TWI564301B - Metal complex dye composition, photoelectric transducing element and photoelectrochemical cell, and method for preparing metal complex dye - Google Patents

Description

Metal complex dye composition, photoelectric conversion element, photoelectrochemical cell, and method for producing metal complex dye

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

The photoelectric conversion element can be used for various photo sensors, photocopiers, photoelectrochemical cells (such as solar cells), and the like. Among the photoelectric conversion elements, various methods such as a metal photoelectric conversion element, a photoelectric conversion element using a semiconductor, a photoelectric conversion element using an organic pigment or a dye, or a photoelectric conversion element in which these are combined are put into practical use. Among them, a solar cell that uses solar energy that is never exhausted does not require fuel and uses endless clean energy, and its formal practical use is expected. Among them, the lanthanide solar cells have been under research since the beginning, and they have also been popularized by the policies of various countries. However, as an inorganic material, the yield and molecular modification naturally have limits.

Therefore, research on dye-sensitized solar cells is being carried out with all efforts. In particular, Graetzel et al. of the University of Technology in Lausanne, Switzerland, developed a dye-sensitized solar cell in which a pigment of a ruthenium complex was immobilized on the surface of a porous titanium oxide film, and the conversion efficiency of the amorphous ruthenium level was achieved. In this way, the dye-sensitized solar cell has attracted the attention of researchers all over the world.

Patent Document 1 discloses that a dye-sensitized photoelectric conversion element using semiconductor fine particles sensitized with a ruthenium complex dye is used. In addition, there has been reported a photoelectric conversion element using a cheap organic dye as a sensitizer, but it cannot be said that it is a photoelectric conversion element having high conversion efficiency.

Therefore, it has been proposed to adsorb semiconductor particles by a specific structure of photosensitizing dyes. A technique for improving photoelectric conversion efficiency (for example, refer to Patent Documents 2 and 3). However, since the photosensitizing dye (pure product) described in Patent Documents 2 and 3 has low solubility in a solvent, the amount of adsorption of the dye to the semiconductor fine particles is insufficient under certain conditions, and the photoelectric conversion efficiency is not sufficient. Therefore, the use of the dye is insufficient. It takes a long time to be large or dissolved, and it is insufficient in terms of productivity.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] US Patent No. 5,463,057

[Patent Document 2] Japanese Patent No. 4576494

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2001-291534

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

As a result of intensive studies, the inventors of the present invention have found that a metal complex dye containing a specific ligand has high solubility in a solvent, and can increase the amount of adsorption of the pigment on the semiconductor fine particles, thereby providing high conversion efficiency. Photoelectric conversion element and photoelectrochemical cell. The present invention has been completed based on this finding.

According to the present invention, the following invention is provided.

<1> A metal complex dye composition comprising a metal complex dye represented by the following formula (1), and a metal complex dye represented by the following formula (5) and/or a metal complex dye represented by the formula (6); based on an area of 254 nm detected by HPLC (High Performance Liquid Chromatography), The content ratio of the metal complex dye represented by the formula (5) and the metal complex dye represented by the formula (6) is 0.5 to 5% in total.

M ¹ (LL ¹ ) _m1 (LL ² ) _m2 (Z ¹ ) ₂ ‧(CI ¹ ) _m3 Formula (1) [In the formula (1), M ¹ represents a metal atom, and LL ¹ is a formula ( 2) The bidentate ligand shown, LL ² is a bidentate ligand represented by the following formula (3); m1 represents 1, m2 represents 1; and Z ¹ represents a ligand selected from the group consisting of isosulfur At least one of a cyano group, an isocyanate group, and an isoselenocyano group; CI ¹ represents a counter ion when a charge is required to neutralize a charge, and m3 is an integer of 0 or more. ]

[In the formula (2), R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ independently represent an acidic group or a salt thereof or a hydrogen atom, and R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ may be the same or different, but R ¹¹ At least one of ~R ¹⁴ and R ²¹ to R ²⁴ is an acidic group or a salt thereof. ]

[In the general formula (3), n1 and n2 independently represent an integer of 0 to 3, and Y ¹ and Y ² independently represent a hydrogen atom or a heteroaryl group represented by the following formula (4), but Ar ¹ and Ar ^{2 are} independently The heteroaryl group represented by the following formula (4) is represented. ]

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

M ¹ (LL ¹ ) _m1 (LL ² ) _m2 (Z ¹ ) (CN) ‧ (CI ¹ ) _m3 Formula (5) [In the formula (5), M ¹ , LL ¹ , LL ² , Z ¹ , The meanings of CI ¹ , m1, m2 and m3 are the same as those in the formula (1). ]

M ¹ (LL ¹ ) _m1 (LL ² ) _m2 (CN) ₂ ‧(CI ¹ ) _m3 Formula (6)

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

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

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

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

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

In the formula (8), R ⁶¹ and R ^{62 each} independently represent an alkyl group, an alkoxy group or an alkynyl group, and A ¹ and A ² independently represent a carboxyl group or a salt thereof. ]

The metal complex dye composition according to any one of the above-mentioned items (5), wherein the metal complex dye represented by the formula (5) is represented by the following formula (9). The metal complex dye represented by the formula (6) is represented by the following formula (10).

