is averaged (using the projected area For the diameter of the circle, it is preferable that the primary particles are 0.001 μm to 1 μm. The average particle size of the dispersion is from 0.01 μm to 100 μm. The method of applying the semiconductor fine particles to the conductive support may be a dry method or another method other than the wet method.

It is preferable to form a short-circuit preventing layer between the transparent conductive film and the photoreceptor layer (also referred to as a semiconductor layer or an oxide semiconductor layer) in order to prevent a reverse current generated by direct contact between the electrolytic solution and the electrode. In order to prevent contact between the photoelectrode and the opposite electrode, it is preferred to use a spacer or a spacer. The semiconductor fine particles are preferably pigments having a large surface area to adsorb a large amount. For example, in a state where the semiconductor fine particles are coated on the support, the surface area thereof is preferably 10 times or more, more preferably 100 times or more, with respect to the projected area. The upper limit is not particularly limited and is usually about 5,000 times. In general, the larger the thickness of the semiconductor fine particle layer, the more the amount of pigment that can be carried per unit area increases, so the light absorption efficiency becomes high, but since the diffusion distance of the generated electrons increases, the charge recombination is generated. The loss also becomes larger. The preferred thickness of the photoreceptor layer containing semiconductor fine particles varies depending on the use of the device, and is typically 0.1 μm to 100 μm. When used as a dye-sensitized solar cell, it is preferably 1 μm to 50 μm, more preferably 3 μm to 30 μm. After the semiconductor fine particles are applied to the support and the particles are in close contact with each other, they can be calcined at a temperature of 100 ° C to 800 ° C for 10 minutes to 10 hours. In the case where glass is used as the support, the film formation temperature is preferably from 400 ° C to 600 ° C.

Further, the coating amount of the semiconductor fine particles per 1 m ^{2 of the} support is preferably 0.5 g to 500 g, more preferably 5 g to 100 g. The amount of the pigment used is preferably from 0.01 millimolar to 100 millimoles per 1 m ^{2 of the} support, more preferably from 0.1 millimolar to 50 millimolar, and particularly preferably 0.1 millimoles ~ 10 millimoles. In this case, it is preferred to use the metal complex dye of the present invention in an amount of 5 mol% or more. Further, the amount of adsorption of the dye with respect to the semiconductor fine particles is preferably 0.001 mmol to 1 mmol, more preferably 0.1 mmol to 0.5 mmol, relative to 1 g of the semiconductor fine particles. By setting the amount of the pigment, the sensitizing effect in the semiconductor fine particles is sufficiently obtained. On the other hand, when the amount of the dye is small, the sensitizing effect is insufficient, and when the amount of the dye is too large, the dye that has not adhered to the semiconductor fine particles floats, which causes the sensitizing effect to be lowered.

In the case where the dye is a salt, the relative ions of the metal complex dye of the present invention are not particularly limited, and examples thereof include an alkali metal ion or a quaternary ammonium ion.

After adsorbing the pigment, the surface of the semiconductor fine particles can also be treated with an amine. Preferred examples of the amines include pyridines (for example, 4-tert-butylpyridine and polyvinylpyridine). These compounds can be used as they are in the case of a liquid or dissolved in an organic solvent. The charge transporting layer is a layer having a function of replenishing electrons to the oxidant of the dye, and is provided between the light receiving electrode and the opposite electrode. Representative examples include a so-called gel electrolyte in which a redox is dissolved in an organic solvent, and a liquid obtained by dissolving a redox pair in an organic solvent is impregnated into a polymer matrix, and contains oxidation. Restore the molten salt and so on.

Instead of the above liquid electrolyte and quasi-solid electrolyte, a solid charge transport system such as a p-type semiconductor or a hole transport material may be used. An organic hole transport material can also be used as the solid charge transport layer.

The redox pair becomes a carrier of electrons, so a certain concentration is required. The preferred concentration is 0.01 mol/L or more, more preferably 0.1 mol/L. Particularly preferred is 0.3 mol/L or more. The upper limit in this case is not particularly limited and is usually about 5 m/L.

The counter electrode is an electrode that operates as a positive electrode of a dye-sensitized solar cell (photoelectrochemical cell). The counter electrode is generally synonymous with the above-described conductive support, but the support is not necessarily required in the configuration in which the strength is sufficiently maintained. The structure of the opposite electrode is preferably a structure having a high current collecting effect. In order to allow light to reach the photosensitive layer, at least one of the conductive support and the counter electrode must be substantially transparent. In the dye-sensitized solar cell of the present invention, it is preferred that the conductive support is transparent and that sunlight is incident from the side of the support. In this case, it is more preferable that the counter electrode has a property of reflecting light. The counter electrode of the dye-sensitized solar cell is preferably a glass or a plastic which is vapor-deposited with a metal or a conductive oxide, and particularly preferably a glass plated with platinum. In the dye-sensitized solar cell, in order to prevent transpiration of the constituent, it is preferred to seal the side surface of the battery by a polymer or an adhesive. The characteristics of the dye-sensitized solar cell of the present invention obtained as described above are preferably 100 mW/cm ² at AM 1.5 G, and the open circuit voltage (Voc) is 0.01 V to 1.5 V, and the short-circuit current density (Jsc) The ratio is 0.001 mA/cm ² to 20 mA/cm ² , the filling factor (FF curve factor or shape factor) is 0.1 to 0.9, and the photoelectric conversion efficiency (η) is 0.001% to 25%.

[Pigment adsorption liquid composition]

In the present invention, it is preferred to use a dye adsorption liquid composition containing the metal complex dye of the present invention to produce a dye adsorption electrode.

More specifically, it is preferred to apply a dye adsorption liquid composition containing the metal complex dye of the present invention to a semiconductor-containing conductive support. The photoreceptor layer is cured to form a dye-adsorbing electrode.

The pigment adsorption liquid composition is obtained by dissolving the metal complex dye of the present invention in a solvent, and may also contain a co-adsorbent or other components as needed.

The solvent described in Japanese Laid-Open Patent Publication No. 2001-291534 is not particularly limited. In the present invention, an organic solvent is preferable, and an alcohol, a guanamine, a nitrile, an alcohol, a hydrocarbon, and a mixed solvent of two or more of them are more preferable. The mixed solvent is preferably a mixed solvent of an alcohol and a solvent selected from the group consisting of guanamines, nitriles, alcohols, and hydrocarbons. Further more preferably, it is a mixed solvent of an alcohol and a guanamine, an alcohol and a hydrocarbon, and a mixed solvent of an alcohol and a guanamine.

The pigment adsorbent composition preferably contains a co-adsorbent, and the co-adsorbent is preferably the above-mentioned co-adsorbent, and among them, a compound represented by the formula (CA) is preferred.

Here, the dye adsorption liquid composition of the present invention can directly use the dye adsorption liquid composition (solution) for forming a photoelectric conversion element or a dye-sensitized solar cell, preferably a metal complex dye or co-adsorption. The concentration of the agent is adjusted to the composition of the dye adsorption liquid. In the present invention, it is preferred to contain 0.001% by mass to 0.1% by mass of the metal complex dye of the present invention.

It is particularly preferable that the pigment adsorption liquid composition adjusts the moisture content. Therefore, in the present invention, it is important to adjust the water content (content ratio) to 0% by mass to 0.1% by mass.

Similarly, in order to effectively achieve the effects of the present invention, the adjustment of the moisture content of the electrolyte in the photoelectric conversion element or the dye-sensitized solar cell is also important, It is preferred to adjust the moisture content (content ratio) of the electrolytic solution to 0% to 0.1%. The adjustment of the electrolytic solution is particularly preferably carried out by a pigment adsorption liquid composition.

