TW201638083A - Photoelectric conversion element, dye-sensitized solar cell, metal complex dye, metal complex dye mixture and dye solution - Google Patents

Abstract

A photoelectric conversion element which is provided with a photosensitive body layer comprising semiconductor fine particles on which the metal complex dyes (1) and (2) described below are supported; a dye-sensitized solar cell; a metal complex dye; a metal complex dye mixture; and a dye solution. Metal complex dye (1): a metal complex dye which comprises a terpyridine wherein one or two carboxyl groups among three carboxyl groups are salts and a bidentate ligand that is composed of a pyridine having a specific substituent at the 3-position and a nitrogen-containing aromatic five-membered ring Metal complex dye (2): a metal complex dye which comprises a terpyridine having three carboxyl groups and a bidentate ligand that is composed of a pyridine having a specific substituent at the 3-position and a nitrogen-containing aromatic five-membered ring.

Description

Photoelectric conversion element, dye-sensitized solar cell, metal complex pigment, metal complex pigment mixture and pigment solution

The present invention relates to a photoelectric conversion element, a dye-sensitized solar cell, a metal complex dye, a metal complex dye mixture, and a dye solution.

The photoelectric conversion element is used in various photosensors such as photosensors, photocopiers, and solar cells. The photoelectric conversion element has been put into practical use in various forms such as a method using a metal, a method using a semiconductor, a method using an organic pigment or a coloring matter, or a combination of these methods. In particular, solar cells using non-exhaustive solar energy require no fuel and use endless clean energy, and their formal practical use is expected. Among them, the solar cells have been researched and developed since a long time ago, and countries have also made policy considerations to promote popularization. However, niobium is an inorganic material and naturally has limitations in terms of improvement in throughput and cost.

Therefore, research on dye-sensitized solar cells is being carried out as much as possible. In particular, the research results of Graetzel and others at the University of Ecole Polytechnique Federale de Lausanne (EPFL) have become 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 photoelectric conversion efficiency as that of amorphous ruthenium. Therefore, a dye-sensitized solar cell that can be manufactured without using an expensive vacuum device has attracted the attention of researchers all over the world. Heretofore, dyes generally referred to as N3, N719, N749 (also known as Black Dye), Z907, and J2 have been developed as metal complex dyes used in dye-sensitized solar cells.

In addition to these pigments, a metal complex dye which exhibits an improvement in photoelectric conversion efficiency of a photoelectric conversion element and a dye-sensitized solar cell has been developed. For example, Patent Document 1 describes a metal complex dye comprising a terpyridine ligand in which three pyridine rings having one carboxyl group are bonded, a pyrazolylpyridine bidentate ligand, and a single tooth coordination. body. Further, Patent Document 2 describes a metal complex dye containing at least a terpyridine ligand containing a carboxyl group and a potassium salt, a lithium salt or a phosphonium salt of a carboxyl group in a specific ratio. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2013-20880 (Patent Document 2) Japanese Patent Laid-Open Publication No. 2014-209589

[Problems to be Solved by the Invention] The carboxyl group or the like which is an acidic group is easily bonded to each other by, for example, hydrogen bonding or the like. Such association (coagulation) is also found in metal complex dyes having a carboxyl group or the like. When the metal complex dye is adsorbed on the semiconductor fine particles, when the metal complex dye is aggregated, the metal complex dye (the state in which the metal complex dyes are superposed) is adsorbed on the surface of the semiconductor fine particles. Therefore, the homogeneous adsorption of the metal complex dye on the semiconductor fine particles is hindered, and the battery performance such as photoelectric conversion efficiency fluctuates. When the association of the metal complex dyes is inhibited and the metal complex dye is uniformly adsorbed on the semiconductor fine particles, the battery performance is theoretically stable. However, in this case, the interval between the metal complex dyes adsorbed on the surface of the semiconductor fine particles becomes large. The surface of the semiconductor fine particles is exposed between the adsorbed metal complex dyes. When the electrolyte comes into contact with the surface, reverse electron transfer occurs from the semiconductor fine particles to the electrolyte, and the open circuit voltage (V _OC ) of the photoelectric conversion element and the dye-sensitized solar cell is lowered.

An object of the present invention is to provide a photoelectric conversion element and a dye-sensitized solar cell having a high open circuit voltage and exhibiting stable photoelectric conversion efficiency, and a metal complex dye, a metal complex dye mixture, and a dye solution used in the above. [Means for solving the problem]

The present inventors have found that, in a metal complex dye containing a terpyridine ligand in which a pyridine ring having one carboxyl group is bonded, the introduction contains a specific ring bonded at the 3-position with respect to the nitrogen atom. a pyridine ring of a radical and a specific nitrogen-containing 5-membered ring ligand as a bidentate ligand for use with a terpyridine ligand, and further metalized in one or both of the three carboxyl groups When the metal complex dye is adsorbed on the semiconductor fine particles in the presence of the complex dye, the photoelectric conversion element and the dye-sensitized solar cell exhibit stable battery performance and a high open circuit voltage. The present invention is based on this finding and is further completed by repeated research.

That is, the problem of the present invention can be achieved by the following means. <1> A photoelectric conversion element comprising a conductive support, a photoreceptor layer containing an electrolyte, a charge transport layer containing an electrolyte, and a photoelectric conversion element of a counter electrode, wherein the photoreceptor layer is carried by the following formula (1) a semiconductor complex dye and a semiconductor fine particle of a metal complex dye represented by the following formula (2);

Formula (1): Ru(L ¹¹ )(L ¹² )(L ¹³ ) Formula (2): Ru(L ²¹ )(L ²² )(L ²³ ) In the formulae (1) and (2), L ¹¹ represents The tridentate ligand represented by the following formula (L11), L ²¹ represents a tridentate ligand represented by the following formula (L21); and L ¹² and L ²² each independently represent a formula (L2) represented by the following formula (L2) 2 tooth ligand; L ¹³ and L ²³ each independently represent a single tooth ligand;

[Chemical 1]

In the formula (L11), M ¹ each independently represents a hydrogen ion or a cation; wherein at least one of the three M ¹ represents a cation, and at least one represents a hydrogen ion;

[Chemical 2]

In the formula, G ¹ represents a group represented by any formula of the following formula (G1-1) to formula (G1-5); and R ²¹ represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, or an amine. a heteroaryl group or an aryl group; R ²² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, an amine group, a heteroaryl group or an aryl group; and X represents an oxygen atom, a sulfur atom, an NRf, a selenium group. An atom, C(Rf) ₂ or Si(Rf) ₂ ; Rf represents a hydrogen atom or an alkyl group; n represents an integer of 0 to 2; wherein, in the case where n is 2, two R ²¹ are not bonded to each other. Forming an aromatic ring;

[Chemical 3]

In the formula, R ¹¹ to R ¹⁸ each independently represent a hydrogen atom, an alkyl group, a heteroaryl group, an aryl group or a halogen atom; and * represents a bond to the pyridine ring of the formula (L2).

(2) The photoelectric conversion element according to the above formula (1), wherein a metal of one of M ¹ in the formula (L11) in the metal complex dye represented by the following formula (1) is a cation chromogen, in the formula (L11) M ¹ is two cationic metal complex dye of formula (2) molar ratio of metal complex dye represented by the set y: z: x is the case The index R _CS indicating the amount of the salt of the carboxyl group satisfies the following formula (A): (A): R _CS = [(y + 2z) / (x + y + z)] × 100 ≦ 200. <3> The photoelectric conversion element according to <1>, wherein the index R _CS satisfies the following formula (B): (B): R _CS = [(y + 2z) / (x + y+z)]×100≦100. The photoelectric conversion element according to any one of <1> to <3> wherein the index R _CS satisfies the following formula (C): (C): R _CS = [(y + 2z) /(x+y+z)]×100≦10. The photoelectric conversion element <5><1> to <4> according to any preceding claim, wherein, L ¹² has as G ¹ in the L ²² and having at least one as G ¹ in formula (G1-2) of the The base of the representation. <6> A dye-sensitized solar cell according to any one of <1> to <5> above. <7> A metal complex dye mixture containing a metal complex dye represented by the following formula (1) and a metal complex dye represented by the following formula (2), wherein the following formula (1) In the metal complex dye represented by the following formula (L11), one of M ¹ is a cationic metal complex dye, and two of M ¹ in the following formula (L11) are cationic metal When the molar ratio of the metal complex dye represented by the following formula (2) is y:z:x, the index R _CS indicating the amount of the salt of the carboxyl group satisfies the following formula ( A): (A): R _CS = [(y + 2z) / (x + y + z)] × 100 ≦ 200

Formula (1): Ru(L ¹¹ )(L ¹² )(L ¹³ ) Formula (2): Ru(L ²¹ )(L ²² )(L ²³ ) In the formulae (1) and (2), L ¹¹ represents The tridentate ligand represented by the following formula (L11), L ²¹ represents a tridentate ligand represented by the following formula (L21); and L ¹² and L ²² each independently represent a formula (L2) represented by the following formula (L2) 2 tooth ligand; L ¹³ and L ²³ each independently represent a single tooth ligand;

[Chemical 4]

Wherein M ¹ each independently represents a hydrogen ion or a cation; wherein at least one of the three M ¹ represents a cation and at least one represents a hydrogen ion;

[Chemical 5]

In the formula, G ¹ represents a group represented by any formula of the following formula (G1-1) to formula (G1-5); and R ²¹ represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, or an amine. a heteroaryl group or an aryl group; R ²² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, an amine group, a heteroaryl group or an aryl group; and X represents an oxygen atom, a sulfur atom, an NRf, a selenium group. An atom, C(Rf) ₂ or Si(Rf) ₂ ; Rf represents a hydrogen atom or an alkyl group; n represents an integer of 0 to 2; wherein, in the case where n is 2, two R ²¹ are not bonded to each other. Forming an aromatic ring;

[Chemical 6]

In the formula, R ¹¹ to R ¹⁸ each independently represent a hydrogen atom, an alkyl group, a heteroaryl group, an aryl group or a halogen atom; and * represents a bond to the pyridine ring of the formula (L2).

<8> A dye solution containing the metal complex dye mixture and the solvent according to <7> above. <9> A metal complex dye, which is represented by the following formula (3): Formula (3): Ru(L ³¹ )(L ¹² )(L ¹³ ) wherein L ³¹ represents the following formula (L31) a 3-dental ligand represented; L ¹² represents a bidentate ligand represented by the following formula (L2); and L ¹³ represents a monodentate ligand;

[Chemistry 7]

Wherein M ³ each independently represents a hydrogen ion, a sodium ion or a cesium ion; wherein, at least one of the three M ³ represents a sodium ion or a cesium ion, and at least one represents a hydrogen ion;

[化8]

In the formula, G ¹ represents a group represented by any formula of the following formula (G1-1) to formula (G1-5); and R ²¹ represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, or an amine. a heteroaryl group or an aryl group; R ²² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, an amine group, a heteroaryl group or an aryl group; and X represents an oxygen atom, a sulfur atom, an NRf, a selenium group. An atom, C(Rf) ₂ or Si(Rf) ₂ ; Rf represents a hydrogen atom or an alkyl group; n represents an integer of 0 to 2; wherein, in the case where n is 2, two R ²¹ are not bonded to each other. Forming an aromatic ring;

[Chemistry 9]

In the formula, R ¹¹ to R ¹⁸ each independently represent a hydrogen atom, an alkyl group, a heteroaryl group, an aryl group or a halogen atom; and * represents a bond to the pyridine ring of the formula (L2).