In the formula (9), R ⁷¹ and R ^{72 each} independently represent an alkyl group, an alkoxy group or an alkynyl group, and A ⁵ and A ⁶ independently represent a carboxyl group or a salt thereof. In the formula (10), R ⁷³ and R ^{74 each} independently represent an alkyl group, an alkoxy group or an alkynyl group, and A ⁷ and A ^{8 are each} independently a carboxyl group or a salt thereof. ]

The metal complex dye composition according to any one of the above aspects, wherein the metal complex dye represented by the formula (5) is represented by the following formula (11). The metal complex dye represented by the formula (6) is represented by the following formula (12).

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

<7> A method for producing a metal complex dye of the following formula (1), comprising: a metal complex dye comprising the following formula (13) by external heating and a general formula (14) The temperature of the mixture of compounds rises.

_{^{M 1 (LL 1) m1 (}} LL 2) m2 (Z 2) m4 ‧ (CI 1) _m5 in formula (13) [in the formula ^{(13), M 1, LL} 1, LL 2, CI 1, m1 and The meaning of m2 is the same as in the formula (1), Z ² is a 1-dentate or 2-dentate ligand, m4 represents an integer of 1 to 2, and when Z ² is a dental ligand, m4 represents 2 and Z ² is 2. In the case of a dental ligand, m4 represents 1, and m5 is an integer of 0 or more. ]

M ¹¹ QCN Formula (14) [In the formula (14), M ¹¹ represents an inorganic or organic ammonium ion, a proton or an alkali metal ion, and Q represents a sulfur atom, an oxygen atom or a selenium atom. ]

M ¹ (LL ¹ ) _m1 (LL ² ) _m2 (Z ¹ ) ₂ ‧(CI ¹ ) _m3 Formula (1) [In the formula (1), M ¹ represents a metal atom, and LL ¹ is a formula ( 2) The bidentate ligand shown, LL ² is a bidentate ligand represented by the following formula (3); m1 represents 1, m2 represents 1, m3 is an integer of 0 or more; and Z ¹ represents a coordination group. The group is at least one selected from the group consisting of isothiocyanato, isocyanate, and isoselenocyano; CI ¹ represents a counter ion when it is necessary to neutralize the charge with ions. ]

[In the formula (2), R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ independently represent an acidic group or a salt thereof or a hydrogen atom, and R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ may be the same or different, but R ¹¹ At least one of ~R ¹⁴ and R ²¹ to R ²⁴ is an acidic group or a salt thereof. ]

[In the general formula (3), n1 and n2 independently represent an integer of 0 to 3, and Y ¹ and Y ² independently represent a hydrogen atom or a heteroaryl group represented by the following formula (4), but Ar ¹ and Ar ^{2 are} independently The heteroaryl group represented by the following formula (4) is represented. ]

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

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

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

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

The method for producing a metal complex dye according to any one of <7>, wherein the general formula (1) is represented by the following general formula (8), and the general formula (13) is The general formula (15) shows that the general formula (14) is represented by the following general formula (16).

In the general formulae (8) and (15), R ⁶¹ , R ⁶² , R ⁹¹ and R ^{92 each} independently represent a hydrogen atom, an alkyl group, an alkoxy group or an alkynyl group, and A ¹ to A ⁴ independently represent a carboxyl group or a salt thereof. M ¹² in the formula (16) represents an inorganic or organic ammonium ion, a proton or an alkali metal ion. ]

The method for producing a metal complex dye according to any one of <7>, wherein the formula (1) is represented by the following formula (17), and the formula (13) is The general formula (18) shows that the general formula (14) is represented by the following general formula (19).

[In the general formulae (17) and (18), R ¹⁰¹ , R ¹⁰² , R ¹¹¹ and R ^{112 each} independently represent an alkynyl group, and A ⁹ to A ¹² independently represent a carboxyl group or a salt thereof, and M ^{13 in the} formula (19) represents an inorganic group. Or organic ammonium ions, protons or alkali metal ions. ]

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

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

<14> A photoelectrochemical cell according to any one of <12> to <13>.

According to the present invention, a photoelectric conversion element and a photoelectrochemical cell having high conversion efficiency and excellent durability can be provided.

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

The inventors of the present invention have repeatedly conducted intensive studies and found that gold containing a specific ligand Since the complex compound dye has high solubility in a solvent, the amount of adsorption of the dye on the semiconductor fine particles can be increased, and a photoelectric conversion element and a photoelectrochemical cell having high conversion efficiency can be provided. The present invention has been completed based on this finding.

A preferred embodiment of the photoelectric conversion element of the present invention will be described below with reference to the schematic cross-sectional view of Fig. 1.