The present invention is applicable to Japanese Patent No. 4260494, Japanese Patent JP-A-2004-146425, JP-A-2000-340269, JP-A-2002-289274, JP-A-2004-152613, and JP-A No. 9-27352 Photoelectric conversion elements, dye-sensitized solar cells. Moreover, it is also applicable to Japanese Patent Laid-Open No. 2004-152613, Japanese Patent Laid-Open No. 2000-90989, Japanese Patent Laid-Open No. 2003-217688, Japanese Patent Laid-Open No. 2002-367686, and Japanese Patent Laid-Open Japanese Patent Laid-Open No. 2001-43907, Japanese Patent Laid-Open No. Hei. No. 2000-340269, Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. 2000-323190, Japanese Patent Laid-Open No. 2000-228234, Japanese Patent Laid-Open No. 2001-266963, Japanese Patent Laid-Open No. 2001-185244, Japanese Patent Laid-Open No. 2001-525108, Japanese Patent Laid-Open Japanese Patent Publication No. 2001-203377, Japanese Patent Laid-Open Publication No. 2000-100483, Japanese Patent Laid-Open No. 2001-210390, Japanese Patent Laid-Open Publication No. JP-A No. 2002-280587, Japanese Patent Laid-Open No. 2001-273937, and Japanese Patent Laid-Open A photoelectric conversion element and a dye-sensitized solar cell described in Japanese Laid-Open Patent Publication No. 2001-320068, and the like.

[Examples]

Hereinafter, the present invention will be described in more detail based on examples, but the present invention It is not limited to this and is explained.

(Example 1)

<Synthesis (Preparation) of Metal Complex Pigment>

Hereinafter, a method for synthesizing the metal complex dye of the present invention (preparation method) The method is described in detail, but the starting materials, the pigment intermediates, and the synthesis (preparation) route are not limited thereby.

[Example of synthesis of pigment 1]

(1) Synthesis of ligands

Under a nitrogen atmosphere, 5.8 g of triethylamine and 12.6 g of chlorodiphenylsilane were added to 60 mL of tetrahydrofuran, and the mixture was stirred at room temperature. 60 mL of a solution of 4.8 g of 2-hydroxypyridine in tetrahydrofuran was slowly added dropwise thereto. After completion of the dropwise addition, stirring was carried out for 3 hours at room temperature. Thereafter, the white solid was separated by filtration, and the obtained solution was concentrated under reduced pressure, whereby 1 g of the desired ligand was obtained. The purity of the resulting product is sufficiently high that it is used directly in a complex forming reaction without further purification.

(2) Mismatch reaction

In the first embodiment of Japanese Patent Laid-Open Publication No. 2009-51999, The 2-phenylpyridine ligand was replaced with the above pyridyloxyalkylalkyl ligand, and the exemplified dye 1 was synthesized by the methods according to Examples 1 to 3 of the publication.

[Illustration of the synthesis of Pigment 2]

(1) Synthesis of ligands

Add triethylamine 5.8 g and 2- in 60 mL of hexane under nitrogen atmosphere 4.8 g of hydroxypyridine was stirred at 0 °C. 7.3 g of 2-chloro-1,3,2-dioxaphospholane was slowly added dropwise thereto. After completion of the dropwise addition, the mixture was warmed to room temperature, and stirred at room temperature for 2 hours. Thereafter, the white solid was separated by filtration, and the resulting solution was concentrated under reduced pressure, whereby 9.6 g of the desired ligand was obtained. The purity of the resulting product was sufficiently high that it was used directly in the mismatch reaction without further purification.

(2) Mismatch reaction

Using the ligand synthesized in the above (1), by exemplifying the dye 1 The exemplified dye 2 was synthesized by the method of synthesis.

[Example of synthesis of pigment 3]

(1) Synthesis of ligands

By J. Org. Chem., 53, 532 (1988) Synthesized by the synthesis method described.

(2) Mismatch reaction

Using the ligand synthesized in the above (1), by exemplifying the dye 1 The exemplified dye 3 was synthesized by the method of synthesis.

[Example Synthesis of Pigment 4]

(1) Synthesis of ligands

Add 2-methylpyridine to 100 mL of tetrahydrofuran under nitrogen 4.7 g, cooled to -78 °C. 31.3 mL of n-butyllithium (1.6 M hexane solution) was gradually added dropwise thereto, and stirred at -78 ° C for 30 minutes. Thereafter, 10.9 g of diphenylchloromethane was gradually added dropwise, and the mixture was heated to room temperature, and stirred at room temperature for 2 hours. The reaction solution was concentrated under reduced pressure, and 100 mL of toluene was added thereto, and stirred at room temperature for 1 hour. The white solid was separated by filtration, and the obtained solution was concentrated under reduced pressure, whereby 4.6 g of the desired ligand was obtained. The purity of the resulting product was sufficiently high that it was used directly in the mismatch reaction without further purification.

(2) Mismatch reaction

Using the ligand synthesized in the above (1), by exemplifying the dye 1 The exemplified dye 4 was synthesized by a method based on the synthesis method.

[Example of synthesis of pigment 5]

(1) Synthesis of ligands

Add 2-methylpyridine to 100 mL of tetrahydrofuran under nitrogen 4.7 g, cooled to -78 °C. 31.3 mL of n-butyllithium (1.6 M hexane solution) was gradually added dropwise thereto, and stirred at -78 ° C for 30 minutes. Thereafter, 60 mL of a 1,03 g tetrahydrofuran solution of 1,2-phenylene phosphorochloridite was gradually added dropwise, and the mixture was warmed to room temperature and stirred at room temperature for 2 hours. The reaction solution was concentrated under reduced pressure, and 100 mL of toluene was added thereto, and stirred at room temperature for 1 hour. The white solid was separated by filtration, and the obtained solution was concentrated under reduced pressure, whereby 7.5 g of the desired ligand was obtained. The purity of the resulting product was sufficiently high that it was used directly in the mismatch reaction without further purification.

(2) Mismatch reaction

Using the ligand synthesized in the above (1), by exemplifying the dye 1 The exemplified dye 5 was synthesized by a method based on the synthesis method.

[Example of synthesis of pigment 6]

(1) Synthesis of ligands

Recorded in Chemical Communications (Chem. Commun.), 5633 (2008) The synthesis method is carried out for synthesis.

(2) Mismatch reaction

Using the ligand synthesized in the above (1), by exemplifying the dye 1 The exemplified dye 6 was synthesized by a method based on the synthesis method.

[Example of synthesis of pigment 7]

Synthesis of Triphenyl Phosphite Complex

(Me ₃ -tctpy)RuCl ₃ 615 mg (Me ₃ -tctpy=4,4',4"-tris(methoxycarbonyl)-2,2' was added to 150 mL of dichloromethane under nitrogen. 6', 2"-terpyridine, 365 mg of triphenyl phosphite, 15 mL of triethylamine, and heating under reflux for 1.5 hours. The reaction solution was concentrated under reduced pressure, and water (300 mL) was added, and the insoluble black solid was recovered by filtration, and washed with 50 mL of water and 50 mL of diethyl ether. The black solid was recrystallized (dichloromethane/hexane) to obtain a dichloro complex 802 mg as a black crystal in which a phosphite was coordinated.

(2) Ring metallization reaction

The dichloro complex 802 mg obtained in the above (1) under a nitrogen atmosphere It was dissolved in 100 mL of tetrahydrofuran, and 232 mg of silver trifluoromethanesulfonate was added thereto, and stirred at room temperature for 30 minutes. The white solid formed was removed by filtration of diatomaceous earth under nitrogen, and 2.0 mL of piperidine was added to the obtained solution, followed by stirring for 30 minutes. The reaction solution was concentrated under reduced pressure, and the obtained black solid was recrystallized (dichloromethane/hexane) to obtain 422 mg of a cyclometalated product.

(3) Hydrolysis of trimethyl ester

The above (2) is produced by the same method as the exemplified dye 1 The trimethyl ester was hydrolyzed to obtain an exemplary pigment 7.