In the present specification, unless otherwise specified, the 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 or formula are present, or when a plurality of substituents or the like are simultaneously defined, unless otherwise specified, Each of the substituents and the like may be the same or different from each other. The same applies to the regulation of the number of substituents and the like. Further, when a plurality of substituents or the like are in close proximity (particularly in the case of adjacent), the substituents or the like may be bonded to each other to form a ring unless otherwise specified. Further, a ring such as an aromatic ring or an aliphatic ring may be further condensed to form a condensed ring.

In the present specification, the expression of the compound (including the complex compound and the coloring matter) is used for the meaning of the salt and the ion thereof in addition to the compound itself. Further, it is indicated that a part of the structure is changed within a range that achieves the target effect. Further, the compound which is not substituted or unsubstituted is not clearly described, and it may have any substituent in the range which has a desired effect. The same applies to the substituent, the linking group and the ligand.

In addition, in this specification, the numerical range shown using "-" shows the range which contains the numerical value of the [---- [Effects of the Invention]

The photoelectric conversion element and the dye-sensitized solar cell of the present invention exhibit high open circuit voltage and stable photoelectric conversion efficiency. Further, the metal complex dye, the metal complex dye mixture, and the dye solution of the present invention can produce a photoelectric conversion element and a dye-sensitized solar cell which exhibit the above-described excellent characteristics. The above and other features and advantages of the present invention will be made apparent by reference to the appended claims.

[Photoelectric Conversion Element and Pigment Sensitized Solar Cell] The photoelectric conversion element of the present invention includes a conductive support, a photoreceptor layer containing an electrolyte, a charge transport layer containing an electrolyte, and a counter electrode (counter electrode). A photoreceptor layer, a charge transport layer, and a counter electrode are sequentially provided on the conductive support.

In the photoelectric conversion element of the present invention, the semiconductor fine particles forming the photoreceptor layer as a whole are supported by the metal complex dye represented by the following formula (1) which is a sensitizing dye, and the formula (2) described later. At least two of the metal complex pigments. Therefore, at least a part of the semiconductor fine particles can carry both of the metal complex dye represented by the formula (1) and the metal complex dye represented by the formula (2), or may carry only one of them. Here, the form in which the metal complex dye is carried on the surface of the semiconductor fine particles includes a form of being adsorbed on the surface of the semiconductor fine particles, a form deposited on the surface of the semiconductor fine particles, and a form in which the forms are mixed. Adsorption includes chemisorption and physical adsorption, preferably chemisorption. The semiconductor fine particles may also carry other metal complex dyes together with the metal complex dyes represented by the formulas (1) and (2) described later.

Moreover, the photoreceptor layer contains an electrolyte. The electrolyte contained in the photoreceptor layer may be of the same kind as the electrolyte contained in the charge transport layer, or may be of a different species, preferably the same species.

The photoelectric conversion element of the present invention is not particularly limited as long as it has a configuration other than the one defined in the present invention, and a known configuration relating to the photoelectric conversion element can be employed. The respective layers constituting the photoelectric conversion element of the present invention may be designed according to the purpose, and may be formed, for example, as a single layer or as a plurality of layers. Further, layers other than the respective layers may be included as needed.

The dye-sensitized solar cell of the present invention is obtained by using the photoelectric conversion element of the present invention. Hereinafter, preferred embodiments of the photoelectric conversion element and the dye-sensitized solar cell of the present invention will be described.

The system 100 shown in FIG. 1 is a system in which the photoelectric conversion element 10 according to the first embodiment of the present invention is applied to a battery application in which an operation unit M (for example, an electric motor) is operated by an external circuit 6. The photoelectric conversion element 10 includes: a conductive support 1; the photoreceptor layer 2 includes an electrolyte between the semiconductor fine particles 22 sensitized by the dye (metal complex dye) 21 and the semiconductor fine particles 22; a layer of charge transfer body layer 3; and an opposite electrode 4. In the photoelectric conversion element 10, the light-receiving electrode 5 includes the conductive support 1 and the photoreceptor layer 2, and functions as a working electrode.

In the system 100 to which the photoelectric conversion element 10 is applied, the light incident on the photoreceptor layer 2 excites the metal complex dye 21. The excited metal complex dye 21 has electrons having high energy, and the electrons are transferred from the metal complex dye 21 to the conduction band of the semiconductor fine particles 22, and further diffused to reach the conductive support 1. At this time, the metal complex dye 21 becomes an oxidant (cation). The electrons reaching the conductive support 1 are operated by the external circuit 6, and reach the oxidized body of the metal complex dye 21 via the counter electrode 4 and the charge transfer body layer 3, thereby reducing the oxidized body, thereby causing the system 100 to be cooled. It functions as a solar battery.

The dye-sensitized solar cell 20 shown in Fig. 2 includes the photoelectric conversion element according to the second embodiment of the present invention. The photoelectric conversion element to be the dye-sensitized solar cell 20 differs from the photoelectric conversion element shown in FIG. 1 in the configuration of the conductive support 41 and the photoreceptor layer 42 and the spacer S, except for the above. Other than this, it is configured similarly to the photoelectric conversion element 10 shown in FIG. That is, the conductive support 41 has a two-layer structure including the substrate 44 and the transparent conductive film 43 formed on the surface of the substrate 44. Further, the photoreceptor layer 42 has a two-layer structure including a semiconductor layer 45 and a light scattering layer 46 which is formed adjacent to the semiconductor layer 45. A spacer S is provided between the conductive support 41 and the opposite electrode 48. In the dye-sensitized solar cell 20, 40 is a light receiving electrode, and 47 is a charge transporting body layer.

In the same manner as the system 100 to which the photoelectric conversion element 10 is applied, the dye-sensitized solar cell 20 functions as a solar cell by causing light to enter the photoreceptor layer 42.

The photoelectric conversion element and the dye-sensitized solar cell of the present invention are not limited to the above-described preferred embodiments, and the configuration and the like of the respective embodiments may be appropriately combined between the embodiments without departing from the scope of the invention. .

In the present invention, materials and members used in the photoelectric conversion element or the dye-sensitized solar cell can be produced by a usual method. For example, U.S. Patent No. 4,927,721, U.S. Patent No. 4,684,537, U.S. Patent No. 5,084,365, U.S. Patent No. 5,084,365, U.S. Patent No. 5,350,644, U.S. Patent No. 5,463,057, U.S. Patent No. 5,525,440, Japanese Patent Laid-Open No. -249790, Japanese Patent Laid-Open No. 2001-185244, Japanese Patent Laid-Open No. 2001-210390, Japanese Patent Laid-Open No. 2003-217688, Japanese Patent Laid-Open No. 2004-220974, and Japanese Patent Publication No. 2008 -135197.

<Metal complex dye mixture> The metal complex dye mixture of the present invention contains a metal complex dye (sometimes referred to as a metal complex dye (1)) represented by the following formula (1) and the following formula (2) A metal complex dye (sometimes referred to as a metal complex dye (2)). By using the metal complex dye mixture, it is possible to impart a high open circuit voltage to the photoelectric conversion element or the like as compared with the case of using the metal complex dye (1) or the metal complex dye (2) alone. Stable photoelectric conversion efficiency.

The reason for this has not been determined, but it is inferred as follows. In other words, in the coexistence of the metal complex dye (1) and the metal complex dye (2), the metal complex dye (1) can prevent aggregation due to carboxyl group association due to electron repulsion or the like. Further, the carboxyl group which is a salt is adsorbed on the semiconductor fine particles earlier than the carboxyl group which is not a salt. On the other hand, when the metal complex dye is adsorbed on the semiconductor fine particles by the carboxyl group, electron repulsion or the like is weakened, and the other metal complex dye can be made close. The metal complex dye which is close to the metal complex dye (1) which is preferentially adsorbed on the semiconductor fine particles is successively adsorbed around the previously adsorbed metal complex dye by the following action or the like. Thereby, the overlap of the metal complex dyes is avoided, and the surface of the semiconductor fine particles is closely adsorbed. The adsorption using such a metal complex pigment as a core (starting point) is caused by the interaction unique to the bidentate ligand L ¹² or L ²² as described below. That is, the bidentate ligands L ¹² and L ²² contain a pyridine ring and a nitrogen-containing 5-membered ring bonded to a specific ring group at the 3-position with respect to a nitrogen atom. In the three-dimensional ligand of the metal complex dye, the three rings of the specific ring group, the pyridine ring, and the nitrogen-containing five member ring are arranged substantially linearly. Therefore, the steric hindrance of the metal complex dye preferentially adsorbed on the semiconductor fine particles and the metal complex dye present in the vicinity is small, and the three rings of the adjacent metal complex dye are mutually exchanged by the three rings. The action (pi-pi stacking) causes the metal complex dye to adsorb around itself. The pyridine ring of the bidentate ligand of the preferentially adsorbed metal complex dye has the greatest influence on the interaction of the pyridine ring of the bidentate ligand of the metal complex dye present in the vicinity. Substituting an alkynyl group or a condensed ring on a specific ring group to form an aromatic group also depends on its orientation or size, but due to a combination of π-π stacking deviation or steric hindrance, etc., an interaction hindering the interaction of the pyridine rings is generated. The effect of the situation is not good. When the photoelectric conversion element and the dye-sensitized solar cell of the present invention are produced by using the metal complex dye mixture of the present invention, the high open circuit voltage (V _OC ) and stable photoelectric conversion efficiency are exhibited.

In the metal complex dye mixture of the present invention, the metal complex dye (1) and the metal complex dye (2) may each contain a plurality of types. For example, in the metal complex dye (1), a metal complex dye of one of M ¹ in the formula (L11) to be described later and a metal of two molecules of M ¹ in the formula (L11) may be used in combination. The complex pigment. The combination of the metal complex dye (1) and the metal complex dye (2) in the metal complex dye mixture is not particularly limited. For example, a metal complex dye having only a different ligand L ¹¹ and a ligand L ²¹ (free carboxyl group or salt) can be used in combination with each other. Further, a combination of the ligand L ¹² and the ligand L ²² and at least one set of the ligand complexes of the ligand L ¹³ and the ligand L ²³ may be used in combination.

In the metal complex dye mixture of the present invention, the group of the ligand L ¹¹ and the ligand L ²¹ , the group of the ligand L ¹² and the ligand L ²² , and the ligand L ¹³ and the ligand The groups of L ²³ can also be combined with each other preferably. For example, at least one of G ¹ of the ligand L ¹² and G ¹ of the ligand L ²² may be a combination of the ligands represented by the formula (G1-2) described later, or may be combined with each other. The ligands of the groups represented by the formula (G1-2) described later are combined with each other.