As shown in FIG. 1, the photoelectric conversion element 10 includes a conductive support 1 and a photoreceptor layer 2, a charge transport layer 3, and a counter electrode 4 which are sequentially disposed thereon. The conductive support 1 and the photoreceptor layer 2 constitute a light receiving electrode 5. The photoreceptor layer 2 has semiconductor fine particles 22 and a sensitizing dye (hereinafter also referred to as a dye) 21 . At least a part of the sensitizing dye 21 is adsorbed to the semiconductor fine particles 22 (the sensitizing dye 21 is in an adsorption equilibrium state, and a part thereof may be present in the charge transport layer 3). The function of the charge transport layer 3 is, for example, as a hole transport layer. The conductive support 1 on which the photoreceptor layer 2 is formed serves as a working electrode in the photoelectric conversion element 10. By operating the photoelectric conversion element 10 by the external circuit 6, the photoelectrochemical cell 100 can function.

The light-receiving electrode 5 includes a conductive support 1 and a photoreceptor layer 2 (semiconductor film) coated on the conductive support 1 and having the sensitizing dye 21 adsorbed on the semiconductor fine particles 22. Light incident on the photoreceptor layer 2 (semiconductor film) excites the pigment. The excitation pigment has high energy electrons. This electron self-sensitizing dye 21 is transmitted to the conduction band of the semiconductor fine particles 22 and then diffused to the conductive support 1 . At this time, the molecule of the sensitizing dye 21 becomes an oxide. The electrons on the electrodes operate by the external circuit 6 and return to oxide, thereby functioning as the photoelectrochemical cell 100. At this time, the light receiving electrode 5 functions as a negative electrode of the battery.

The photoreceptor layer 2 is composed of semiconductor fine particles 22 containing a dye which adsorbs a later-described pigment. The layer is composed of a porous semiconductor layer. This pigment may be a pigment or the like partially dissociated in the electrolyte. The photoreceptor layer 2 is designed according to the purpose and has a multilayer structure.

As described above, the photoreceptor layer 2 contains the semiconductor fine particles 22 to which the specific dye is adsorbed, and thus the light-receiving sensitivity is high, and when used as the photoelectrochemical cell 100, high photoelectric conversion efficiency is obtained, and high durability is obtained.

(metal complex pigment composition)

The metal complex dye composition of the present invention comprises a metal complex dye represented by the following formula (1), a metal complex dye represented by the following formula (5), and/or the following A metal complex dye represented by the formula (6).

The content of the metal complex dye represented by the formula (5) and the content represented by the formula (6) is 0.5 to 5% in total based on the area of 254 nm detected by HPLC.

M ¹ (LL ¹ ) _m1 (LL ² ) _m2 (Z ¹ ) ₂ ‧(CI ¹ ) _m3 Formula (1) [M ¹ represents a metal atom in the formula (1), and LL ¹ is a formula (2) ) The 2-dentate ligand shown, LL ² is a 2-dentate ligand represented by the following formula (3); m1 and m2 are both 1, m3 is an integer of 0 or more; and Z ¹ is a ligand; From at least one of isothiocyanato, isocyanate, and isoselenocyano, Z ¹ may be the same or different from each other, preferably the same; CI ¹ represents a counter ion when the charge is neutralized. ]

[In the formula (2), R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ independently represent an acidic group or a salt thereof or a hydrogen atom, and R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ may be the same or different, but R ¹¹ At least one of ~R ¹⁴ and R ²¹ to R ²⁴ is an acidic group or a salt thereof. ]

In the general formula (3), n1 and n2 independently represent an integer of 0 to 3, and Y ¹ and Y ² independently represent a hydrogen atom or a heteroaryl group represented by the following formula (4), and Ar1 and Ar2 independently represent the following a heteroaryl group represented by the formula (4). ]

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

M ¹ (LL ¹ ) _m1 (LL ² ) _m2 (Z ¹ ) (CN) ‧ (CI ¹ ) _m3 Formula (5) [In the formula (5), M ¹ , LL ¹ , LL ² , Z ¹ , The meanings of CI ¹ , m1, m2 and m3 are the same as those in the formula (1). ]

M ¹ (LL ¹ ) _m1 (LL ² ) _m2 (CN) ₂ ‧(CI ¹ ) _m3 Formula (6) [In the formula (6), M ¹ , LL ¹ , LL ² , Z ¹ , CI ¹ , The meanings of m1, m2 and m3 are the same as those in the formula (1). ]

(A) a metal complex dye represented by the formula (1) (A1) metal atom M ¹

M ¹ represents a metal atom. M ^{1 is} preferably a metal capable of 4 or 6 coordination, more preferably ruthenium, iron, osmium, copper, tungsten, chromium, molybdenum, nickel, palladium, platinum, cobalt, rhodium, ruthenium, osmium, manganese or zinc. . It is especially good for 钌, 锇, iron or copper. It is preferably a price of 2.