[Example of synthesis of pigment 8]

(1) Synthesis of ligands

Add 8-bromoquinoline 10.4 to 150 mL of tetrahydrofuran under nitrogen atmosphere. g, cooled to -78 °C. 31.3 mL of n-butyllithium (1.6 M hexane solution) was gradually added dropwise thereto, and stirred at -78 ° C for 30 minutes. Thereafter, 10.9 g of diphenylchloromethane was gradually added dropwise, and the mixture was heated to room temperature, and stirred at room temperature for 2 hours. 100 mL of water and 150 mL of ethyl acetate were added to the reaction solution to carry out liquid separation, and the crude product obtained by concentrating the organic layer was purified by silica gel column chromatography to obtain 12.7 g of the desired ligand.

(2) Mismatch reaction

Using the ligand synthesized in the above (1), by exemplifying the dye 1 The exemplified dye 8 was synthesized by a method based on the synthesis method.

[Example of synthesis of pigment 9]

(1) Synthesis of ligands

Add 8-bromoquinoline 10.4 g to 150 mL of hexane under nitrogen Cool to 0 ° C. 31.3 mL of n-butyllithium (1.6 M hexane solution) was gradually added dropwise thereto, and stirred at 0 ° C for 1 hour. Slowly add 60 mL of a solution of 1,2-phenylphosphoric acid phosphine 10.03 g in tetrahydrofuran, and then warm to room temperature and let it at room temperature. Stir for 2 hours. The white solid was separated by filtration, and the obtained solution was concentrated under reduced pressure, whereby 13.2 g of the desired ligand was obtained. The purity of the resulting product was sufficiently high that it was used directly in the mismatch reaction without further purification.

(2) Mismatch reaction

Using the ligand synthesized in the above (1), by exemplifying the dye 1 The exemplified dye 9 was synthesized by a method based on the synthesis method.

[Example of Synthesis of Pigment 10]

(1) Synthesis of ligands

Under a nitrogen atmosphere, 8.2 g of 8-chloroquinoline and 6.6 g of sodium thiophenoxide were added to 100 mL of ethanol, and the mixture was heated under reflux for 6 hours. Thereafter, the mixture was cooled to room temperature and concentrated under reduced pressure. 100 mL of water and 150 mL of ethyl acetate were added to carry out liquid separation, and the crude product obtained by concentrating the organic layer was purified by silica gel column chromatography to obtain 12.0 g of the desired ligand.

(2) Mismatch reaction

The exemplified dye 10 was synthesized by the method of synthesizing the dye 1 as an example using the ligand synthesized in the above (1).

[Example Synthesis of Pigment 11]

(1) 7-bromofluorene t-Boc protection

Under a nitrogen atmosphere, 9.8 g of 7-bromoindole, 12.0 g of di-tert-butyl dicarbonate, and 9.2 g of 4-dimethylaminopyridine were added to 100 mL of acetonitrile, and the mixture was stirred at room temperature for 15 minutes. The crude product obtained by concentrating the reaction solution under reduced pressure was purified by silica gel column chromatography to obtain 14.8 g of the object.

(2) Synthesis of ligands

Under a nitrogen atmosphere, 14.8 g of N-t-Boc-7-bromoindole was added to 150 mL of tetrahydrofuran and cooled to -78 °C. 31.3 mL of a third butyllithium (1.6 M pentane solution) was gradually added dropwise thereto, and stirred at -78 ° C for 30 minutes. Thereafter, 10.9 g of diphenylchloromethane was gradually added dropwise, and the mixture was heated to room temperature, and stirred at room temperature for 2 hours. 100 mL of water and 150 mL of ethyl acetate were added to the reaction solution to carry out liquid separation, and the organic layer was concentrated to dissolve the crude product in dichloromethane (500 mL). Into, 10 mL of trifluoroacetic acid was added and the mixture was stirred at room temperature for 1 hour. The crude product obtained by concentrating under reduced pressure was purified by silica gel column chromatography to obtain 9.7 g of the desired ligand.

(3) Mismatch reaction

The trimethyl phosphite complex of the precursor of the complex can be synthesized by a method of synthesizing the triphenyl phosphite complex described in the synthesis (1) of the dye 7. Under a nitrogen atmosphere, 633 mg of a trimethyl phosphite complex, 269 mg of a ligand, and 5 mL of piperidine were added to 100 mL of ethanol, followed by heating under reflux for 5 hours. The reaction solution was concentrated under reduced pressure, and the obtained black solid was recrystallized (dichloromethane/hexane), whereby 762 mg of the target compound was obtained.

(4) Hydrolysis of trimethyl ester

The trimethyl ester produced in the above (3) was hydrolyzed by the same method as the exemplified dye 1, to obtain an exemplary dye 11.

[Example of synthesis of pigment 12]

(1) Synthesis of ligands

Under a nitrogen atmosphere, 14.8 g of N-t-Boc-7-bromoindole was added to 150 mL of hexane and cooled to 0 °C. 31.3 L of a third butyllithium (1.6 M pentane solution) was gradually added dropwise thereto, and stirred at 0 ° C for 30 minutes. 7.3 g of 2-chloro-1,3,2-dioxolane was slowly added dropwise, and the mixture was warmed to room temperature, and stirred at room temperature for 2 hours. The white solid was separated by filtration and the obtained solution was concentrated under reduced pressure, whereby 15.1 g of the desired ligand was obtained. The purity of the resulting product was sufficiently high that it was used directly in the mismatch reaction without further purification.

(2) Mismatch reaction

Using the ligand synthesized in the above (1), the exemplary dye 12 was synthesized by a method in which the synthesis method of the dye 1 was exemplified. t-Boc protection is deprotected based on the process of forming a mismatch.

[Example Synthesis of Pigment 13]

(1) Synthesis of ligands

Under nitrogen atmosphere, 14.8 g of Nt-Boc-7-bromofluorene, 5.5 g of thiophenol, 1.2 g of tetrakis(triphenylphosphine)palladium and 5.3 g of sodium butoxide were added to 120 mL of ethanol. Heating under reflux for a few hours. 100 mL of water and 150 mL of ethyl acetate were added to the reaction solution to carry out liquid separation, and the organic layer was concentrated to dissolve the crude product in 500 mL of dichloromethane, and 10 mL of trifluoroacetic acid was added at room temperature. Stir for 1 hour. The crude product obtained by concentrating under reduced pressure was purified by silica gel column chromatography to obtain 12.7 g of the desired ligand.

(2) Mismatch reaction

The exemplified dye 13 was synthesized by the method of synthesizing the dye 1 as an example using the ligand synthesized in the above (1).

[Example Synthesis of Pigment 14]

(1) Synthesis of ligands

Under a nitrogen atmosphere, 10.7 g of 7-bromobenzothiophene was added to 150 mL of tetrahydrofuran and cooled to -78 °C. 31.3 mL of n-butyllithium (1.6 M hexane solution) was gradually added dropwise thereto, and stirred at -78 ° C for 30 minutes. Thereafter, 10.9 g of diphenylchloromethane was gradually added dropwise, and the mixture was heated to room temperature, and stirred at room temperature for 2 hours. 100 mL of water and 150 mL of ethyl acetate were added to the reaction solution to carry out liquid separation, and the crude product obtained by concentrating the organic layer was purified by silica gel column chromatography to obtain 13.9 g of the desired ligand.

(2) Mismatch reaction

Using the ligand synthesized in the above (1), the exemplary dye 14 was synthesized by a method in which the synthesis method of the dye 1 was exemplified.

[Example of synthesis of pigment 15]

(1) Synthesis of ligands

Add 7-bromobenzothiophene 10.7 to 150 mL of hexane under nitrogen atmosphere. G was cooled to 0 °C. 31.3 mL of n-butyllithium (1.6 M hexane solution) was gradually added dropwise thereto, and stirred at 0 ° C for 30 minutes. 40 mL of a solution of 1,2-phenylphenylphosphoric acid phosphine 8.7 g in tetrahydrofuran was gradually added dropwise, and the mixture was warmed to room temperature, and stirred at room temperature for 2 hours. The white solid was separated by filtration and the obtained solution was concentrated under reduced pressure, whereby 17.1 g of the desired ligand was obtained. The purity of the resulting product was sufficiently high that it was used directly in the mismatch reaction without further purification.

(2) Mismatch reaction

Using the ligand synthesized in the above (1), the exemplary dye 15 was synthesized by a method in which the synthesis method of the dye 1 was exemplified.