The content ratio of the metal complex dye (1) and the metal complex dye (2) in the metal complex dye mixture is not particularly limited. In the present invention, each metal complex dye is defined relative to the metal complex dye (1) and metal by an index R _CS (0 < R _CS < 300) indicating the amount of the carboxyl group relative to the amount of all the carboxyl groups present. The content ratio of the total amount of the complex dye (2). The index R _CS indicating the amount of the salt of the carboxyl group is a metal complex dye in which one of M ¹ in the formula (L11) in the metal complex dye (1) is a cation, and the formula (L11) In the case where the two cation metal complex dyes of M ¹ and the metal complex dye (2) have a molar ratio of y:z:x, [(y+2z)/(x+y) +z)] × 100 is indicated. The index R _CS indicating the amount of the present is 300 if all the carboxyl groups of the metal complex dye are salts, and 0 if all the carboxyl groups are not salts. In the present invention, the index R _CS indicating the amount of the salt of the carboxyl group is not particularly limited, and it is preferable to satisfy the following formula (A) in terms of both the improvement of the open circuit voltage and the stability of the photoelectric conversion efficiency. . In addition to the improvement of the stability of the photoelectric conversion efficiency, the effect of improving the open circuit voltage is further increased, and it is preferable to satisfy the following formula (B). In terms of being able to achieve a high level of stability between the open circuit voltage and the photoelectric conversion efficiency, it is preferable to satisfy the following formula (C). (A): R _CS = [(y + 2z) / (x + y + z)] × 100 ≦ 200 (B): R _CS = [(y + 2z) / (x + y + z)] × 100 ≦100 (C): R _CS = [(y + 2z) / (x + y + z)] × 100 ≦ 10 The lower limit of the index R _CS is not particularly limited, and is preferably 0.01 or more. More preferably, it is 0.05 or more.

In the metal complex dye mixture, the index R _CS indicating the amount of the salt of the carboxyl group can be set by a suitable method. For example, it is possible to synthesize a metal complex dye (1) and a metal complex dye (2), respectively, and mix them so as to be an index R _CS indicating the amount of the present. Further, it can be set such that all of the carboxyl groups present in the metal complex dye in the metal complex dye mixture become a carboxyl group or a salt which is all a carboxyl group, and an index R _CS indicating the amount of the presence is obtained. The basic compound or acid (saltification of a carboxyl group or hydrolysis of a salt of a carboxyl group) is added in a manner.

The metal complex dye mixture may contain a dye other than the metal complex dye (1) and the metal complex dye (2). Examples of such a dye include a Ru complex dye other than the metal complex dye (1) and the metal complex dye (2), a squarylium cyanine dye, an organic dye, a porphyrin dye, or a phthalocyanine dye. Preferably, it is a Ru complex dye, a squarylium dye or an organic dye. When the metal complex dye (1) and the metal complex dye (2) are used in combination with other dyes, the total mass of the metal complex dye (1) and the metal complex dye (2)/others The quality of the pigment is preferably 95/5 to 10/90, more preferably 95/5 to 50/50, and even more preferably 95/5 to 60/40, and particularly preferably 95/5 to 65/35. It is 95/5~70/30.

- The metal complex dye (1) represented by the formula (1) is a metal complex dye represented by the following formula (1).

Formula (1): Ru(L ¹¹ )(L ¹² )(L ¹³ ) wherein L ¹¹ represents a tridentate ligand represented by the following formula (L11).

[化10]

In the formula, three M ¹ each independently represent a hydrogen ion or a cation. The cation which can be used as M ¹ is not particularly limited, and examples thereof include positive counter ions (excluding hydrogen ions) in the counter ion CI described below. Among them, an alkali metal ion, a cerium ion or an ammonium ion is preferred, and a sodium ion, a cerium ion or an ammonium ion is more preferred, and a sodium ion or a cerium ion is further more preferable, and a sodium ion is particularly preferable. The alkali metal ion, the cerium ion, and the ammonium ion are respectively described in the counter ion CI described later. L ¹¹ is a partially salted ligand of M ¹ having a hydrogen ion and a cation, and M ^{1 which} may be a cation may be one or two, or may be a M ¹ salted ligand L ¹¹ and two A mixture of ligands L ¹¹ in which M ¹ is salted. Further, to a cationic M ¹ may be any of a carboxyl group M ^1.

L ¹² represents a bidentate ligand represented by the following formula (L2).

[11]

In the formula, G ¹ represents a group represented by any formula of the following formula (G1-1) to formula (G1-5). G ^{1 is} preferably a group represented by any formula of the following formula (G1-1) to formula (G1-3) and formula (G1-5), and more preferably represented by the following formula (G1-2). base.

[化12]

In the formula, R ¹¹ to R ¹⁸ each independently represent a hydrogen atom, an alkyl group, a heteroaryl group, an aryl group or a halogen atom. * represents a bond to the pyridine ring of the formula (L2).

The alkyl group, the heteroaryl group, the aryl group and the halogen atom in R ¹¹ to R ¹⁸ are each preferably a corresponding group in the substituent Z ^R described later.

The alkyl group which can be used as R ¹¹ to R ¹⁸ is more preferably an alkyl group substituted with an electron-donating group, and still more preferably an alkyl group substituted with a halogen atom, particularly a fluorine atom. The number of the halogen atoms to be substituted in the alkyl group substituted with a halogen atom is not particularly limited, and is preferably one or more, and preferably the number of hydrogen atoms of the alkyl group is not more than 1, more preferably one to six, furthermore Good for 1 to 3. Among them, the alkyl group substituted with a halogen atom is preferably a perhaloalkyl group in which all hydrogen atoms of the alkyl group are substituted, more preferably a perfluoroalkyl group, still more preferably a trifluoromethyl group.

The aryl group which may be employed as R ¹¹ to R ¹⁸ is more preferably an aryl group substituted with an electron-donating group, and still more preferably an aryl group substituted with a halogen atom, particularly a fluorine atom. The number of halogen atoms to be substituted in the aryl group substituted with a halogen atom is not particularly limited, and is preferably one or more, and preferably the number of hydrogen atoms of the aryl group is at most 2, more preferably 2 to 5, furthermore Good for 3 to 5. Among them, the aryl group substituted by a halogen atom is preferably a phenyl group substituted by a halogen atom, and examples thereof include 2,3,4,5-tetrafluorophenyl.

R ¹¹ , R ¹³ , R ¹⁵ , R ¹⁷ and R ¹⁸ are each preferably a hydrogen atom or an alkyl group in the respective groups, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, still more preferably A hydrogen atom. R ¹² , R ¹⁴ and R ¹⁶ are each preferably an alkyl group, an aryl group or a heteroaryl group in the respective groups, more preferably an alkyl group or an aryl group, more preferably an alkyl group substituted by a fluorine atom or a fluorine group. The atom-substituted aryl group is further more preferably an alkyl group substituted by a fluorine atom, particularly preferably a trifluoromethyl group.

In the formula (L2), R ²¹ represents an alkyl group, an alkynyl group, an alkenyl group, an alkoxy group, an alkylthio group, an amine group, a heteroaryl group or an aryl group. R ²² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, an amine group, a heteroaryl group or an aryl group. n represents an integer of 0 to 2. However, in the case where n is 2, two R ²¹ are not bonded to each other to form an aromatic ring. X represents an oxygen atom, a sulfur atom, NRf, a selenium atom, C(Rf) ₂ or Si(Rf) ₂ . Rf represents a hydrogen atom or an alkyl group. * represents a bond to the pyridine ring in the formula (L2).

Each of the groups defined by R ²¹ , R ²² and Rf is preferably a corresponding one of the substituents Z ^R described later. R ²¹ is preferably an alkyl group, an alkoxy group, an alkylthio group, an amine group, an aryl group or a heteroaryl group in the above groups, more preferably an alkyl group, an alkoxy group, an alkylthio group, an amine group or a hetero group. The aryl group is further more preferably an alkyl group, an alkoxy group or an alkylthio group. n is preferably 0 or 1, more preferably 0. In the case where n is 2, two R ²¹ may be bonded to each other to form a ring, and adjacent R ²¹ and R ²² may be bonded to form a ring. At this time, the ring formed is a ring other than an aromatic ring (an aryl ring and a heteroaryl ring). For example, an unsaturated hydrocarbon ring which does not exhibit an aromatic property such as a cyclopentadiene ring, a heterocyclic ring which does not exhibit an aromatic property, such as a 1,4-dioxane ring or a 2,3-dihydropyrazine ring, may be mentioned.

R ²² is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group or an amine group in the above groups, more preferably an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group or an amine group. Further, it is more preferably an alkyl group, an alkenyl group, an alkylthio group or an amine group.

X is preferably an oxygen atom or a sulfur atom, more preferably a sulfur atom.

In the group represented by the formula (L2), the ring containing X is preferably a group represented by any one of the following formulae (G2-1a) to (G2-4a), and preferably a formula (G2-) The group represented by 1a) or (G2-4a) is more preferably a group represented by the formula (G2-1a).

[Chemistry 13]

In the formulae (G2-1a) to (G2-4a), R ²² and X are synonymous with R ²² and X in the formula (L2), and the preferred ranges are also the same. R ²³ represents a hydrogen atom, an alkyl group, an alkynyl group, an alkenyl group, an alkoxy group, an alkylthio group, an amine group, a heteroaryl group or an aryl group. Each group which can be used as R ²³ has the same meaning as each group which can be used as R ^{21 of the} formula (L2), and the preferred range is also the same, and particularly preferably a hydrogen atom.

Z ² and Z ³ each independently represent an oxygen atom, a sulfur atom, NRb, C(Rb) ₂ , a selenium atom or Si(Rb) ₂ . Z ^{2 is} preferably NRb or CRb ₂ , and Z ^{3 is} preferably an oxygen atom or a sulfur atom, more preferably an oxygen atom. Rb each independently represents a hydrogen atom or an alkyl group. The alkyl group in Rb is preferably an alkyl group of the substituent Z ^R described later.

In the formula (1), L ¹³ represents a monodentate ligand. L ¹³ is not particularly limited, and examples thereof include NCS ^- , NCO ^- , OCN ^- , SCN ^- , halide (Cl ^- , Br ^- , I ^- ), CN ^- , H ₂ O or NCN ₂ ^-, etc., preferably NCS ^- , NCO ^- , OCN ^- , SCN ^- , CN ^- , or a halide, more preferably NCS ^- , CN ^- , or a halide, further preferably NCS ^- .

The metal complex dye (2) represented by the formula (2) is a metal complex dye represented by the following formula (2). The metal complex dye (2) is the same as the metal complex dye (1) except for the three-dentate ligand, and the preferred range is also the same.

Formula (2): Ru(L ²¹ )(L ²² )(L ²³ ) wherein L ²¹ represents a tridentate ligand represented by the following formula (L21). L ²² represents a bidentate ligand represented by the formula (L2). The L ^{22 is} synonymous with the L ¹² , and the preferred range is also the same. L ²³ represents a monodentate ligand. The L ^{23 is} synonymous with the L ¹³ and the preferred range is also the same.

[Chemistry 14]

The metal complex dye-metal complex dye (3) represented by the formula (3) is a metal complex dye represented by the following formula (3). The metal complex dye is the same as the metal complex dye (1) except for the cation of the 3-dentate ligand, and the preferred range is also the same.

Formula (3): Ru(L ³¹ )(L ¹² )(L ¹³ ) wherein L ³¹ represents a tridentate ligand represented by the following formula (L31). L ¹² represents a bidentate ligand represented by the formula (L2). L ¹² L ¹² is synonymous with the formula (1), and preferred ranges are also the same. L ¹³ represents a monodentate ligand. L L ^{13 13} This is synonymous with Formula (1), and preferred ranges are also the same.

[化15]

M ³ each independently represents a hydrogen ion, a sodium ion or a cesium ion. Among them, at least one of the three M ³ represents a sodium ion or a cesium ion, and at least one represents a hydrogen ion. The metal complex dye represented by the formula (3) is a form of the metal complex dye (1), and can be preferably used together with the metal complex dye (2) for the metal complex of the present invention. In the pigment mixture.

The metal complex dye (1) and the metal complex dye (2) also each contain a form of a counter ion (CI) containing a charge for neutralizing the dye.