(A2) Ligand LL ¹

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

In the general formula (2), R ¹¹ to R ¹⁴ and R ²¹ to R ^{24 each} independently represent an acidic group or a salt thereof or a hydrogen atom, and R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ may be the same or different. R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ may, for example, be a hydrogen atom or an acidic group (e.g., a carboxyl group, a sulfonic acid group, a hydroxyl group or a hydroxamic acid group (the carbon number is preferably from 1 to 20, for example, -CONHOH, -CONCH). ₃ OH or the like, a phosphonium group (for example, -OP(O)(OH) ₂ or the like) or a phosphonium group (such as -P(O)(OH) ₂ or the like), or the like. The acidic group may be bonded via a linking group, and a group obtained by combining an acidic group such as a carboxyl group, a sulfonic acid group, a hydroxyl group or a hydroxamic acid group via a linking group is also included in the acidic group. At least one of R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ is an acidic group or a salt thereof. When R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ are acidic groups, the acidic group is preferably an acidic group such as a carboxyl group, a sulfonic acid group or a phosphonium group or a salt thereof, or a carboxyl group or a phosphonium group, from the viewpoint of electron injection. The base or the salts are more preferred, and a carboxyl group or a salt thereof is particularly preferred. When R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ are an acidic group or a salt thereof or a hydrogen atom, the metal complex dye can be efficiently adsorbed to the semiconductor fine particles.

(A3) Ligand LL ²

The ligand LL ² is a bidentate ligand represented by the following formula (3). M2 indicating the number of ligands LL ² represents 1. The double key can be either E or Z.

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

In the formula (4), R ³¹ to R ³³ independently represent a hydrogen atom, an alkyl group, an alkoxy group or an alkynyl group, and at least one of R ³¹ to R ³³ is an alkyl group, an alkoxy group or an alkynyl group, and an alkyl group or an alkyne group. More preferred, alkynyl is especially preferred. The bases may be linear or branched, and the carbon number is preferably 2 to 15, 3 to 12 is better, and 4 to 8 is particularly preferred. When the metal complex dye composition having such a hydrophobic substituent is used to adsorb the dye therein to the semiconductor fine particles, the water present in the electrolyte in the charge transport layer can be prevented from approaching, and the pigment can be inhibited from desorbing from the semiconductor fine particles. When the number of carbon atoms of the hydrophobic substituent is too large, it not only hinders the approach of water, but also hinders the proximity of, for example, iodine in the electrolyte, and the reduction by the redox system cannot be smoothly performed.

When Y ¹ or Y ² is represented by the formula (4), it is preferred that Y ¹ or Y ^{2 is} conjugated to a pyridine ring and Ar ¹ and Ar ^{2 are} conjugated to a pyridine ring. Along with the electron donating property of Y ¹ or Y ² represented by the general formula (4), the groups are conjugated such that the highest occupied molecular orbital (HOMO) position is aligned to the metal atom M ¹ in the metal complex dye. It is improved, and it can absorb light in a long wavelength region (long wave). In the formula (4), X is a sulfur atom, an oxygen atom, a selenium atom or NR ⁴ , and R ⁴ is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. The X in the general formula (4) is preferably a sulfur atom or a selenium atom, more preferably a sulfur atom, from the viewpoints of stability, oxidative easiness, and ease of synthesis of the nucleophilic species. When the ligand LL ² has such a structure, it is possible to exhibit an effect of suppressing deterioration in battery performance and long-wavelength due to desorption of the dye.

The ligand LL ^{2 is} preferably represented by the following formula (7): wherein R ⁴¹ to R ⁴³ and R ⁵¹ to R ⁵³ independently represent a hydrogen atom, an alkyl group, an alkoxy group or an alkynyl group. At least one of R ⁴¹ to R ⁴³ is an alkyl group, an alkoxy group or an alkynyl group. At least one of R ⁵¹ to R ⁵³ is an alkyl group, an alkoxy group or an alkynyl group. X ¹ and X ² are each independently a sulfur atom, an oxygen atom, a selenium atom or NR ⁷ , and R ⁷ is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. The double button can be E or Z type. R ⁴¹ to R ^{43 are} preferably an alkyl group or an alkynyl group. R ⁵¹ to R ^{53 are} preferably an alkyl group or an alkynyl group. In the general formula (7), X ¹ and X ^{2 are} preferably a sulfur atom or a selenium atom, and a sulfur atom is more preferable. When the ligand LL ^{2 has} such a structure, when n1 and n2 of the general formula (3) are 1, the effect of being difficult to oxidize and stable can be obtained as compared with the case of being 2 or more.

The metal complex dye represented by the above formula (1) is preferably represented by the formula (8), R ⁶¹ and R ^{62 are} independently an alkyl group, an alkoxy group or an alkynyl group, and A ¹ and A ^{2 are} independently a carboxyl group or salt. R ⁶¹ and R ^{62 are} preferably an alkyl group or an alkynyl group. The metal complex dye represented by the formula (1) has a structure in which light of a long wavelength region is absorbed by the high electron donating property of the thiophene. Further, the vinyl thiophene bonded to the bipyridyl ring and the substituent bonded to the thiophene can exclude the water from approaching, and can inhibit the desorption of the pigment from the semiconductor fine particles. Further, electron injection can be efficiently performed by a carboxyl group or a salt thereof, and light having a long wavelength region can be absorbed by an isothiocyanate group having high electron donating property.