[Example Synthesis of Pigment 16]

The commercially available 1,2-bis(dimethylalkylalkyl)benzene was used as a ligand, and the exemplary dye 16 was synthesized by the method of synthesizing the dye 11 as an example.

[Example of synthesis of pigment 17]

(1) Synthesis of ligands

Under a nitrogen atmosphere, 14.0 g of 1,2-bis(dichlorophosphino)benzene and 11.0 g of catechol were added to 500 mL of toluene, followed by heating under reflux for 12 hours. After the reaction The solution was concentrated under reduced pressure, and the obtained product was sufficiently high in purity of 17.7 g, and thus was used in the direct reaction without further purification.

(2) Mismatch reaction

The exemplified dye 17 was synthesized by the method of synthesizing the dye 1 as an example using the ligand synthesized in the above (1).

[Example of synthesis of pigment 18]

The exemplified dye 18 was synthesized by a method based on the synthesis method of the exemplified dye 11, using commercially available 1,2-benzenedithiol as a ligand.

[Example Synthesis of Pigment 19]

(1) Synthesis of ligands

P,P'-(9,9-dimethyl-9H-dibenzopyran-4,5-diyl) bis[N,N,N',N was added to 500 mL of toluene under nitrogen atmosphere. '-Tetraethyl-phosphonium diamine] 27.3 g, phenol 18.8 g, and heated under reflux for 12 hours. The solution after the reaction was concentrated under reduced pressure, and the obtained product, 32.1 g, was sufficiently pure, and thus was used in the mixture reaction without further purification.

(2) Mismatch reaction

Under a nitrogen atmosphere, (1) the ligand 643 mg, (Me ₃ -tctpy) RuCl ₃ 615 mg, and triethylamine 5 mL were added to a mixed solvent of 500 mL of ethanol and 100 mL of water for 6 hours. It is heated to reflux. The reaction solution was concentrated under reduced pressure, and the obtained crude product was purified on a Sephadex LH-20 column to obtain 1182 mg of the target compound as a black crystal.

(3) Hydrolysis of trimethyl ester

The trimethyl ester produced in the above (2) was hydrolyzed by the same method as the exemplified dye 1, to obtain an exemplary dye 19.

[Example Synthesis of Pigment 20]

(1) Synthesis of ligands

The raw materials of the above process can be obtained by: 2-bromoiodobenzene and 2-bromoaniline as a raw material, protected by t-Boc of bis(4-bromophenyl)amine as described in the International Journal of Applied Chemistry (Angew. Chem., Int. Ed.), 49, 8205 (2010) The method is a standard method, and the bis(2-bromophenyl)amine synthesized by the synthesis method described in J. Am. Chem. Soc., 126, 8755 (2004) is carried out. t-Boc protection.

Under a nitrogen atmosphere, 21.4 g of N-t-Boc-bis(2-bromophenyl)amine was added to 150 mL of hexane and cooled to -78 °C. 62.5 mL of a third butyllithium (1.6 M pentane solution) was gradually added dropwise thereto, and stirred at -78 ° C for 30 minutes. 21.1 g of bis(diethylamino)phosphoric acid phosphide was gradually added dropwise, and the mixture was warmed to room temperature, and stirred at room temperature for 2 hours. Thereafter, the reaction liquid was concentrated under reduced pressure, and toluene (500 mL) was added. After adding 18.8 g of phenol, heating was carried out for 12 hours. The solution after the reaction was concentrated under reduced pressure, and the obtained product was purified to a purity of 35.0 g, and was used in the mixture reaction without further purification.

(2) Mismatch reaction

Using the ligand synthesized in the above (1), the exemplary dye 20 is synthesized by a method in which the synthesis method of the dye 19 is exemplified.

[Example Synthesis of Pigment 21]

(1) Synthesis of ligands

Under a nitrogen atmosphere, 21.4 g of N-t-Boc-bis(2-bromophenyl)amine was added to 150 mL of tetrahydrofuran and cooled to -78 °C. 62.5 mL of a third butyllithium (1.6 M pentane solution) was gradually added dropwise thereto, and stirred at -78 ° C for 30 minutes. 21.8 g of diphenylchloromethane was gradually added dropwise, and the mixture was warmed to room temperature, and stirred at room temperature for 2 hours. After adding 100 mL of water and 150 mL of ethyl acetate to the reaction solution, liquid separation was carried out, and the organic layer was concentrated, and the obtained crude product was dissolved in 500 mL of dichloromethane, and 10 mL of trifluoroacetic acid was added thereto at room temperature. Stir for 1 hour. The crude product obtained by concentrating under reduced pressure was purified by silica gel column chromatography to obtain 25.0 g of the desired ligand.

(2) Mismatch reaction

The exemplified dye 21 was synthesized by the method of synthesizing the exemplified dye 19 using the ligand synthesized in the above (1).

[Example of Synthesis of Pigment 22]

The exemplified dye 22 is synthesized by a method of synthesizing the exemplified dye 19 using a ligand synthesized by a known method described in Organometallics, 26, 6522 (2007).

[Example of Synthesis of Pigment 23]

(1) Synthesis of ligands

The bis(2-bromophenyl) sulfide as a raw material can be synthesized by the method described in International Chemical Engineering (Angew. Chem., Int. Ed.), 47, 1726 (2008).

Under a nitrogen atmosphere, 17.2 g of bis(2-bromophenyl) sulfide was added to 150 mL of tetrahydrofuran and cooled to 0 °C. 62.5 mL of n-butyllithium (1.6 M hexane solution) was gradually added dropwise thereto, and stirred at 0 ° C for 30 minutes. 21.8 g of diphenylchloromethane was gradually added dropwise, and the mixture was warmed to room temperature, and stirred at room temperature for 2 hours. 100 mL of water and 150 mL of ethyl acetate were added to the reaction solution to carry out liquid separation, and the crude product obtained by concentrating the organic layer was purified by silica gel column chromatography to obtain 25.1 g of the desired ligand.

(2) Mismatch reaction

Using the ligand synthesized in the above (1), the exemplary dye 23 is synthesized by a method in which the synthesis method of the dye 19 is exemplified.

[Example of synthesis of pigment 24]

(1) Synthesis of ligands

(2-Bromophenyl)phenyl sulfide as a raw material can be synthesized by a method described in International Chemical Engineering (Angew. Chem., Int. Ed.), 47, 1726 (2008).

Under a nitrogen atmosphere, 26.5 g of bis(2-bromophenyl) sulfide was added to 150 mL of tetrahydrofuran and cooled to 0 °C. 62.5 mL of n-butyllithium (1.6 M hexane solution) was gradually added dropwise thereto, and stirred at 0 ° C for 30 minutes. 5.8 g of dichloromethyl silane was gradually added dropwise, and the mixture was warmed to room temperature, and stirred at room temperature for 2 hours. 100 mL of water and 150 mL of ethyl acetate were added to the reaction solution to carry out liquid separation, and the crude product obtained by concentrating the organic layer was purified by silica gel column chromatography to obtain 25.6 g of the desired ligand.

(2) Mismatch reaction

The exemplified dye 24 was synthesized by the method of synthesizing the exemplified dye 19 using the ligand synthesized in the above (1).

[Example of synthesis of pigment 25]

(1) Synthesis of ligands

Add 1,3-dibromobenzene 132 mg and bis(3,5-bis(trifluoromethyl)phenyl)phosphine 457 mg to 5 mL of acetone and stir at 55 ° C for 1 hour under nitrogen atmosphere. . The precipitate formed was recovered by filtration while cooling to 0 ° C, and dissolved in 10 mL of water. Sodium acetate 130 mg was added and stirred at room temperature for 1 hour. To the reaction solution, 10 mL of ethyl acetate was added to carry out liquid separation, and the crude product obtained by concentrating the organic layer was purified by silica gel column chromatography to obtain 96 mg of the desired ligand.

(2) Mismatch reaction

The exemplified dye 25 was synthesized by the method of synthesizing the exemplified dye 19 using the ligand synthesized in the above (1).