In the case where the counter ion CI is a positive counter ion, for example, the counter ion CI is an inorganic or organic ammonium ion (for example, a tetraalkylammonium ion such as tetrabutylammonium or triethylbenzylammonium or a pyridinium ion).鏻 ions (for example, tetraalkylphosphonium ions such as tetrabutylphosphonium ions, alkyltriphenylphosphonium ions, etc.), alkali metal ions (such as sodium ions, lithium ions, potassium ions, cesium ions, etc.), alkaline earth metal ions, Metal complex ion or hydrogen ion. The positive counter ion is preferably an inorganic or organic ammonium ion (tetraethylammonium ion, tetrabutylammonium ion, tetrahexylammonium ion, tetraoctylammonium ion, tetradecylammonium ion, etc.), an alkali metal ion or Hydrogen ion.

In the case where the counter ion CI is a negative counter ion, for example, the counter ion CI may be an inorganic anion or an organic anion. For example, hydroxide ions, halogen anions (for example, fluoride ions, chloride ions, bromide ions, iodide ions, etc.), substituted or unsubstituted alkyl carboxylate ions (acetate ion, trifluoroacetic acid) may be mentioned. Root ion, etc.), substituted or unsubstituted aryl carboxylate ion (benzoate ion, etc.), substituted or unsubstituted alkylsulfonate ion (methanesulfonate ion, triflate ion, etc.) ), substituted or unsubstituted aryl sulfonate ion (eg p-toluenesulfonate ion, p-chlorobenzenesulfonate ion, etc.), aryl disulfonate ion (eg 1,3-benzenedisulfonate ion, 1 , 5-naphthalene disulfonate ion, 2,6-naphthalene disulfonate ion, etc.), alkyl sulfate ion (such as methyl sulfate ion, etc.), sulfate ion, thiocyanate ion, perchlorate ion, Tetrafluoroborate ion, hexafluorophosphate ion, picrate ion. Further, as the charge-balancing counter ion, an ionic polymer or another dye having an opposite charge to 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. The negative counter ion is preferably a halogen anion, a substituted or unsubstituted alkyl carboxylate ion, a substituted or unsubstituted alkyl sulfonate ion, a substituted or unsubstituted aryl sulfonate ion, An aryl disulfonate ion, a perchlorate ion, a hexafluorophosphate ion, more preferably a halogen anion or a hexafluorophosphate ion.

The metal complex dye (1) and the metal complex dye (2) can be synthesized, for example, by the method described in Japanese Patent Laid-Open Publication No. 2013-084594, and Japanese Patent No. 4298799. The method and application described in the respective descriptions of the method described in the specification, the US Patent Application Publication No. 2013/0018189A1, the U.S. Patent Application Publication No. 2012/0073660 A1, the U.S. Patent Application Publication No. 2012/0111410 A1, and the U.S. Patent Application Publication No. 2010/0258175 A1 Method, Chemical Communication (Chem. Commun.), published in Angew. Chem. Int. Ed. (2011, 50, pp. 2054 to 2058) (2014, 50, p. 6379-M. The method described in the 6381 page), the method described in the references cited in the literature, the patent document relating to a solar cell, a known method, or a method according to the methods.

The maximum absorption wavelength of the respective metal complex dyes in the solution is preferably in the range of 300 nm to 900 nm, more preferably in the range of 350 nm to 850 nm, and particularly preferably in the range of 370 nm to 800 nm. Further, it is preferable that the absorption wavelength region covers the entirety of 300 nm to 900 nm.

Specific examples of the metal complex dye (1) and the metal complex dye (2) include the respective metal complex dyes and the like synthesized in the examples described later, but the present invention is not limited to these metal errors. Compound pigment. In the case where the metal complex dye shown in the examples contains a ligand having a hydrogen ion dissociable group, the ligand may also be dissociated as needed to emit hydrogen ions.

<Substituent Group Z ^R > The substituent in the present invention may be a substituent selected from the following substituent group Z ^R . The substituent group Z ^R is a group of substituents that do not contain an acidic group. In the present specification, when only a substituent is described, the substituent group Z ^{R is} referred to. Further, in the case where only each group, for example, an alkyl group, is described, a preferred range and a specific example of the corresponding group of the substituent group Z ^R are applied. In the present specification, when an alkyl group is described as being distinguished from a cycloalkyl group, the alkyl group is used in the sense of including a linear alkyl group and a branched alkyl group. On the other hand, when an alkyl group is not described in a difference from a cycloalkyl group (only when it is described as an alkyl group), and unless otherwise specified, an alkyl group contains a linear alkyl group and a branched alkyl group. It is used in the meaning of a group and a cycloalkyl group. a compound (alkoxy group, alkylthio group, alkenyloxy group, or the like) containing a group having a cyclic structure (alkyl group, alkenyl group, alkynyl group, etc.), and a compound containing a group having a cyclic structure (described above) Alkyl esters, etc.) are also the same in this respect. In the description of the substituent group Z ^R described below, for example, in order to clarify the group of the linear or branched structure and the group of the cyclic structure, such as an alkyl group and a cycloalkyl group, the above may be separately described.

Examples of the group contained in the substituent group Z ^R include the following groups and a combination of a plurality of the following groups. An alkyl group (preferably having a carbon number of 1 to 20, more preferably 1 to 12, such as methyl, ethyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 1-ethylpentyl, 2-ethylhexyl, benzyl, 2-ethoxyethyl or trifluoromethyl), alkenyl (preferably having a carbon number of 2 to 20, more preferably 2 to 12, for example Vinyl, allyl, butenyl or oleyl), alkynyl (preferably having a carbon number of 2 to 20, more preferably 2 to 12, such as ethynyl, butynyl, octynyl or phenylacetylene a group, a cycloalkyl group (preferably having a carbon number of 3 to 20), a cycloalkenyl group (preferably having a carbon number of 5 to 20), and an aryl group (preferably having a carbon number of 6 to 26, such as a phenyl group or a 1-naphthalene group). a group, a 4-methoxyphenyl group, a 2-chlorophenyl group, a 3-methylphenyl group, a difluorophenyl group or a tetrafluorophenyl group, or a heterocyclic group (preferably having a carbon number of 2 to 20, more preferably a 5-membered or 6-membered heterocyclic group having at least one oxygen atom, a sulfur atom or a nitrogen atom. The heterocyclic group contains an aromatic heteroaryl group and an aliphatic heterocyclic group which does not exhibit aromaticity. The aryl group is, for example, 2-pyridyl, 2-thienyl, 2-furyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazole a base, a 2-thiazolyl or 2-oxazolyl), alkoxy group (preferably having a carbon number of from 1 to 20, more preferably from 1 to 12, such as a methoxy group, an ethoxy group, a propoxy group, or a hexyloxy group) , octyloxy or benzyloxy), alkenyloxy (preferably having a carbon number of 2 to 20, more preferably 2 to 12), alkynyloxy group (preferably having a carbon number of 2 to 20, more preferably 2 to 12) a cycloalkoxy group (preferably having a carbon number of 3 to 20), an aryloxy group (preferably having a carbon number of 6 to 26), a heterocyclic oxy group (preferably having a carbon number of 2 to 20),

Alkoxycarbonyl (preferably having 2 to 20 carbon atoms), cycloalkoxycarbonyl (preferably having 4 to 20 carbon atoms), aryloxycarbonyl (preferably having 6 to 20 carbon atoms), and amine groups Preferably, the carbon number is from 0 to 20, and includes an alkylamino group, an alkenylamino group, an alkynylamino group, a cycloalkylamino group, a cycloalkenylamino group, an arylamino group, a heterocyclic amino group, for example, an amine group, N,N-Dimethylamino, N,N-diethylamino, N-ethylamino, N-allylamino, N-(2-propynyl)amine, N-ring Hexylamino, N-cyclohexenylamino, N,N-diphenylamino, anilino, pyridylamino, imidazolylamino, benzimidazolylamino, thiazolylamino, benzo a thiazolylamino group or a triazinylamino group, an aminoximino group (preferably an amine sulfonyl group having a carbon number of 0 to 20, preferably an alkyl group, a cycloalkyl group or an aryl group), or a mercapto group (preferably An amine having 1 to 20 carbon atoms, an anthraceneoxy group (preferably having 1 to 20 carbon atoms), an amine carbenyl group (preferably having 1 to 20 carbon atoms, preferably an alkyl group, a cycloalkyl group or an aryl group) Hyperthyroidism),

a mercaptoamine group (preferably having a carbon number of 1 to 20), a sulfonylamino group (preferably a sulfonylamino group having a carbon number of 0 to 20, preferably an alkyl group, a cycloalkyl group or an aryl group), an alkyl sulfide Base (preferably having a carbon number of 1 to 20, more preferably 1 to 12, such as methylthio, ethylthio, isopropylthio, pentylthio, hexylthio, octylthio or benzylthio), ring An alkylthio group (preferably having a carbon number of 3 to 20), an arylthio group (preferably having a carbon number of 6 to 26), an alkylsulfonyl group, a cycloalkylsulfonyl group or an arylsulfonyl group (preferably Carbon number 1 to 20),

a decyl group (preferably a decyl group having 1 to 20 carbon atoms, preferably substituted by an alkyl group, an aryl group, an alkoxy group and an aryloxy group) or a decyloxy group (preferably having a carbon number of 1 to 20, preferably It is a decyloxy group substituted by an alkyl group, an aryl group, an alkoxy group and an aryloxy group, a hydroxyl group, a cyano group, a nitro group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom).

More preferably, the group selected from the substituent group Z ^R is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkoxycarbonyl group or a cycloalkane. An oxycarbonyl 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, an alkoxycarbonyl group, an amine group, a mercaptoamino group or Cyano group.

When a compound, a substituent or the like contains an alkyl group, an alkenyl group or the like, these may be substituted or unsubstituted. Further, when an aryl group, a heterocyclic group or the like is contained, these may be monocyclic or condensed, and may be substituted or unsubstituted.

Next, a preferred embodiment of the main components of the photoelectric conversion element and the dye-sensitized solar cell will be described.

<Electrically Conductive Support> The conductive support is not particularly limited as long as it has conductivity and can support the photoreceptor layer 2 and the like. The conductive support is preferably an electrically conductive support 1 formed of a conductive material such as a metal, or a conductive film 43 comprising a glass or plastic and a transparent conductive film 43 formed on the surface of the substrate 44. Sex support 41.

Among them, a conductive support 41 of a transparent conductive film 43 of a metal oxide is more preferably provided on the surface of the substrate 44. Such a conductive support 41 can be obtained by coating a surface of the substrate 44 with a conductive metal oxide to form a transparent conductive film 43. The transparent polymer film described in Paragraph No. 0153 of JP-A-2001-291534 is exemplified as the substrate 44 formed of plastic. 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 metal oxide is preferably tin oxide (TO), and particularly preferably indium oxide-tin (tin-doped indium oxide; ITO) or fluorine-doped tin oxide (FTO). The coating amount of the metal oxide at this time is preferably from 0.1 g to 100 g per 1 m ^{2 of the} substrate 44. In the case where the conductive support 41 is used, it is preferable that light is incident from the substrate 44 side.