The metal complex dye represented by the above formula (1) has ^one each of LL ¹ and LL ² , and the dye is adsorbed on the surface of the semiconductor fine particles by the acidic group portion of LL ¹ and has an alkyl group, an alkoxy group or an alkynyl group. The LL ^{2 of the} hydrophobic group is disposed on the opposite side of the spatially semiconducting fine particle layer, and is effective for suppressing water contact and pigment desorption.

(A4) ligand Z ¹

The ligand Z ¹ is at least one selected from the group consisting of isothiocyano group, isocyanate group, and isoselenocyano group. These groups have high electron donating properties and contribute to the long-wavelength of the pigment. The ligand Z ^{1 is} preferably an isothiocyano group or an isoselenocyano group.

(A5) counter ion CI ¹

CI ¹ in the formula (1) represents a counter ion when it is necessary to neutralize the charge with ions. Generally, whether the pigment is a cation or an anion or whether it has a positive ionic charge depends on the metal, ligand, and substituent in the pigment. The number m3 of the ions CI ¹ is an integer of 0 or more.

The substituent may have a dissociable group or the like, and the dye of the formula (1) may be dissociated to have a negative charge. At this time, the charge of the entire dye of the general formula (1) becomes electrically neutral due to the ion CI ¹ .

When the ion CI ¹ is a positive ion, it is, for example, an inorganic or organic ammonium ion (such as a tetraalkylammonium ion, a pyridinium ion or the like), an alkali metal ion or a proton.

When the ion CI ¹ is a negative ion, it may be, for example, an inorganic or organic anion, and may be exemplified by a halogen anion (for example, a fluoride ion, a chloride ion, a bromide ion, an iodide ion, or the like) or a substituted arylsulfonic acid ion (for example, p-toluenesulfonate). Acid ion, p-chlorobenzenesulfonate ion, etc., aryl disulfonic acid ion (for example, 1,3-benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalene disulfonic acid ion, etc.) ), alkyl sulfate ion (such as methyl sulfate ion, etc.), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroboric acid ion, hexafluorophosphate ion, picric acid ion, acetic acid ion, trifluoromethane Acid ions, etc. Further, the charge equalization may use an ionic polymer or other dye having an opposite charge to the dye, and a metal counter ion (for example, biphenyl-1,2-dithiol nickel (III) or the like) may be used.

(B) metal complex pigment of the formula (5) or (6)

The metal complex dye composition of the present invention contains, in addition to the metal complex dye represented by the above formula (1), a specific amount of the metal complex dye represented by the following formula (5) and the following formula. (6) At least one of the above-mentioned compounds, the blending ratio is 0.5% of the area detected by 254 nm of HPLC, and the total content of the one shown by the formula (5) and the formula (6) is 0.5 of the composition. ~5%.

The metal complex dye of the formula (5) has one cyano group as a ligand, and the formula (6) has two cyano groups as a ligand. In the formula (5), M ¹ , LL ¹ , LL ² , Z ¹ , CI ¹ , m1, m2 and m3 have the same meanings as in the above formula (1), and M ¹ and LL ¹ in the formula (6) The meanings of LL ² , Z ¹ , CI ¹ , m1, m2 and m3 are the same as those of the above formula (1), and are omitted for repetition. From the viewpoints of performance such as conversion efficiency, it is preferred that M ¹ , LL ¹ , LL ² , Z ¹ , CI ¹ , m1, m2 and m3 in the general formulae (5) and (6) have the meanings and formula (1) The same in the middle.

M ¹ (LL ¹ ) _m1 (LL ² ) _m2 (Z ¹ )(CN)‧(CI ¹ ) _m3 Formula (5)

M ¹ (LL ¹ ) _m1 (LL ² ) _m2 (CN) ₂ ‧(CI ¹ ) _m3 Formula (6)

The cyano group has a lower electron donating property than the aforementioned isothiocyanato group. Therefore, the metal complex dye represented by the formula (5) having one cyano group and the formula (6) having two cyano groups have a lower HOMO level and a shorter wavelength, so that they are adsorbed on When the semiconductor fine particles are used as a sensitizing dye, light on the long-wave side cannot be effectively utilized, resulting in a decrease in conversion efficiency.