[Example of synthesis of pigment 26]

The ligand synthesized by the known method described in Chem. Commun., 46, 1136 (2010) is synthesized by the method of synthesizing the dye 19 as an example. .

[Example of synthesis of pigment 27]

(composition of ligands)

N-t-Boc-2,5-dimethylpyrrole which is a raw material of the above-mentioned scheme can be described by Tetrahedron Lett., 50, 7169 (2009). Synthetic and synthetic.

N-t-Boc-2,5-dimethylpyrrole 9.8 g was added to 150 mL of hexane under nitrogen to cool to -78 °C. 62.5 mL of a third butyllithium (1.6 M pentane solution) was gradually added dropwise thereto, and stirred at -78 ° C for 30 minutes. 21.1 g of bis(diethylamino)phosphoric acid phosphide was gradually added dropwise, and the mixture was warmed to room temperature, and stirred at room temperature for 2 hours. Thereafter, the reaction liquid was concentrated under reduced pressure, and toluene (500 mL) was added. After adding 18.8 g of phenol, heating was carried out for 12 hours. The solution after the reaction was concentrated under reduced pressure, and the obtained product, 31.0 g, was sufficiently pure, and thus was used in the mixture reaction without further purification.

(2) Mismatch reaction

The exemplified dye 27 was synthesized by the method of synthesizing the exemplified dye 19 using the ligand synthesized in the above (1).

[Example Synthesis of Pigment 28]

(1) Mismatch reaction

Under a nitrogen atmosphere, RuCl ₂ (P(OPh) ₃ ) ₃ 552 g and Me ₃ -tctpy 210 mg were added to 50 mL of benzene and heated under reflux for 1 hour. The precipitate formed was recovered by filtration, and 150 mL of acetone and 75 mL of ethanol were added. To the solution was added 830 mg of triphenyl phosphite and stirred at room temperature for 3 hours. The reaction solution was concentrated under reduced pressure, and the obtained crude product was purified on a Sephadex LH-20 column to obtain 429 mg of the target compound as a black crystal.

(2) Hydrolysis of trimethyl ester

The method generated in the above (1) is produced by the same method as the exemplified dye 1 The trimethyl ester is hydrolyzed to obtain an exemplary dye 28.

[Example of synthesis of pigment 29]

(1) t-Boc protection of pyrazole

The starting compound of the above scheme can be synthesized by the following method. Commercially available 2-bromo-6-methylpyridine was used as a starting material and converted to 2-ethylindenyl-6- by the method described in Dalton Trans., 349 (1999). Methyl pyridine. It is converted to 3 by the method of synthesizing 3-trifluoromethyl-5-(2-pyridyl)pyrazole described in Chem. Commun., 2628 (2003). -Trifluoromethyl-5-(6-methyl-2-pyridyl)pyrazole.

Add 3-trifluoromethyl-5-(6-methyl-2-pyridyl)pyrazole 11.4 g, dibutyl succinate 12.0 g, 4-dimethyl dimethylacetate in 100 mL of acetonitrile under nitrogen atmosphere. The amidopyridine was 9.2 g and stirred at room temperature for 15 minutes. The crude product obtained by concentrating the reaction solution under reduced pressure was purified by silica gel column chromatography to obtain 16.1 g of the target compound.

(2) Synthesis of ligands

Under a nitrogen atmosphere, 16.1 g of N-t-Boc-3-trifluoromethyl-5-(6-methyl-2-pyridyl)pyrazole was added to 150 mL of hexane and cooled to 0 °C. 31.3 mL of a third butyllithium (1.6 M pentane solution) was gradually added dropwise thereto, and stirred at 0 ° C for 30 minutes. 7.3 g of 2-chloro-1,3,2-dioxaphospholane was slowly added dropwise, and the mixture was warmed to room temperature and allowed to stand at room temperature for 2 hours. Stir. The solution obtained by separating the white solid by filtration was concentrated under reduced pressure to obtain 17.5 g of the desired ligand. The purity of the resulting product was sufficiently high that it was used directly in the mismatch reaction without further purification.

(2) Mismatch reaction

The exemplified dye 29 was synthesized by the method of synthesizing the exemplified dye 19 using the ligand synthesized in the above (1).

[Preparation of paste]

(Paste A) A titanium dioxide slurry was prepared by adding spherical TiO ₂ particles (anatase, an average particle diameter of 25 nm, hereinafter referred to as spherical TiO ₂ particles A) to a nitric acid solution and stirring. Next, a cellulose-based binder as a thickener was added to the titanium dioxide slurry, and kneaded to prepare a paste.

(Paste 1) prepared by adding spherical TiO ₂ particles A and spherical TiO ₂ particles (anatase, average particle diameter of 200 nm, hereinafter referred to as spherical TiO ₂ particles B) to a nitric acid solution and stirring Titanium dioxide slurry. Next, a cellulose-based binder as a thickener was added to the titanium dioxide slurry, and kneading was carried out to prepare a paste (mass of TiO ₂ particles A: mass of TiO ₂ particles B = 30:70).

(Paste 2) In the paste A, rod-shaped TiO ₂ particles (anatase having a diameter of 100 nm and an aspect ratio of 5 or less, referred to as rod-shaped TiO ₂ particles C) were mixed to prepare rod-shaped TiO ₂ particles C. Quality: mass of paste A = 30:70 paste.

Made with the Japanese patents by the order shown below In the photoelectrode having the same configuration as the photoelectrode 12 shown in FIG. 5, which is described in the above-mentioned Japanese Patent Publication No. 2002-289274, the photoelectrode is used in addition to the photoelectrode of FIG. 3 of JP-A-2002-289274. A dye-sensitized solar cell 1 having a scale of 10 mm × 10 mm, which is composed of the dye-sensitized solar cell 20 in the same manner. The specific structure is shown in Fig. 2 attached. 41 is a transparent electrode, 42 is a semiconductor electrode, 43 is a transparent conductive film, 44 is a substrate, 45 is a semiconductor layer (photoreceptor layer), 46 is a light scattering layer, 40 is a photoelectrode, 20 is a dye-sensitized solar cell, and CE is The counter electrode, E is an electrolyte, and S is a spacer.

A transparent electrode in which a fluorine-doped SnO ₂ conductive film (having a film thickness of 500 nm) was formed on a glass substrate. Next, the paste 1 was screen printed on the SnO ₂ conductive film, and then dried. Thereafter, calcination was carried out in the air at 450 °C. Further, the screen printing and the firing were repeated using the paste 2, whereby a semiconductor electrode having the same structure as that of the semiconductor electrode 42 shown in FIG. 2 was formed on the SnO ₂ conductive film (the area of the light-receiving surface was 10 mm × 10 mm, layer The thickness is 10 μm, the thickness of the semiconductor layer is 6 μm, the layer thickness of the light-scattering layer is 4 μm, and the content of the rod-shaped TiO ₂ particles C contained in the light-scattering layer is 30% by mass. A photoelectrode of a complex pigment.

Next, the metal complex dye is adsorbed onto the semiconductor electrode (pigment adsorption electrode precursor) in the following manner. First, the anhydrous metal condensate dehydrated by magnesium ethoxide is used as a solvent to dissolve the metal complex dye described in Table 1 below in a manner of 3 × 10 ^-4 mol/L, and further added to The metal complex pigment 1 mole is a 20 molar molar mixture of chenodeoxycholic acid and bile acid as a co-adsorbent to prepare each pigment solution. The metal complex dye of the dye solution was 0.059% by mass, and the amount of water was measured by Karl Fischer titration. As a result, the water content was less than 0.01% by mass. Next, the semiconductor electrode was immersed in the solution, whereby the photoelectrode 40 in which the metal complex dye of about 1.5 × 10 ^-7 mol/cm ² was adsorbed to the semiconductor electrode was completed.