The conductive support 1 and the conductive support 41 are preferably substantially transparent. The term "substantially transparent" means that the transmittance of light (wavelength: 300 nm to 1200 nm) is 10% or more, preferably 50% or more, and particularly preferably 80% or more. The thickness of the conductive support 1 and the conductive support 41 is not particularly limited, but is preferably 0.05 μm to 10 mm, more preferably 0.1 μm to 5 mm, and particularly preferably 0.3 μm to 4 mm. In the case where the transparent conductive film 43 is included, the thickness of the transparent conductive film 43 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 1 and the conductive support 41 may have a light management function on the surface. For example, an antireflection film in which an oxide film having a high refractive index and a low refractive index is laminated and laminated as described in Japanese Laid-Open Patent Publication No. 2003-123859, and the like, may be provided in Japanese Patent Laid-Open Publication No. 2002-260746. The light guide function described.

<Photosensitive Layer> The photoreceptor layer is not particularly limited as long as it includes the semiconductor fine particles 22 and the electrolyte carrying the dye 21 . Preferably, the photoreceptor layer 2 and the photoconductor layer 42 are listed.

- Semiconductor fine particles (layer formed by semiconductor fine particles) - The semiconductor fine particles 22 are preferably a chalcogenide of a metal (for example, an oxide, a sulfide, a selenide, etc.) or have a perovskite type crystal structure. Microparticles of the compound. The metal chalcogen compound 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 compound having a perovskite crystal structure is preferably exemplified by barium titanate, calcium titanate or the like. Particularly preferred among these are titanium oxide (titanium dioxide), zinc oxide, tin oxide, and tungsten oxide.

The crystal structure of titanium dioxide may be an anatase type, a brookite type, or a rutile type, and an anatase type or a brookite type is preferable. The titanium dioxide nanotube, the nanowire, and the nanorod may be used singly or in combination with titanium dioxide microparticles.

The particle diameter of the semiconductor fine particles 22 is preferably 0.001 μm to 1 μm in primary particles and 0.01 μm in average particle diameter in terms of average particle diameter (the diameter when the projected area is converted into a circle). 100 μm. Examples of the method of coating the semiconductor fine particles 22 on the conductive support 1 or the conductive support 41 include a wet method, a dry method, and other methods.

The semiconductor fine particles 22 preferably have a large surface area to facilitate adsorption of the pigment 21 . For example, in a state where the semiconductor fine particles 22 are coated on the conductive support 1 or the conductive support 41, 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.

The preferred thickness of the layer (photoreceptor layer) formed of the semiconductor fine particles is not limited depending on the use of the photoelectric conversion element, and is typically 0.1 μm to 100 μm. In the case of being used as a dye-sensitized solar cell, it is more preferably 1 μm to 50 μm, still more preferably 3 μm to 30 μm.

The semiconductor fine particles 22 are preferably applied to the conductive support 1 or the conductive support 41, and then calcined at a temperature of 100 to 800 ° C for 10 minutes to 10 hours to adhere the particles to each other. In the case where glass is used as the material of the conductive support 1 or the substrate 44, the film formation temperature is preferably 60 to 600 °C.

The coating amount of the semiconductor fine particles 22 on the surface area per 1 m ^{2 of the} conductive support 1 or the conductive support 41 is preferably 0.5 g to 500 g, more preferably 5 g to 100 g.

Between the conductive support 1 or the conductive support 41 and the photoreceptor layer 2 or the photoreceptor layer 42, the electrolyte contained in the photoreceptor layer 2 or the photoreceptor layer 42 is prevented from coming into direct contact with the conductive support 1 or the conductive support 41. The reverse current generated is preferably a short circuit preventing layer. Further, in order to prevent contact between the light receiving electrode 5 or the light receiving electrode 40 and the opposite electrode 4 or the opposite electrode 48, it is preferable to use a spacer S (refer to FIG. 2) or a spacer.

- Pigment - In the photoelectric conversion element 10 and the dye-sensitized solar cell 20, a metal complex dye mixture containing the metal complex dye (1) and the metal complex dye (2) is used as the sensitizing dye 21. The metal complex pigment mixture is as described above.

The amount of the dye to be used is preferably from 0.01 millimolar to 100 millimolar, more preferably from 0.1 millimole to 50 millimeters per 1 m ^{2 of the} conductive support 1 or the conductive support 41. Moer, especially good is 0.1 millimoles to 10 millimoles. Further, the amount of adsorption of the pigment 21 to the semiconductor fine particles 22 is preferably 0.001 millimoles to 1 millimole, more preferably 0.1 millimoles to 0.5 millimoles, per 1 g of the semiconductor fine particles 22. By setting the amount of the pigment, the sensitizing effect in the semiconductor fine particles 22 can be sufficiently obtained. The content ratio of each of the metal complex dyes to the metal complex dye (1) and the metal complex dye (2) is preferably an index indicating the amount of the carboxyl group relative to all the carboxyl groups. R _CS is specified. Preferably, R is an index representing the _CS index R represents the same dye mixture of the metal complex is present in an amount present in an amount of the _CS.

After the dye is carried on the semiconductor fine particles 22, the surface of the semiconductor fine particles 22 may be treated with an amine compound. Preferred examples of the amine compound include a pyridine compound (for example, 4-tert-butylpyridine or polyvinylpyridine). When these amine compounds are liquid, they can be used as they are, or they can be used by dissolving in an organic solvent.

- Co-Adsorbent - In the present invention, it is preferred to further use a co-adsorbent together with a metal complex dye mixture or a pigment which is used in combination as needed. Such a co-adsorbent is preferably a co-adsorbent having one or more acidic groups (preferably a carboxyl group or a salt thereof), and examples thereof include 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, palmitic acid, dodecanoic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and sub-Asian. Sesame oil and so on. Examples of the compound having a steroid skeleton include cholic acid, glycocholic acid, chenodeoxycholic acid, hyocholic acid, deoxycholic acid, and lithocholic. Acid), ursodeoxycholic acid, etc. Preferred are cholic acid, deoxycholic acid, and chenodeoxycholic acid, and more preferred is deoxycholic acid. The co-adsorbent is preferably a co-adsorbent represented by the formula (CA) described in Paragraph No. 0125 to Paragraph No. 0129 of JP-A-2014-82187, and JP-A-2014-82187 The description of paragraph number 0125 to paragraph number 0129 is directly incorporated into the present specification.

The co-adsorbent is adsorbed on the semiconductor fine particles 22 to have an effect of suppressing an inefficient association of the metal complex pigment and preventing a redox system from the surface of the semiconductor fine particles to the electrolyte. The effect of reverse electron transfer. The amount of the co-adsorbent used is not particularly limited, and from the viewpoint of effectively exhibiting the effect, it is preferably from 1 mol to 200 mol, more preferably 1 mol of the metal complex dye. It is 10 moles to 150 moles, and the best is 20 moles to 50 moles.

- Light Scattering Layer - In the present invention, the light scattering layer is different from the semiconductor layer 45 in that it has a function of scattering incident light. In the dye-sensitized solar cell 20, the light-scattering layer 46 preferably contains rod-like or plate-shaped metal oxide fine particles. The metal oxide used in the light-scattering layer 46 is, for example, a chalcogen compound (oxide) of the metal described as a compound forming the semiconductor fine particles. In the case where the light scattering layer 46 is provided, it is preferable that the thickness of the light scattering layer is 10% to 50% of the thickness of the photoreceptor layer. The light-scattering layer 46 is preferably a light-scattering layer described in Japanese Laid-Open Patent Publication No. 2002-289274, the disclosure of which is incorporated herein by reference.

<Charge Transfer Body Layer> The charge transport layer 3 and the charge transport layer 47 used in the photoelectric conversion device of the present invention are layers having a function of supplementing electrons to the oxidant of the dye 21, and are provided on the light receiving electrode 5 or the light receiving electrode 40 and are opposite to each other. Between the electrode 4 or the opposite electrode 48. The charge transporting body layer 3 and the charge transporting body layer 47 contain an electrolyte. Here, the "charge-containing body layer-containing electrolyte" means a form including the following two forms: a form in which the charge-transporting body layer contains only an electrolyte, and a form in which a substance other than the electrolyte and the electrolyte is contained. The charge transporting body layer 3 and the charge transporting body layer 47 may be in the form of a solid, a liquid, a gel, or any of these mixed states.

- Electrolyte - Examples of the electrolyte include a liquid electrolyte in which a redox is dissolved in an organic solvent, a molten salt containing a redox pair, and a liquid obtained by dissolving a redox pair in an organic solvent. A so-called gel electrolyte or the like formed in a polymer matrix. Among them, a liquid electrolyte is preferred in terms of photoelectric conversion efficiency.

Examples of the redox pair include iodine and iodide (preferably an iodide salt, an iodinated ionic liquid, preferably lithium iodide, tetrabutylammonium iodide, tetrapropylammonium iodide, iodide Combination of propylidene oxime), alkyl viologen (eg, methyl viologen chloride, hexyl viologen bromide, benzyl viologen tetrafluoroborate) in combination with its reducing body, polyhydroxybenzene (eg, para-benzene) Combination of diphenol, naphthalenediol, etc.) with its oxidant, combination of a divalent iron complex and a trivalent iron complex (for example, a combination of red blood salt and yellow blood salt), and a two-valent cobalt mismatch a combination of a substance and a trivalent cobalt complex. Preferred among these are a combination of iodine and iodide or a combination of a divalent cobalt complex and a trivalent cobalt complex, particularly preferably a combination of iodine and iodide.

The cobalt complex is preferably a complex represented by the formula (CC) described in Paragraph No. 0144 to Paragraph No. 0156 of JP-A-2014-82189, Japanese Patent Laid-Open No. 2014-82189 The description of paragraph number 0144 to paragraph number 0156 of the publication is directly incorporated into the present specification.

In the case where the electrolyte uses a combination of iodine and iodide, it is preferred to further use a 5-membered ring or a 6-membered ring of an iodide salt of a nitrogen-containing aromatic cation.

The organic solvent used in the liquid electrolyte and the gel electrolyte is not particularly limited, and is preferably an aprotic polar solvent (for example, acetonitrile, propylene carbonate, ethylene carbonate, dimethylformamide, dimethyl group). Aamu, cyclobutyl hydrazine, 1,3-dimethylimidazolidinone, 3-methyloxazolidinone, etc.). Particularly, the organic solvent used in the liquid electrolyte is preferably a nitrile compound, an ether compound, an ester compound or the like, more preferably a nitrile compound, particularly preferably acetonitrile or methoxypropionitrile.

The molten salt or the gel electrolyte is preferably a molten salt or a gel electrolyte described in Paragraph No. 0205 and Paragraph No. 0208 to Paragraph No. 0213 of Japanese Patent Laid-Open No. Hei. No. 2014-139931, Japanese Patent Laid-Open No. Hei No. 2014-139931 The description of paragraph number 0205 and paragraph number 0208 to paragraph number 0213 of the publication is directly incorporated into the present specification.

The electrolyte may contain, in addition to the pyridine compound such as 4-tert-butylpyridine, an aminopyridine compound, a benzimidazole compound, an aminotriazole compound, an aminothiazole compound, an imidazole compound, an aminotriazine compound, a urea compound, A guanamine compound, a pyrimidine compound or a nitrogen-free heterocycle is used as an additive.

Further, in order to improve the photoelectric conversion efficiency, a method of controlling the moisture of the electrolytic solution may be employed. As a preferable method of controlling moisture, a method of controlling the concentration or a method of coexisting the dehydrating agent can be mentioned. It is preferred to adjust the moisture content (content ratio) of the electrolytic solution to 0% by mass to 0.1% by mass. Iodine can also be used as a cage compound for iodine and cyclodextrin. Further, a cyclic ruthenium may be used, and an antioxidant, a hydrolysis inhibitor, a decomposition inhibitor, and zinc iodide may also be added.