However, when the metal complex dye represented by the formula (5) and the content of the formula (6) are 0.5 to 5% of the metal complex dye composition, the area detected by 254 nm of HPLC is Therefore, the conversion efficiency is not lowered, and the solubility of the dye in the solution can be dramatically improved, and the amount of dye adsorption on the semiconductor fine particles can be improved, and the photoelectric conversion efficiency can be improved. Further, the dye solution can be prepared in a short period of time, and the productivity of the photoelectric conversion element production can be improved. The reason why the solubility of the dye in the solution is improved is still uncertain, but it is considered that although the basic skeleton is common to the metal complex dye represented by the general formula (1), it is contained. 0.5 to 5% of a metal complex dye having a cyano group having different chemical properties, so the crystal arrangement of the metal complex dye is different from that of 0.5% or less.

The content of the metal complex dye represented by the formula (5) and the content represented by the formula (6) is 0.5 to 5% based on the area detected by 254 nm of HPLC, and is a value obtained by analysis under the following conditions: The column is YMC-Pack ODS-AM312 manufactured by YMC Corporation, 150 mm × 6.0 mm ID, flow rate is 0.75 ml/min, oven is 40 ° C, and the composition of the eluent is tetrahydrofuran/water = 63/37 (containing 0.1% trifluoroacetic acid buffer). Liquid), the measurement time is 50 minutes.

When the metal complex dye represented by the formula (5) is represented by the following formula (9) and the metal complex dye represented by the formula (6) is represented by the following formula (10), the formula (9) The total content of the metal complex dye shown in the formula (10) is preferably 0.5 to 5% based on the area of the 254 nm detected by HPLC. In the formula (9), R ⁷¹ and R ^{72 are} independently an alkyl group, an alkoxy group or an alkynyl group, and A ⁵ and A ^{6 each} independently represent a carboxyl group or a salt thereof. In the formula (10), R ⁷³ and R ^{74 each} independently represent an alkyl group, an alkoxy group or an alkynyl group, and A ⁷ and A ⁸ independently represent a carboxyl group or a salt thereof. R ⁷¹ and R ^{72 are} preferably an alkyl group or an alkynyl group. R ⁷³ and R ^{74 are} preferably an alkyl group or an alkynyl group. The metal complex dye represented by the formula (5) is represented by the formula (6), and the total content of the metal complex dyes is 0.5 in terms of the area detected by HPLC at 254 nm. When the concentration is ~5%, the absorption of the dye is long-wavered due to the electron-donating property of the thiophene ring, and the conversion efficiency is lowered by the cyano group without causing short-wavelength, and the solubility is improved. The total content of the metal complex dye represented by the formula (5) and the content represented by the formula (6) is preferably 0.5 to 4.5%, more preferably 0.5 to 4%, based on the area of the 254 nm detected by HPLC. 0.5~3.5% is especially good.

The metal complex dye represented by the formula (5) is preferably represented by the following formula (11), and the metal complex dye represented by the formula (6) is represented by the following formula (12). In the general formulae (11) and (12), R ⁸¹ to R ⁸⁴ independently represent an alkynyl group, and A ¹³ to A ¹⁶ independently represent a carboxyl group or a salt thereof. Since the metal complex dye of this structure is an alkynyl group from R ⁸¹ to R ⁸⁴ , it exhibits an effect of long-wavelength absorption and ε increase by the π-π ^* transition of LL ² due to elongation of the conjugated system. It is also estimated that since R ⁸¹ to R ⁸⁴ are alkynyl groups, the planarity of the metal complex dye of this structure with respect to the thiophene ring R ⁸¹ to R ⁸⁴ is increased, or the π electrons are increased, and it is possible that the pigment is adsorbed to the semiconductor particles. In the state of the surface, a preferable association which contributes to long-wavelength is likely to occur between molecules. R ⁸¹ to R ^{84 are} preferably a linear or branched alkynyl group having a carbon number of 3 to 13, and more preferably a carbon number of 3 to 8, and a particularly preferred one having a carbon number of 4 to 7.

The metal complex dye composition preferably dissolves the metal complex dye of the formula (1) and the metal complex dye represented by the formula (5) and/or the compound represented by the formula (6) in an organic form. In the solvent. Such an organic solvent may, for example, be an alcohol solvent (methanol, ethanol, isopropanol, etc.), a nitrile solvent (acetonitrile, propylene, methoxypropionitrile, valeronitrile, etc.), an ester solvent (ethyl acetate, γ -butyl). Lactone, etc., guanamine solvent (dimethylformamide, dimethylacetamide, N-methylpyrrolidone), halogen solvent (dichloromethane, dichloroethane, chlorobenzene, chloroform, etc.) There are no particular restrictions on benzene, toluene, xylene, and the like. Further, it may be a mixed solvent containing a plurality of solvents.

(C) Method for producing metal complex pigment

The metal complex dye of the formula (1) of the present invention can be produced by a method comprising the step of externally heating a metal complex dye comprising the following formula (13) and the following formula (14) The temperature of the mixture of compounds rises.