Next, a platinum electrode (the thickness of the Pt film was 100 nm) having the same shape and size as that of the above-described photoelectrode was prepared as a counter electrode, and an iodine-based redox solution containing iodine and lithium iodide was prepared as the electrolyte E. Further, a spacer S (trade name "Surlyn") manufactured by DuPont Co., Ltd. having a shape matching the size of the semiconductor electrode is prepared, and the photoelectrode 40 and the counter electrode CE are opposed to each other via the spacer S, and the electrolyte is filled inside. The dye-sensitized solar cell (sample No. 101 - sample No. 129, sample number c11, and sample number c12) was completed.

(experiment method)

The battery characteristic test was performed, and the photoelectric conversion efficiency was measured based on the short-circuit current density (Jsc, unit mA/cm ² ) of the dye-sensitized solar cell, the open circuit voltage (Voc, unit is v), and the fill factor (FF). %)]. The battery characteristic test can be carried out by using a solar simulator (manufactured by WACOM), WXS-85H, and irradiating 1000 W/m ² from a xenon lamp passing through an AM1.5 filter. Simulate sunlight. The photoelectric conversion efficiency η (%) was determined by measuring the current-voltage characteristics using an IV tester.

Further, the charge injection efficiency and the reduction rate can be obtained as follows.

(charge injection efficiency)

It was determined by the fluorescence quenching method. First, two kinds of photoelectrodes were produced: a photoelectrode in which a metal complex dye was adsorbed on the TiO ₂ and a photoelectrode prepared in the same manner as in the case of using ZrO ₂ instead of TiO ₂ . The fluorescence spectra of the two types of photoelectrodes were measured, and the integrated values were calculated. Since charge injection is not generated in the photoelectrode using ZrO ₂ , the fluorescence intensity from the dye is stronger than that of the photoelectrode using TiO ₂ . When the integrated value of ZrO ₂ adsorption is I ₀ and the integrated value of TiO ₂ adsorption is I, 1-I/I ₀ is obtained as the charge injection efficiency. The fluorescence spectrum can be measured using Fluorolog manufactured by Horiba, Ltd.

(reduction rate)

The nanosecond transition absorption spectrum of the dye-sensitized solar cell was measured, and the time waveform was fitted by the following formula to obtain τ and α.

Using the obtained τ and α, the oxidized pigment was obtained by the following formula. Original speed k. Here, τ represents the excitation lifetime, and α represents the expansion index in the expansion index function. Moreover, y is the difference in absorbance, A and B are constants, and t is time.

The reduction rate k is the sum of the reduction rate k ₁ from the reverse electron transfer of titanium oxide and the reduction rate k ₂ from iodine. On the other hand, a dye-sensitized solar cell containing no iodine-based redox was separately prepared, and the reduction rate was determined in the same manner. This reduction rate coincides with the reduction rate k ₁ of the reverse electron transfer from titanium oxide. Using the two values of k ₁ and k ₂ obtained by the above measurements, the reduction ratio was obtained by k ₂ /(k ₁ +k ₂ ). In the measurement of the nanosecond transition absorption spectrum, the excitation light is a SLII-10 type Yttrium-Aluminum-Garnet (YAG) laser and a SLOPO type wavelength conversion unit (wavelength of 410 nm~ manufactured by Continuum). 700 nm), Xe lamp (150 W) was used for the detection light, and the nanosecond transition absorption measurement system manufactured by UNISOKU Co., Ltd. was used for the detection system.

On the other hand, the dye-sensitized solar cell (unit A) prepared as described above was subjected to the battery property test as described above, and then subjected to a battery property test at 80 ° C for 300 hours in a dark place as a heat resistance test. The rate of decrease in photoelectric conversion efficiency was determined. Further, the reduction rate was obtained by [(initial photoelectric conversion efficiency - photoelectric conversion efficiency after dark passage of time) / initial photoelectric conversion efficiency] × 100.

Further, for the unit A produced separately under the same conditions, a continuous irradiation test was carried out as follows to determine the rate of decrease in photoelectric conversion efficiency.

After the cell was subjected to the cell characteristics test and the initial photoelectric conversion efficiency was determined, the light irradiation was continued for 300 hours. Thereafter, the battery characteristic test was again performed, and the photoelectric conversion efficiency after continuous irradiation was determined, and the rate of decrease in photoelectric conversion efficiency was determined.

Here, the reduction rate is obtained by [(initial photoelectric conversion efficiency - photoelectric conversion efficiency after continuous irradiation) / initial photoelectric conversion efficiency] × 100.

These results are summarized in Table 1 below.

Here, TBA represents a tetrabutylammonium ion, Ph represents a phenyl group, and Me represents a methyl group.

The dye-sensitized solar cells of the present invention have high short-circuit current density (Jsc) and high photoelectric conversion efficiency (η) with respect to the comparative example. The read short-circuit current density (Jsc) is improved due to an increase in charge injection efficiency and a reduction rate.

Further, the dye-sensitized solar cell of the present invention is a unit in a dark place, a rate of decrease in photoelectric conversion efficiency over time at 80 ° C, and a rate of decrease in photoelectric conversion efficiency of the unit after continuous light irradiation, compared with the comparative example. Low, showing high durability. The comparative example having only one monodentate phosphorus ligand has low durability, and the durability is remarkably improved by using a multidentate ligand or introducing two or more monodentate phosphorus ligands.

(Example 2)

The photoelectrode was subjected to CdSe quantum dot treatment by the following method, and the dye-sensitized solar cell shown in Fig. 3 was produced using an electrolytic solution using a cobalt complex.

Spraying 16 times of ethanol solution of bis(acetonitrile) titanium diisopropoxide (IV) on the surface of FTO glass (1) (manufactured by Nippon Sheet Glass Co., Ltd., surface resistance of 8 Ωsq ^-1 ), at 450 ° C Calcination for more than 30 minutes. A layer of about 6.2 μm was deposited by screen printing on the substrate with a transparent layer of about 2.1 μm at 20 nm-TiO ₂ and 60 nm-TiO ₂ (manufactured by Showa Titanium Co., Ltd.). The light scattering layer was post-treated with an aqueous solution of TiCl _{4 to form} an FTO/TiO ₂ film 2.

The FTO/TiO ₂ film 2 was immersed in a 0.03 M Cd(NO ₃ ) ₂ ethanol solution in a glove bag under an inert gas atmosphere for 30 seconds, and then in a 0.03 M selenide ethanol solution. Dip for 30 seconds. Thereafter, the mixture was washed in ethanol for 1 minute or more, and the excess precursor was removed and dried. The immersion→cleaning→drying process was repeated five times to deposit CdSe quantum dots 23 on the semiconductor fine particles 22, and surface-stabilization treatment was performed by CdTe to prepare a CdSe-treated photoelectrode.

Selenide (Se ^2- ) is added to the 0.030 M SeO ₂ ethanol solution by adding 0.068 g of NaBH ₄ (in a concentration of 0.060 M) in an Ar or N ₂ environment. Preparation was carried out.

The CdSe-treated photoelectrode was immersed in a dye solution containing a metal complex dye of the above Table 1 [0.3 mM acetonitrile / tert-butanol (1:1) solution of the metal complex dye] for 4 hours. After the metal complex dye described in Table 1 is adsorbed on the photoelectrode, the photoelectrode and the counter electrode 4 (on the FTO glass, a solution of hexachloroplatinic acid in 2-propanol (0.05 M) at 400 ° C The electrode formed by chemically depositing Pt for 20 minutes was sandwiched between 25 μm thick Surlyn (manufactured by DuPont Co., Ltd.) and sealed by thermal fusion. An electrolyte of cobalt complex (0.75 M Co(o-phen) ₃ ²⁺ , 0.075 M Co(o-phen) ₃ ³⁺ , 0.20 M LiClO will be used due to the previously opened pores on the opposite side of the electrode side. ₄ acetonitrile/ethylene carbonate (4:6/v:v) solution was injected into the gap between the electrodes, and then borrowed from a thin plate and a glass slide by BYELEL (manufactured by DuPont Co., Ltd.). The well was closed by heat to prepare a dye-sensitized solar cell (unit A'). Here, the o-phen of the above cobalt complex is 1,10-morpholine.