Instead of the above liquid electrolyte and pseudo-solid electrolyte, a solid charge transport layer such as a p-type semiconductor or a hole transport material such as CuI, CuNCS or the like can be used. Further, an electrolyte described in "Nature", Vol. 486, p. 487 (2012) or the like can also be used. The organic charge transport layer can also use an organic hole transport material. The organic hole transporting material is preferably described in paragraph number 0214 of JP-A-2014-139931, and the description of paragraph number 0214 of JP-A-2014-139931 is directly incorporated into the present. In the manual.

The redox pair is a carrier for electrons, and therefore it is preferably contained in a certain concentration. The preferred concentration is 0.01 mol/L or more in total, more preferably 0.1 mol/L or more, and particularly preferably 0.3 mol/L or more. The upper limit in this case is not particularly limited and is usually about 5 mol/L.

<Counter Electrode> The counter electrode 4 and the counter electrode 48 preferably function as a positive electrode of the dye-sensitized solar cell. The counter electrode 4 and the counter electrode 48 may be configured to have the same configuration as the conductive support 1 or the conductive support 41. However, in the configuration in which the strength is sufficiently maintained, the substrate 44 is not necessarily required. The structure of the counter electrode 4 and the counter electrode 48 is preferably a structure having a high current collecting effect. In order to allow light to reach the photoreceptor layer 2 and the photoreceptor layer 42, at least one of the conductive support 1 or the conductive support 41 and the counter electrode 4 or the counter electrode 48 must be substantially transparent. In the dye-sensitized solar cell of the present invention, it is preferable that the conductive support 1 or the conductive support 41 is transparent and the sunlight is incident from the conductive support 1 or the conductive support 41 side. In this case, it is more preferable that the opposite electrode 4 and the opposite electrode 48 have a property of reflecting light. The counter electrode 4 and the counter electrode 48 of the dye-sensitized solar cell are preferably glass or plastic in which a metal or a conductive oxide is vapor-deposited, and particularly preferably a glass in which platinum is vapor-deposited. In the dye-sensitized solar cell, in order to prevent evapotranspiration of the constituent, it is preferred to seal the side surface of the battery by a polymer or an adhesive.

[Photoelectric conversion element and method for producing a dye-sensitized solar cell] The photoelectric conversion element and the dye-sensitized solar cell of the present invention can contain at least each of the metal complex dye (1) and the metal complex dye (2). A metal complex dye mixture and a solvent dye solution (the dye solution of the present invention) are produced. The metal complex dye (1) and the metal complex dye (2) contained in the dye solution of the present invention have the same preferred ranges as described above.

The solvent to be described in Japanese Laid-Open Patent Publication No. 2001-291534 is exemplified, but is not particularly limited thereto. In the present invention, an organic solvent is preferred, and further, an alcohol solvent, a guanamine solvent, a nitrile solvent, a ketone solvent, a hydrocarbon solvent, and a mixed solvent of two or more kinds thereof are more preferable. The mixed solvent is preferably a mixed solvent of an alcohol solvent and a solvent selected from the group consisting of a guanamine solvent, a nitrile solvent, a ketone solvent, or a hydrocarbon solvent. Further preferred is a mixed solvent of an alcohol solvent and a guanamine solvent, a mixed solvent of an alcohol solvent and a hydrocarbon solvent, a mixed solvent of an alcohol solvent and a nitrile solvent, and particularly preferably a mixed solvent of an alcohol solvent and a guanamine solvent, and an alcohol solvent. A mixed solvent of a nitrile solvent. Specifically, preferred is a mixed solvent of at least one of methanol, ethanol, propanol and tert-butanol with at least one of dimethylformamide and dimethylacetamide, methanol, ethanol, propanol and A mixed solvent of at least one of tributanol and acetonitrile.

The pigment solution of the present invention may also contain other components as needed. Preferably, the dye solution contains a co-adsorbent, and the co-adsorbent is preferably the co-adsorbent. Here, in the case of producing the photoelectric conversion element or the dye-sensitized solar cell of the dye solution of the present invention, in order to directly use the solution, a dye solution in which the concentration of the metal complex dye or the co-adsorbent is adjusted is preferable. In the present invention, it is preferred that the dye solution of the present invention contains 0.001% by mass to 0.1% by mass of the metal complex dye of the present invention. The amount of the co-sorbent used is as described above.

The pigment solution preferably has a moisture content adjusted. In the present invention, it is preferred to adjust the moisture content to 0% by mass to 0.1% by mass.

In the present invention, it is preferred that the dye solution (1) and the metal complex dye (2) or a dye containing the same be carried on the surface of the semiconductor fine particles by using the dye solution. Photoreceptor layer. That is, it is preferred to apply (including a dipping method) the dye solution on the semiconductor fine particles provided on the conductive support to dry or harden it to form a photoreceptor layer.

Further, a charge transfer body layer or a counter electrode or the like is further provided on the light-receiving electrode including the photoreceptor layer produced as described above, whereby the photoelectric conversion element of the present invention can be obtained.

The dye-sensitized solar cell is manufactured by connecting the external circuit 6 to the conductive support 1 and the counter electrode 4 of the photoelectric conversion element produced as described above.

When the photosensitive layer is formed using the dye solution of the present invention, a photoelectric conversion element and a dye-sensitized solar cell exhibiting a high open circuit voltage and stable photoelectric conversion efficiency can be produced. [Examples]

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

Example 1 [Synthesis of Metal Complex Pigment] The metal complex dye D-1 to the metal complex dye D-25 synthesized in the present example, and the metal complex dye C- for comparison were shown below. 1 to the structure of the metal complex dye C-8, the metal complex dye B-1, and the metal complex dye B-2. In the following specific examples, Et represents an ethyl group, Bn represents a benzyl group, and Bu represents a butyl group.

[Chemistry 16]

[化17]

[化18]

[Chemistry 19]

[Chemistry 20]

(Synthesis of Metal Complex Pigment B-1) The metal complex dye B-1 was synthesized in accordance with the following scheme. The meanings of the abbreviations in the following procedures and descriptions are as follows. Ph: phenyl THF: tetrahydrofuran Et: ethyl ^t Bu : tert-butyl Me: methyl DMF: N,N-dimethylformamide TfOH: trifluoromethanesulfonic acid

[Chem. 21]

(i) Synthesis of Compound (1-3) In a three-necked flask, Compound (1-1) (1.50 g, 7.50 mmol), Compound (1-2) (2.65 g, 8.25 mmol), and cesium carbonate (3.18 g) were charged. Nitrogen replacement was carried out with 9.75 mmol), THF (7.5 mL) and water (0.75 mL). Tetrakis(triphenylphosphine)palladium(IV) (433 mg, 0.275 mmol) was added to the mixed solution, and the reaction was carried out at 75 ° C for 4 hours. After the reaction solution was left to cool and returned to room temperature, water and ethyl acetate were added to carry out liquid separation. The obtained organic layer was dried over magnesium sulfate, filtered and concentrated. The obtained crude product was purified by silica gel column chromatography to give Compound (1-3) (1.28 g, yield: 60%).

(ii) Synthesis of Compound (1-4) In a three-necked flask, Compound (1-3) (4.60 g, 16.0 mmol), potassium third potassium hydride (3.59 g), ethyl trifluoroacetate (4.55 g) were charged. 32.0 mmol) and toluene (138 mL) were reacted at 80 ° C for 2 hours. The reaction solution was allowed to stand to cool to room temperature, and then a saturated aqueous ammonium chloride solution and ethyl acetate were added to carry out liquid separation. The obtained organic layer was dried over magnesium sulfate, filtered and concentrated. To the obtained crude, hydrazine monohydrate (1.92 g, 38.4 mmol) and ethanol (23 mL) were added, and the reaction was carried out at 80 ° C for 3 hours. After the reaction solution was allowed to stand to cool to room temperature, concentrated hydrochloric acid was added thereto and stirred for 30 minutes, and the reaction solution was neutralized with an aqueous sodium hydrogencarbonate solution. Water and ethyl acetate were added to the obtained reaction solution to carry out liquid separation. The obtained organic layer was dried over magnesium sulfate, filtered and concentrated. The obtained crude product was purified by silica gel column chromatography to give Compound (1-4) (5.06 g, yield: 83%).

(iii) Synthesis of Compound (1-6) In a three-necked flask, Compound (1-5) (3.52 g, 5.73 mmol), Compound (1-4) (2.06 g, 5.43 mmol) and DMF (18 mL) were charged. The reaction was carried out at 140 ° C for 1 hour. The crude product obtained by concentration was purified by silica gel column chromatography to give Compound (1-6) (2.91 g, yield: 55%).

(iv) Synthesis of Compound (1-7) A three-necked flask was charged with Compound (1-6) (1.50 g, 1.63 mmol), ammonium thiocyanate (1.24 g, 16.3 mmol) and DMF (30 mL). The reaction was carried out for 5 hours at 120 °C. After the reaction solution was left to cool and returned to room temperature, water and ethyl acetate were added to carry out liquid separation. The obtained organic layer was dried over magnesium sulfate, filtered and concentrated. The obtained crude product was purified by silica gel column chromatography to give Compound (1-7) (954 mg, yield: 62%).

(v) Synthesis of Metal Complex Pigment B-1 A three-necked flask was charged with a compound (1-7) (945 mg, 1.00 mmol), THF (15 mL), methanol (15 mL), and a 3N aqueous sodium hydroxide solution. (2.0 mL), the reaction was carried out for 1 hour at room temperature. The reaction solution was neutralized to pH 3.0 using a 1 N trifluoromethanesulfonic acid/methanol solution, and the precipitated solid was collected by filtration, and washed with methanol to obtain a metal complex dye B-1 (885 mg, yield). 98%).

(Synthesis of Metallic Complex Pigment B-2) The metal complex dye B-2 was synthesized in the same manner as the metal complex dye B-1.

(Synthesis of Metal Complex Dye D-1 and Metal Complex Dye D-2) In a 0.05 mol/L methanol solution of the metal complex dye B-1, a metal complex dye B- is added. 1 is a 1 mol/L aqueous solution or a methanol solution of 1 equivalent (1/3 equivalent of the carboxyl group) or 2 equivalents (2/3 equivalent of the carboxyl group) of a base (sodium hydroxide). The carboxyl group is partially salted. Each of the obtained solutions was concentrated to obtain a metal complex dye D-1 and a metal complex dye D-2.

The metal complex dye B-1 synthesized as described above, and the metal complex dye D-1 and the metal complex dye D-2 were subjected to acid-base neutralization titration. As a result, it was confirmed that a carboxylate (salt of a carboxyl group) was produced in proportion to the amount of the base added. The formation of a carboxylate was confirmed in the same manner below.