M ¹ (LL ¹ ) _m1 (LL ² ) _m2 (Z ² ) _m4 ‧(CI ¹ ) _m5 Formula (13)

M ¹ , LL ¹ , LL ² , CI ¹ , m1 and m2 in the formula (13) have the same meanings as in the formula (1). Z ² is a 1 or 2 tooth ligand. Z ^{2 is} preferably a halogen atom (fluorine, chlorine, bromine, iodine), water, dimethylformamido, -OC(=O)-(CH ₂ ) _p -C(=O)-O-(p The integer above Table 0 is preferably 0 to 6, more preferably 0 to 4, more preferably 0 to 2, more preferably chlorine atom, water or dimethylformamide, and particularly preferably a chlorine atom. M4 is an integer of 1 to 2, when Z ² is a dental ligand, m4 represents 2, and when Z ² is a 2-dentate ligand, m4 represents 1. When m4 is 2, Z ² may be the same or different from each other, and is preferably the same. M5 is an integer of 0 or more.

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

M ¹¹ QCN Formula (14) [In the formula (14), M ¹¹ represents an inorganic or organic ammonium ion, a proton or an alkali metal ion, and Q represents a sulfur atom, an oxygen atom or a selenium atom. ]

M ^{11 is} preferably an inorganic or organic ammonium ion (for example, NH ₄ ⁺ , NBu ₄ ⁺ , NEt ₃ H ⁺ ), an alkali metal ion (for example, Na ⁺ , K ⁺ , Li ⁺ ), more preferably NH ₄ ⁺ , NBu. ₄ ⁺ , K ⁺ , especially good for NH ₄ ⁺ , K ⁺ . The Q is preferably a sulfur atom or a selenium atom, and more preferably a sulfur atom, in terms of the absorption wavelength of the metal complex dye of the formula (1), that is, the electron donating property of the QCN as a ligand.

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

M ¹ (LL ¹ ) _m1 (LL ² ) _m2 (Z ¹ ) ₂ ‧(CI ¹ ) _m3 Formula (1)

In the formula (1), M ¹ represents a metal atom, LL ¹ is a bidentate ligand represented by the following formula (2), and LL ² is a bidentate ligand represented by the following formula (3). And m1 and m2 each represent 1; Z ¹ represents a ligand which is at least one selected from the group consisting of isothiocyanato, isocyanate and isocyanium. Z ¹ may be the same or different, preferably the same. ; CI ¹ denotes a counter ion when it is necessary to neutralize the charge with ions; m3 is an integer of 0 or more.

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

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

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

The descriptions of the above general formulae (1) to (4) are the same as those described above, and are omitted because they are repeated.

The metal complex dye of the present invention can be produced by a method comprising the following steps, that is, a metal complex dye containing the above formula (13) and the above formula (14) by external heating The mixture of compounds is heated to raise the temperature. The liquid mixture containing the metal complex dye of the above formula (13) and the compound of the above formula (14) is preferably an organic solvent, and may be exemplified by an alcohol solvent (methanol, ethanol, propanol, isopropanol, butyl). Alcohol, etc.), nitrile solvent (acetonitrile, propionitrile, methoxypropionitrile, valeronitrile, etc.), ester solvent (ethyl acetate, γ -butyrolactone, etc.), guanamine solvent (dimethylformamide, Dimethylacetamide, N-methylpyrrolidone), halogen solvent (dichloromethane, dichloroethane, chlorobenzene, chloroform, etc.), benzene, toluene, xylene, etc., but not particularly limited to the organic solvents . Further, it may be a mixed solvent containing a plurality of solvents or a mixed solvent with water. The organic solvent is preferably an alcohol solvent, a nitrile solvent or a guanamine solvent, more preferably an alcohol solvent or a guanamine solvent, and a guanamine solvent is preferred.

The method of heating the mixture of the metal complex dye of the formula (13) and the compound of the formula (14) to increase the temperature must be a method of heating from the outside. The method of heating from the outside refers to a method of heating by heat transfer from an external heat source. The heat source is not particularly limited, and examples thereof include a heat source that converts electric energy into heat, a heat source that is burned, and the like. The heat obtained from the heat sources can be heated via the medium to heat the mixture. The medium can be exemplified by oil, water (water vapor), and the like. The method of irradiating microwaves or the like is to heat the microwave energy into heat by the absorption of the microwave by the substance, and it can be said that the heating is from the inside and is not included in the external heating. The internal heating of the microwave or the like is different from the external heating, and the metal complex is directly heated, and the metal complex dye or the general formula of the general formula (13) contained in the mixture may occur due to excessive heating energy. The decomposition of the compound of 14) or the metal complex dye of the formula (1) is not preferable for the production of the metal complex dye of the present invention. The method of external heating is preferably a method of heating the mixture by means of an oil bath or steam. The heating temperature and reaction time can be appropriately selected depending on the metal complex dye to be reacted or the solvent to be used. The heating temperature is preferably 90 to 170 ° C, 90 to 160 ° C is better, 100 to 150 ° C is particularly good, and 100 to 140 ° C is the best. The reaction time is preferably from 30 minutes to 12 hours, more preferably from 1 to 8 hours, and particularly preferably from 2 to 6 hours.