In the same manner, a dye-sensitized solar cell (unit B') was produced using the same iodine-based redox solution containing iodine and lithium iodide as in Example 1.

The cobalt complex added to the electrolyte can be prepared by the method described in Chemical Communications, Vol. 46, pp. 8788 to 8790 (2010).

With respect to each of the dye-sensitized solar cells produced as described above, the short-circuit current density, the open circuit voltage, the fill factor, and the photoelectric conversion efficiency [η (%)] were measured and durability (reduction rate 1) in the same manner as in the first embodiment. Evaluation of the reduction rate 2) It was confirmed that the dye-sensitized solar cell using the metal complex dye of the present invention obtained good performance and improved effects in the same manner as in Example 1.

The invention will be described based on this embodiment, but we do not limit our invention in any of the details of the description, unless otherwise specified, and should not violate the spirit of the invention shown in the scope of the accompanying patent application. The scope is broadly explained.

The present application claims priority to Japanese Patent Application No. 2012-042466, the entire disclosure of which is hereby incorporated by Instructions.

1‧‧‧Electrical support

2‧‧‧Photoreceptor layer

3‧‧‧ electrolyte layer

4‧‧‧relative electrode

5‧‧‧Photoelectrode

6‧‧‧ Circuitry

10‧‧‧ photoelectric conversion components

21‧‧‧Metal complex pigment

22‧‧‧Semiconductor particles

24‧‧‧Co-adsorbent

100‧‧‧System for the use of pigment-sensitized solar cells

M‧‧‧Action Agency

Claims (14)