Further, the obtained metal complex dye D-1 and metal complex dye D-2 were identified by ¹ H-NMR measurement (DMSO-d6). Metal complex dye D-1: δ = 0.86 (t, J = 7.2 Hz, 3H), 1.28 - 1.39 (m, 6H), 1.64 - 1.71 (m, 2H), 2.88 (t, J = 7.2 Hz, 2H), 7.02 (d, J=3.6 Hz, 1H), 7.08 (s, 1H), 7.68 (d, J=3.6 Hz, 1H), 7.77 (dd, J=5.6 Hz, 1.6 Hz, 2H), 7.95 (d, J=5.6 Hz, 2H), 8.20 (d, J=8.4 Hz, 1H), 8.39 (dd, J=8.4 Hz, 2.0 Hz, 1H), 8.98 (s, 2H), 9.12 (s, 2H) ), 9.62 (d, J=2.0 Hz, 1H) Metal complex dye D-2: δ = 0.86 (t, J = 7.2 Hz, 3H), 1.28 - 1.39 (m, 6H), 1.64 - 1.71 (m , 2H), 2.88 (t, J=7.2 Hz, 2H), 7.02 (d, J=3.6 Hz, 1H), 7.06 (s, 1H), 7.67 (d, J=3.6 Hz, 1H), 7.71 (dd , J=5.6 Hz, 1.6 Hz, 2H), 7.85 (d, J=5.6 Hz, 2H), 8.17 (d, J=8.4 Hz, 1H), 8.35 (dd, J=8.4 Hz, 2.0 Hz, 1H) , 8.83 (s, 2H), 8.97 (s, 2H), 9.63 (d, J=2.0 Hz, 1H)

(Synthesis of metal complex dye D-3 to metal complex dye D-25 and metal complex dye C-1 to metal complex dye C-8) in metal complex dye D-1 and metal In the same manner as the synthesis of the metal complex dye D-1 and the metal complex dye D-2, the metal complex dye D-3 is synthesized in the same manner as in the synthesis of the complex dye D-2. ~ Metal complex dye D-14. A metal complex dye in which a carboxyl group is not salted is synthesized in the same manner as the metal complex dye B-1, and the metal complex dye D-1 and the metal complex dye D are mixed with the metal complex dye. In the same manner as in the synthesis of -2, the carboxyl group is partially salted to synthesize the metal complex dye D-15 to the metal complex dye D-25. The metal complex dye C-1, the metal complex dye C-5, and the metal complex dye C-7 in which the carboxyl group is not salted are synthesized in the same manner as the metal complex dye B-1. The metal complex dye C-1, the metal complex dye C-5, and the metal complex dye C-7 are used in the same manner as the synthesis of the metal complex dye D-1 and the metal complex dye D-2. The carboxyl group is partially salted to synthesize the metal complex dye C-2 to the metal complex dye C-4, the metal complex dye C-6, and the metal complex dye C-8.

Each of the synthesized metal complex dyes was subjected to mass spectrometry (MS) measurement, and was identified based on the following results. D-1: ESI-MS m/z = 926.1 (M+H ⁺ ) D-2: ESI-MS m/z=948.0 (M+H ⁺ ) D-3: ESI-MS m/z = 1145.4 (M +H ⁺ ) D-4: ESI-MS m/z = 1386.6 (M+H ⁺ ) D-5: ESI-MS m/z = 1095.2 (M+H ⁺ ) D-6: ESI-MS m/z ^{= 1286.4 (m + H +)} D-7: ESI-MS m / z = 1164.3 (m + H +) D-8: ESI-MS m / z = 1420.6 (m + H +) D-9: ESI- MS m/z = 942.0 (M + H ⁺ ) D - 10: ESI-MS m/z = 980.0 (M+H ⁺ ) D-11: ESI-MS m/z=910.1 (M+H ⁺ ) D- 12: ESI-MS m/z = 916.1 (M+H ⁺ ) D-13: ESI-MS m/z=1036.0 (M+H ⁺ ) D-14: ESI-MS m/z=1167.9 (M+H ⁺ ) D-15: ESI-MS m/z = 958.0 (M+H ⁺ ) D-16: ESI-MS m/z=984.1 (M+H ⁺ ) D-17: ESI-MS m/z=938.1 (M+H ⁺ ) D-18: ESI-MS m/z = 910.1 (M+H ⁺ ) D-19: ESI-MS m/z=1006.1 (M+H ⁺ ) D-20: ESI-MS m /z=925.1 (M+H ⁺ ) D-21: ESI-MS m/z=959.0 (M+H ⁺ ) D-22: ESI-MS m/z=858.1 (M+H ⁺ ) D-23: ESI-MS m/z=903.1 (M+H ⁺ ) D-24: ESI-MS m/z=1121.2 (M+H ⁺ ) D-25: ESI-MS m/z=894.1 (M+H ⁺ ) C-1: ESI-MS m/z = 904.1 (M+H ⁺ ) C-2: ESI-MS m/z=926.1 (M+H ⁺ ) C-3: ESI-MS m/z=1145.4 (M +H ⁺ ) C-4: ESI-MS m/z = 942.0 (M+H ⁺ ) C-5: ESI-MS m/z=914.1 (M+H ⁺ ) C-6: ESI-MS m/z=1155.3 (M+H ⁺ ) C-7: ESI-MS m/z = 954.1 (M+H ⁺ ) C-8: ESI-MS m/z=956.1 (M+H ⁺ ) B-1: ESI-MS m /z=904.1(M+H ⁺ ) B-2: ESI-MS m/z =936.0 (M+H ⁺ )

[Production of dye-sensitized solar cell] Ten dye-sensitized solar cells 20 shown in Fig. 2 were produced using each of the metal complex dyes synthesized in the above [synthesis of metal complex dye]. Mm × 5 mm size). This production was carried out by the method shown below. Each of the dye-sensitized solar cells 20 produced was evaluated for the following properties.

(Preparation of Photoreceptor Precursor) A fluorine-doped SnO ₂ conductive film (transparent conductive film 43 and film thickness: 500 nm) was formed on a glass substrate (substrate 44, thickness: 4 mm) to prepare a conductive support 41. Then, a titanium oxide paste "18NR-T" (manufactured by DyeSol Co., Ltd.) was screen-printed on the SnO ₂ conductive film, and dried at 120 °C. Next, the titanium oxide paste "18NR-T" was screen-printed again and dried at 120 ° C for 1 hour. Thereafter, the dried titanium oxide paste was fired in air at 500 ° C to form a semiconductor layer 45 (layer thickness: 12 μm). Further, a titanium oxide paste "18NR-AO" (manufactured by Daisaku Co., Ltd.) was screen-printed on the semiconductor layer 45, and dried at 120 ° C for 1 hour. Thereafter, the dried titanium oxide paste was calcined at 500 ° C to form a light-scattering layer 46 (layer thickness: 5 μm) on the semiconductor layer 45. The photoreceptor layer 42 was formed on the SnO ₂ conductive film as described above (area of the light-receiving surface: 5 mm × 5 mm, layer thickness: 17 μm, and no metal complex dye was carried), and an unsupported metal complex was prepared. The light-receiving electrode precursor of the pigment.

(Pigment liquid preparation) First, in a mixed solvent of 1:1 (volume ratio) of third butanol and acetonitrile dehydrated with magnesium ethoxide, the concentration is 2 × 10 ^-4 mol/L. Each of the synthesized metal complex pigments further contains 20 mol of deoxycholic acid as a co-adsorbent with respect to 1 mol of the metal complex dye to prepare a pigment of each of the metal complex pigments. Solution. Next, the dye solutions of the prepared metal complex dyes were mixed so that the molar ratios x, y, and z described in Table 1 were mixed to prepare respective dye solutions. The index R _CS indicating the amount of the salt of the carboxyl group in the dye solution is expressed as "indicator R _CS " in Table 1.

(Pigment adsorption) In each dye solution, the light-receiving electrode precursor was immersed at 25 ° C for 20 hours, and was dried from the dye solution. The light-receiving electrode 40 in which each metal complex dye mixture is carried on the light-receiving electrode precursor is produced as described above.

(Assembling of Pigment-Sensitized Solar Cell) A platinum electrode (thickness of a Pt film: 100 nm) having the same shape and size as that of the conductive support 41 was produced as the counter electrode 48. Further, as the electrolytic solution, 0.1 M (mol/L) of iodine, 0.1 M of lithium iodide, 0.5 M of 4-tert-butylpyridine, and 0.6 M of 1,2-dimethyl-3-propyl group were used. The imidazolium iodide was dissolved in acetonitrile to prepare a liquid electrolyte. Further, a spacer S "Surlyn" (trade name, manufactured by DuPont) having a shape matching the size of the photoreceptor layer 42 was prepared. Each of the light-receiving electrodes 40 produced as described above and the counter electrode 48 are thermally pressed against each other via the spacer S, and then the liquid is filled between the photoconductor layer 42 and the counter electrode 48 from the electrolyte injection port. The electrolyte forms a charge transporting body layer 47. The outer periphery of the battery prepared as described above and the electrolyte injection port were sealed and cured by using resin XNR-5516 (trade name, manufactured by Nagase Chemical Co., Ltd.) to produce each dye-sensitized solar cell (sample No. 1 to test) Sample No. 40, sample No. r01 and sample No. r02, and sample No. c01 to sample No. c05).

(Measurement of Open Circuit Voltage and Photoelectric Conversion Efficiency) Regarding each of the dye-sensitized solar cells of each sample number to be produced, the open circuit voltage (V _OC ) and the photoelectric conversion efficiency (η) were measured by the following methods. By using a solar simulator (manufactured by WACOM) under the trade name "WXS-85H", each dye-sensitized solar cell is irradiated with 1000 W from a xenon lamp that passes through an AM1.5 filter. The battery characteristics were tested by simulating sunlight of /m ² , and the current-voltage characteristics were measured using an IV tester. The photoelectric conversion efficiency was determined from the measured current-voltage characteristics. Moreover, the open circuit voltage measured at this time is read. The dye-sensitized solar cell of each sample number was measured for 10 samples for the current-voltage characteristics. The dye-sensitized solar cell of the present invention (sample No. 01 to sample No. 40) is a dye-sensitized solar cell (sample number c01 to sample number c05) in which the measured photoelectric conversion efficiency is compared. Higher value.

(Evaluation of Stability of Photoelectric Conversion Efficiency) The standard deviation σ of the photoelectric conversion efficiency of the obtained ten samples was obtained for each of the dye-sensitized solar cells of each sample number, and the photoelectricity was evaluated by the standard deviation σ. Stability of conversion efficiency. In the present invention, E above the stability evaluation of the photoelectric conversion efficiency is a pass level of the test, and preferably D or more. When the standard deviation σ A of the photoelectric conversion efficiency of the ten samples is 0.02 or less, B: When the ratio exceeds 0.02 and is 0.04 or less, C: When the ratio exceeds 0.04 and is 0.06 or less, D: 0.06 or more and 0.08 or less. Case E: When the value exceeds 0.08 and is 0.10 or less F: When the value exceeds 0.10

(Evaluation of Open Circuit Voltage) For each of the dye-sensitized solar cells of each sample number, the open circuit voltage (measured value) of 10 samples was arithmetically averaged to obtain an average value of the open circuit voltage. The evaluation of the open circuit voltage was performed based on the average value of the open circuit voltage (V _r01 ) of the dye-sensitized solar cell (sample No. r01) for reference, and was evaluated by the following criteria. In the present invention, the C or more of the evaluation of the open circuit voltage is a pass level of the test, and preferably B or more. When the average value of the open circuit voltage is 1.05 times or more with respect to the open circuit voltage average value (V _r01 ), B: 1.0 times or more and less than 1.05 times C: 0.98 or more and less than 1.0 times. : less than 0.98

(Measurement of Adsorption Amount of Metal Complex Pigment) In the specific dye solution prepared by the above method, the light-receiving electrode precursor was immersed at 25 ° C for 20 hours, and then pulled out to measure the adsorbed metal complex. The amount of adsorption of the pigment. In addition, the amount of adsorption is measured by washing a light-receiving electrode to which a metal complex dye is adsorbed by a solution of tetrabutylammonium hydroxide in methanol, thereby desorbing the metal complex dye from the light-receiving electrode precursor, and using a high-efficiency liquid The phase chromatography (HPLC: High Performance Liquid Chromatography) was measured by the amount of adsorption (mmol/cm ² ) of the projected area of the layer formed by the semiconductor fine particles. The results are shown in Table 1.