A photoelectric conversion element comprising at least a photoreceptor layer containing a semiconductor and a metal complex dye represented by the following formula (1) or (2): M(L1)(L2)(L3) _mL1 (X) _mX . (Y) _mY (1) M (L1) (L3) _mL2 (X) _mX . (Y) _mY Formula (2) [wherein M represents Fe ²⁺ , Ru ²⁺ or Os ²⁺ ; L1 represents a ligand of a bidentate to tetradentate having an acidic group and a nitrogen-containing aromatic heterocyclic skeleton; L2 represents a ligand of a dident or a trident having a deuterium atom, a phosphorus atom or a sulfur atom which does not have an unsaturated bond as a coordinating atom; and L3 represents a deuterium atom, a phosphorus atom or a sulfur atom having no unsaturated bond as Monodentate ligand of a coordinating atom; mL1 represents an integer from 0 to 2; mL2 represents an integer from 2 to 4; X represents a ligand of a single or two teeth; mX represents an integer from 0 to 3; Y represents a must The relative ion in the case of electric charge; mY is an integer from 0 to 2]. The photoelectric conversion element according to claim 1, wherein the L2 is a ligand represented by any one of the following formulas (4) to (6): Wherein D1 is selected from the group consisting of -Si(R ⁷ ) ₂ , -P(R ⁷ ) ₂ , -P(R ⁷ ), -S(R ⁷ ) and -S, the ruthenium atom, the phosphorus atom and the sulfur atom Arranged on the metal; R ⁷ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; D2 is an atom coordinated to the metal, selected from the group consisting of a nitrogen atom, a carbon atom, a germanium atom, and a phosphorus Atom and sulfur atom; Za represents a group of atoms forming a ring; E represents -O-, -N(R ⁸ )-, -C(R ⁸ ) ₂ -, -C(=R ⁸ ')-, -C(= O)- or -C(=NR ⁸ )-; R ⁸ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; R ⁸ ' represents an alkylene group, an alkenylene group or a sub Cycloalkyl; here, R ⁸ or R ⁸ ' may also bond with Za to form a ring] Wherein d represents 0 or 1; Zb represents a group of atoms forming a ring; D3 is selected from the group consisting of -Si(R ⁹ ) ₂ , -P(R ⁹ ) ₂ , -P(R ⁹ ), -S(R ⁹ ) And -S, the germanium atom, the phosphorus atom and the sulfur atom are coordinated to the metal; D4 is selected from the group consisting of -O-, -N-, -N(R ⁹ )-, -Si(R ⁹ )-, -P(R ⁹ )-, -P- and -S-, the oxygen atom, nitrogen atom, germanium atom, phosphorus atom and sulfur atom are coordinated to the metal; R ⁹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aromatic group Oxy or heteroaryl; here, Zb may be bonded to each other to form a ring] Wherein D5 is selected from the group consisting of -Si(R ¹⁰ ) ₂ , -P(R ¹⁰ ) ₂ , -P(R ¹⁰ ), -S(R ¹⁰ ) and -S, the ruthenium atom, the phosphorus atom and the sulfur atom Arranged on the metal; R ¹⁰ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; D6 is an atom coordinated to a metal selected from a nitrogen atom, a carbon atom, a halogen atom, a phosphorus Atom and sulfur atom; Zc represents a group of atoms forming a ring; E represents -O-, -N(R ¹¹ )-, -C(R ¹¹ ) ₂ -, -C(=R ¹¹ ')-, -C(= O)- or -C(=NR ¹¹ )-; R ¹¹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; and R ¹¹ ' represents an alkylene group, an alkenylene group or a sub Cycloalkyl; here, R ¹¹ or R ¹¹ ' may also bond with Zc to form a ring]. The photoelectric conversion element according to claim 1, wherein the L2 is a ligand represented by any one of the formulas (7) to (12): Wherein D1 is selected from the group consisting of -Si(R ⁷ ) ₂ , -P(R ⁷ ) ₂ , -P(R ⁷ ), -S(R ⁷ ) and -S, the ruthenium atom, the phosphorus atom and the sulfur atom Arranged on the metal; R ⁷ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; D2 is an atom coordinated to the metal, selected from the group consisting of a nitrogen atom, a carbon atom, a germanium atom, and a phosphorus Atom and a sulfur atom; R ¹² each independently represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; n12 represents an integer of 0 to 4; and E represents -O-, -N(R ⁸ )- , -C(R ⁸ ) ₂ -, -C(=R ⁸ ')-, -C(=O)- or -C(=NR ⁸ )-; R ⁸ represents a hydrogen atom, an alkyl group, an alkoxy group, An aryl group, an aryloxy group or a heteroaryl group; R ⁸ ' represents an alkylene group, an alkenylene group or a cycloalkylene group; here, R ⁸ or R ⁸ ' may also bond with R ¹² to form a ring] Wherein D1 is selected from the group consisting of -Si(R ⁷ ) ₂ , -P(R ⁷ ) ₂ , -P(R ⁷ ), -S(R ⁷ ) and -S, the ruthenium atom, the phosphorus atom and the sulfur atom Arranged on the metal; R ⁷ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; D2a is an atom coordinated to the metal, selected from a nitrogen atom, a phosphorus atom and a sulfur atom; ¹³ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; n13 represents an integer of 0 to 3; and E represents -O-, -N(R ⁸ )-, -C(R ⁸ ) ₂ - , -C(=R ⁸ ')-, -C(=O)- or -C(=NR ⁸ )-; R ⁸ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group. R ⁸ ' represents an alkylene group, an alkenylene group or a cycloalkylene group; here, R ⁸ or R ⁸ ' may also bond with R ¹³ to form a ring] Wherein R ¹⁴ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; n14 represents an integer of 0 to 4; and D3 is selected from -Si(R ⁹ ) ₂ , -P(R ⁹ ) ₂ , -P(R ⁹ ), -S(R ⁹ ) and -S, wherein the ruthenium atom, the phosphorus atom and the sulfur atom are coordinated to the metal; R ⁹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, Aryloxy or heteroaryl] Wherein R ¹⁵ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; n15 represents an integer of 0 to 4; and D3 is selected from -Si(R ⁹ ) ₂ , -P(R ⁹ ) ₂ , -P(R ⁹ ), -S(R ⁹ ) and -S, the germanium atom, the phosphorus atom and the sulfur atom are coordinated to the metal; D4 is selected from -O-, -N-, -N (R ⁹ -, -Si(R ⁹ )-, -P(R ⁹ )-, -P- and -S-, the oxygen atom, nitrogen atom, ruthenium atom, phosphorus atom and sulfur atom are coordinated to the metal; R ⁹ Represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; here, each of the R ¹⁵ groups present on the two benzene rings may be bonded to each other to form a ring] Wherein D5 is selected from the group consisting of -Si(R ¹⁰ ) ₂ , -P(R ¹⁰ ) ₂ , -P(R ¹⁰ ), -S(R ¹⁰ ) and -S, the ruthenium atom, the phosphorus atom and the sulfur atom Arranged on the metal; R ¹⁰ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; D6 is an atom coordinated to a metal selected from a nitrogen atom, a carbon atom, a halogen atom, a phosphorus Atom and a sulfur atom; R ¹⁶ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; n16 represents an integer of 0 to 3; and E represents -O-, -N(R ¹¹ )-, -C (R ¹¹ ) ₂ -, -C(=R ¹¹ ')-, -C(=O)- or -C(=NR ¹¹ )-; R ¹¹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, An aryloxy or heteroaryl group; R ¹¹ ' represents an alkylene group, an alkenylene group or a cycloalkylene group; here, R ¹¹ or R ¹¹ ' may also bond with R ¹⁶ to form a ring] Wherein D5 is selected from the group consisting of -Si(R ¹⁰ ) ₂ , -P(R ¹⁰ ) ₂ , -P(R ¹⁰ ), -S(R ¹⁰ ) and -S, the ruthenium atom, the phosphorus atom and the sulfur atom Arranged on the metal; R ¹⁰ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; D6 is an atom coordinated to a metal selected from a nitrogen atom, a carbon atom, a halogen atom, a phosphorus Atom and a sulfur atom; R ¹⁷ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; n17 represents an integer of 0 to 3; and E represents -O-, -N(R ¹¹ )-, -C (R ¹¹ ) ₂ -, -C(=R ¹¹ ')-, -C(=O)- or -C(=NR ¹¹ )-; R ¹¹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, An aryloxy or heteroaryl group; R ¹¹ ' represents an alkylene group, an alkenylene group or a cycloalkylene group; here, R ¹¹ or R ¹¹ ' may also bond with R ¹⁷ to form a ring]. The photoelectric conversion element according to any one of the items 1 to 3, wherein the L3 in the formula (1) or the formula (2) is selected from the group consisting of Si(R ⁹ ) ₃ and P(R ^{9 )} ₃ , P(R ⁹ ) ₂ , S(R ⁹ ) ₂ , S(R ⁹ ) [R ⁹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group]. The photoelectric conversion element according to any one of claims 1 to 3, wherein the L1 is a ligand represented by the following formula (3): [wherein, c represents 0 or 1; R ¹ to R ³ represent an acidic group, and R ⁴ to R ⁶ represent a substituent; and b1 to b3 and c1 to c3 represent an integer of 0 or more and 4 or less]. The photoelectric conversion element according to any one of claims 1 to 3, wherein X in the formula (1) or (2) is NCS ^- , Cl ^- , Br ^- , I ^- , CN ^- , NCO ^- , H ₂ O or NCN ₂ ^- . The photoelectric conversion element according to any one of claims 1 to 3, wherein Y in the formula (1) or (2) is a halide ion, an arylsulfonate ion, or an aryl group Sulfonic acid ion, alkyl sulfate ion, sulfate ion, thiocyanate ion, perchloric acid ion, tetrafluoroboric acid ion, hexafluorophosphate ion, acetate ion, trifluoromethanesulfonate ion, ammonium ion, alkali metal ion or hydrogen ion. The photoelectric conversion element according to any one of claims 1 to 3, wherein the redox-based compound contained in the electrolyte is a cobalt complex. A dye-sensitized solar cell comprising the photoelectric conversion element according to any one of claims 1 to 3. A metal complex dye represented by the following formula (1) or formula (2): M(L1)(L2)(L3) _mL1 (X) _mX . (Y) _mY (1) M (L1) (L3) _mL2 (X) _mX . (Y) _mY Formula (2) [wherein M represents Fe ²⁺ , Ru ²⁺ or Os ²⁺ ; L1 represents a ligand of a bidentate to tetradentate having an acidic group and a nitrogen-containing aromatic heterocyclic skeleton; L2 represents a ligand of a dident or a trident having a deuterium atom, a phosphorus atom or a sulfur atom which does not have an unsaturated bond as a coordinating atom; and L3 represents a deuterium atom, a phosphorus atom or a sulfur atom having no unsaturated bond as Monodentate ligand of a coordinating atom; mL1 represents an integer from 0 to 2; mL2 represents an integer from 2 to 4; X represents a ligand of a single or two teeth; mX represents an integer from 0 to 3; Y represents a must The relative ion in the case of electric charge; mY is an integer from 0 to 2]. The metal complex dye according to claim 10, wherein the L2 is a ligand represented by any one of the following formulas (4) to (6): Wherein D1 is selected from the group consisting of -Si(R ⁷ ) ₂ , -P(R ⁷ ) ₂ , -P(R ⁷ ), -S(R ⁷ ) and -S, the ruthenium atom, the phosphorus atom and the sulfur atom Arranged on the metal; R ⁷ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; D2 is an atom coordinated to the metal, selected from the group consisting of a nitrogen atom, a carbon atom, a germanium atom, and a phosphorus Atom and sulfur atom; Za represents a group of atoms forming a ring; E represents -O-, -N(R ⁸ )-, -C(R ⁸ ) ₂ -, -C(=R ⁸ ')-, -C(= O)- or -C(=NR ⁸ )-; R ⁸ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; R ⁸ ' represents an alkylene group, an alkenylene group or a sub Cycloalkyl; here, R ⁸ or R ⁸ ' may also bond with Za to form a ring] Wherein d represents 0 or 1; Zb represents a group of atoms forming a ring; D3 is selected from the group consisting of -Si(R ⁹ ) ₂ , -P(R ⁹ ) ₂ , -P(R ⁹ ), -S(R ⁹ ) And -S, the germanium atom, the phosphorus atom and the sulfur atom are coordinated to the metal; D4 is selected from the group consisting of -O-, -N-, -N(R ⁹ )-, -Si(R ⁹ )-, -P(R ⁹ )-, -P- and -S-, the oxygen atom, nitrogen atom, germanium atom, phosphorus atom and sulfur atom are coordinated to the metal; R ⁹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aromatic group Oxy or heteroaryl; Zb may be bonded to each other to form a ring] Wherein D5 is selected from the group consisting of -Si(R ¹⁰ ) ₂ , -P(R ¹⁰ ) ₂ , -P(R ¹⁰ ), -S(R ¹⁰ ) and -S, the ruthenium atom, the phosphorus atom and the sulfur atom Arranged on the metal; R ¹⁰ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; D6 is an atom coordinated to a metal selected from a nitrogen atom, a carbon atom, a halogen atom, a phosphorus Atom and sulfur atom; Zc represents a group of atoms forming a ring; E represents -O-, -N(R ¹¹ )-, -C(R ¹¹ ) ₂ -, -C(=R ¹¹ ')-, -C(= O)- or -C(=NR ¹¹ )-; R ¹¹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heteroaryl group; and R ¹¹ ' represents an alkylene group, an alkenylene group or a sub Cycloalkyl; here, R ¹¹ or R ¹¹ ' may also bond with Zc to form a ring]. A dye-sensitizing liquid composition for a dye-sensitized solar cell, which contains 0.001% by mass to 0.1% by mass of the metal complex pigment as described in claim 10 or 11 in the organic solvent, and water The inhibition is 0.1% by mass or less. A dye-adsorbing electrode for a dye-sensitized solar cell, which is given half The pigment adsorption liquid composition according to claim 12 is applied onto the conductive support of the conductor, and the dye adsorption liquid composition is cured to form a photoreceptor layer. A method for producing a dye-sensitized solar cell, which is prepared by using the materials of the dye-adsorbing electrode, the electrolyte, and the counter electrode according to claim 13 of the patent application, and assembling the materials using the materials.