[Table 1] Table 1

The following are known from the results of Table 1. The dye-sensitized solar cell of the present invention (sample No. 1 to sample No. 40) is a metal complex dye represented by the formula (1) and a metal complex dye represented by the formula (2) is adsorbed to the semiconductor fine particles. on. As a result, the stability of the photoelectric conversion efficiency is improved, and the open circuit voltage is also highly excellent. In the dye-sensitized solar cell of the present invention, when the index R _CS indicating the amount of the salt of the carboxyl group is 200 or less, the improvement of the open circuit voltage and the stability of the photoelectric conversion efficiency can be achieved, and if it is 100 or less, the open circuit voltage The improvement effect is further increased. When the index R _CS indicating the amount of presence is 10 or less, the stability of the open circuit voltage and the photoelectric conversion efficiency can be achieved at a high level. Further, in the dye-sensitized solar cell of the present invention, if M ¹ of the formula (L11) is a sodium ion, an ammonium ion or a cerium ion, both the open circuit voltage and the photoelectric conversion efficiency are excellent. In the dye-sensitized solar cell of the present invention, X of the formula (L2) of the ligands L ¹² and L ²² is a sulfur atom, and G ¹ of the formula (L2) is a group represented by the formula (G1-2). , the open circuit voltage is high, and the stability of the photoelectric conversion efficiency is greatly improved. If the monodentate ligand is an NCS base, the stability of the open circuit voltage and photoelectric conversion efficiency is high. It is understood that even in the case where the ligands of L ¹² and L ²² of the respective metal complex dyes have different structures, the above-described excellent performance improvement effect is obtained. Further, it is understood that the amount of adsorption of the metal complex dye of the dye-sensitized solar cell of the present invention is also high.

A metal complex dye mixture containing a metal complex dye represented by the formula (1) and a metal complex dye represented by the following formula (2) in a specific range, and containing the metal The dye solution of the complex dye mixture and the solvent, and the metal complex dye represented by the formula (3) can be suitably used in the production of the dye-sensitized solar cell exhibiting excellent characteristics.

On the other hand, even if the metal complex dye having the following ligand is used at a ratio of the index R _CS indicating the amount of the salt of the carboxyl group to 0.1, the open circuit voltage is low, and the stability of the photoelectric conversion efficiency is also poor (sample No. c01 to sample number c03), wherein the ligand is a thiophenyl group having a ring group containing X corresponding to the formula (L2), and is bonded to the 4-position with respect to the nitrogen atom of the pyridine ring. body. In addition, even if the metal complex dye having the following ligand is used in a ratio of the index R _CS indicating the amount of the salt of the carboxyl group to 0.1, the open circuit voltage is low and the stability of the photoelectric conversion efficiency is also poor (sample No. c04), the ligand is a ligand of the formula (L2) wherein R ²² has an ethynyl group. In addition, when the ring group corresponding to the ring group containing X of the formula (L2) is a benzothiophene ring, the open circuit voltage is low even when the index R _CS indicating the amount of the salt of the carboxyl group is 0.1. The stability of the photoelectric conversion efficiency was also poor (sample No. c05).

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 accompanying claims. Explain widely with scope.

The present application claims priority to Japanese Patent Application No. 2015-054032, filed on Jan. This manual.

1, 41‧‧‧ Conductive support
2, 42‧‧‧ photoreceptor layer
3, 47‧‧‧ charge transfer body layer
4, 48‧‧‧ relative electrode
5, 40‧‧‧Acceptance electrode
6‧‧‧External circuit
10‧‧‧ photoelectric conversion components
20‧‧‧Pigment sensitized solar cells
21‧‧‧ pigment
22‧‧‧Semiconductor particles
43‧‧‧Transparent conductive film
44‧‧‧Substrate
45‧‧‧Semiconductor layer
46‧‧‧Light scattering layer
100‧‧‧Systems for applying photoelectric conversion elements to battery applications
M‧‧‧ action unit (eg electric motor)
S‧‧‧ spacers

1 is a cross-sectional view schematically showing an enlarged view of a circular portion in a layer in a system in which a photoelectric conversion element according to a first embodiment of the present invention is applied to a battery. FIG. 2 is a cross-sectional view schematically showing a dye-sensitized solar cell including the photoelectric conversion element according to the second embodiment of the present invention.

1‧‧‧Electrical support

2‧‧‧Photoreceptor layer

3‧‧‧ Charge Transfer Body Layer

4‧‧‧relative electrode

5‧‧‧Photoelectrode

6‧‧‧External circuit

10‧‧‧ photoelectric conversion components

21‧‧‧ pigment

22‧‧‧Semiconductor particles

100‧‧‧Systems for applying photoelectric conversion elements to battery applications

M‧‧‧ action unit (eg electric motor)

Claims (9)

A photoelectric conversion element comprising a conductive support, a photoreceptor layer containing an electrolyte, a charge transport layer containing an electrolyte, and a photoelectric conversion element of a counter electrode, the photoreceptor layer containing a compound represented by the following formula (1) a metal complex dye and a semiconductor fine particle of a metal complex dye represented by the following formula (2); Formula (1): Ru(L ¹¹ )(L ¹² )(L ¹³ ) Formula (2): Ru(L) ²¹ ) (L ²² ) (L ²³ ) In the formula (1) and the formula (2), L ¹¹ represents a tridentate ligand represented by the following formula (L11), and L ²¹ represents a formula represented by the following formula (L21). a tridentate ligand; L ¹² and L ²² each independently represent a bidentate ligand represented by the following formula (L2); and L ¹³ and L ²³ each independently represent a monodentate ligand; In the formula (L11), M ¹ each independently represents a hydrogen ion or a cation; wherein at least one of the three M ¹ represents a cation, and at least one represents a hydrogen ion; In the formula, G ¹ represents a group represented by any formula of the following formula (G1-1) to formula (G1-5); and R ²¹ represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, or an amine. a heteroaryl group or an aryl group; R ²² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, an amine group, a heteroaryl group or an aryl group; and X represents an oxygen atom, a sulfur atom, an NRf, a selenium group. An atom, C(Rf) ₂ or Si(Rf) ₂ ; Rf represents a hydrogen atom or an alkyl group; n represents an integer of 0 to 2; wherein, in the case where n is 2, two R ²¹ are not bonded to each other. Forming an aromatic ring; In the formula, R ¹¹ to R ¹⁸ each independently represent a hydrogen atom, an alkyl group, a heteroaryl group, an aryl group or a halogen atom; and * represents a bond to the pyridine ring of the formula (L2). The photoelectric conversion element as defined in claim 1, item range, wherein one of said formula (1) in the metal complex dye represented by the formula (L11) M ¹ is a metal cation The complex ^ratio pigment, the metal complex dye of the cation of M ¹ in the formula (L11), and the molar ratio of the metal complex dye represented by the formula (2) are set to y: In the case of z:x, the index R _CS indicating the amount of the salt of the carboxyl group satisfies the following formula (A): (A): R _CS = [(y + 2z) / (x + y + z)] × 100 ≦200. The photoelectric conversion element according to claim 1, wherein the index R _CS satisfies the following formula (B): (B): R _CS = [(y + 2z) / (x + y + z) ] × 100 ≦ 100. The photoelectric conversion element according to claim 1, wherein the index R _CS satisfies the following formula (C): (C): R _CS = [(y + 2z) / (x + y + z) ] × 100≦10. The photoelectric conversion element according to any one of the items 1 to 4, wherein at least one of G ¹ of the L ¹² and G ¹ of the L ²² is the formula (G1-2) The base represented. A dye-sensitized solar cell using the photoelectric conversion element according to any one of claims 1 to 5. A metal complex dye mixture containing a metal complex dye represented by the following formula (1) and a metal complex dye represented by the following formula (2), which is represented by the following formula (1) Among the metal complex dyes, one of M ¹ in the following formula (L11) is a cationic metal complex dye, and two of M ¹ in the following formula (L11) are cationic metal complex dyes. When the molar ratio of the metal complex dye represented by the following formula (2) is y:z:x, the index R _CS indicating the amount of the salt of the carboxyl group satisfies the following formula (A): (A): R _CS = [(y + 2z) / (x + y + z)] × 100 ≦ 200 Formula (1): Ru (L ¹¹ ) (L ¹² ) (L ¹³ ) Formula (2): Ru (L ²¹ ) (L ²² ) (L ²³ ) In the formula (1) and the formula (2), L ¹¹ represents a tridentate ligand represented by the following formula (L11), and L ²¹ represents the following formula (L21). a three-dental ligand represented by the formula; L ¹² and L ²² each independently represent a bidentate ligand represented by the following formula (L2); and L ¹³ and L ²³ each independently represent a monodentate ligand; Wherein M ¹ each independently represents a hydrogen ion or a cation; wherein at least one of the three M ¹ represents a cation and at least one represents a hydrogen ion; In the formula, G ¹ represents a group represented by any formula of the following formula (G1-1) to formula (G1-5); and R ²¹ represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, or an amine. a heteroaryl group or an aryl group; R ²² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, an amine group, a heteroaryl group or an aryl group; and X represents an oxygen atom, a sulfur atom, an NRf, a selenium group. An atom, C(Rf) ₂ or Si(Rf) ₂ ; Rf represents a hydrogen atom or an alkyl group; n represents an integer of 0 to 2; wherein, in the case where n is 2, two R ^{21 are} not bonded to each other to form Aromatic ring In the formula, R ¹¹ to R ¹⁸ each independently represent a hydrogen atom, an alkyl group, a heteroaryl group, an aryl group or a halogen atom; and * represents a bond to the pyridine ring of the formula (L2). A pigment solution containing the metal complex dye mixture and solvent as described in claim 7 of the patent application. A metal complex dye represented by the following formula (3): Formula (3): Ru(L ³¹ )(L ¹² )(L ¹³ ) wherein L ³¹ represents a formula represented by the following formula (L31) a dental ligand; L ¹² represents a bidentate ligand represented by the following formula (L2); and L ¹³ represents a monodentate ligand; Wherein M ³ each independently represents a hydrogen ion, a sodium ion or a cesium ion; wherein, at least one of the three M ³ represents a sodium ion or a cesium ion, and at least one represents a hydrogen ion; In the formula, G ¹ represents a group represented by any formula of the following formula (G1-1) to formula (G1-5); and R ²¹ represents an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylthio group, or an amine. a heteroaryl group or an aryl group; R ²² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, an amine group, a heteroaryl group or an aryl group; and X represents an oxygen atom, a sulfur atom, an NRf, a selenium group. An atom, C(Rf) ₂ or Si(Rf) ₂ ; Rf represents a hydrogen atom or an alkyl group; n represents an integer of 0 to 2; wherein, in the case where n is 2, two R ^{21 are} not bonded to each other to form Aromatic ring In the formula, R ¹¹ to R ¹⁸ each independently represent a hydrogen atom, an alkyl group, a heteroaryl group, an aryl group or a halogen atom; and * represents a bond to the pyridine ring of the formula (L2).