The metal complex dye of the formula (13) can be obtained by introducing LL ¹ and LL ^{2 to} a compound having Ru as shown in the following scheme. The Ru source is not particularly limited, and examples thereof include ruthenium chloride or a hydrate thereof, d-1-6 described later, and the like, and d-1-6 which is a valence of Ru which is valence of 2 is preferable. The order of introduction of LL ¹ and LL ² is not particularly limited, but is preferably introduced from LL ² . Z ^{2 is} often dependent on the Ru source, and may be an additive (potassium iodide, potassium bromide, KO-C(=O)-(CH ₂ ) _p -C(=O)-OK (p is an integer of 0 or more), etc.) Change with use. Further, the solvent can be coordinated to form Z ² . Further, the compound (14) is added to the obtained solution containing the metal complex dye of the formula (13), and the mixture is heated from the outside to obtain a metal complex dye of the formula (1).

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

It is preferred that the metal complex dye of the formula (13) is represented by the following formula (15) and the compound of the formula (14) is represented by the following formula (16) to produce the following formula ( 8) A method of the metal complex pigment shown. In the general formulae (8) and (15), R ⁶¹ , R ⁶² , R ⁹¹ and R ^{92 each} independently represent a hydrogen atom, an alkyl group, an alkoxy group or an alkynyl group, and A ¹ to A ⁴ independently represent a carboxyl group or a salt thereof. In the formula (16), M ¹² represents an inorganic or organic ammonium ion, a proton or an alkali metal ion. R ⁶¹ , R ⁶² , R ⁹¹ and R ^{92 are} preferably an alkyl group or an alkynyl group. When the metal complex dye (13) and the compound of the formula (14) are in such a structure, since the metal complex dye (13) has a thiophene ring which is stable to the compound (14) of the nucleophilic species, it is possible to suppress the undesired The desired nucleophilic reaction is such that the chlorine having a high desorption energy and a low nucleophilic energy becomes a decomposing group, whereby the metal complex dye of the formula (8) in which the NCS group is selectively coordinated to the deuterium atom can be efficiently produced.

It is preferred that the metal complex dye of the formula (13) is represented by the following formula (18) and the compound of the formula (14) is represented by the following formula (19) to produce the following formula ( 17) A method of the metal complex pigment shown. In the general formulae (17) and (18), R ¹⁰¹ , R ¹⁰² , R ¹¹¹ and R ^{112 each} independently represent an alkynyl group, and A ⁹ to A ¹² independently represent a carboxyl group or a salt thereof. In the formula (19), M ¹³ represents an inorganic or organic ammonium ion, a proton or an alkali metal ion. R ¹⁰¹ , R ¹⁰² , R ¹¹¹ and R ^{112 are} preferably a linear or branched alkynyl group having a carbon number of 3 to 13, and a carbon number of 3 to 8 is more preferable, and a carbon number of 4 to 7 is particularly preferable.

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

The following is a specific example of the dye having the structure represented by the formula (1) used in the present invention, but the present invention is not limited thereto. Further, when the dye in the following specific examples contains a ligand having a proton-dissociable group, the ligand may be dissociated as needed to form a salt with the counter ion. Further, an isomer based on a double bond site or an isomer based on the position of a complex of a complex compound may be present, but the isomer may be of any type or a mixture.

(D) Charge transporter

In the electrolyte composition used in the photoelectric conversion element 10 of the present invention, the redox pair may, for example, be iodine and an iodide (e.g., lithium iodide or tetrabutylammonium iodide, Combination of tetrapropylammonium iodide, etc., alkyl viologen (such as methyl violet, hexyl bromide, benzyl violet tetrafluoroborate) and its reducing compound, polyhydroxyl a combination of a benzene (such as hydroquinone, naphthalenediol, etc.) and an oxide thereof, a combination of a divalent iron complex and a trivalent iron complex (for example, a red blood salt and a yellow blood salt), among which It is a combination of iodine and iodide.

The cation of the iodide salt is preferably a nitrogen-containing aromatic cation of a 5- or 6-membered ring. In particular, when the compound represented by the formula (1) is not an iodide salt, the following iodide salt is preferably used in combination: Japanese Patent Laid-Open Publication No. WO95/18456, Japanese Patent Laid-Open No. Hei 8-259543, No. 65, No. Pyridinium salt, imidazolium salt, triazolium salt, etc. described in 923 (1997).

The electrolyte composition used in the photoelectric conversion element 10 of the present invention preferably contains iodine together with the heterocyclic quaternary chlorine compound. The content of iodine is preferably 0.1 to 20% by weight, more preferably 0.5 to 5% by weight based on the total amount of the electrolyte composition.

The electrolyte composition used in the photoelectric conversion element 10 of the present invention may contain a solvent. The solvent content in the electrolyte composition is preferably 50% by weight or less, more preferably 30% by weight or less, particularly preferably 10% by weight or less based on the total amount of the composition.

In order to obtain high ion mobility at a low viscosity or to increase an effective carrier concentration at a high dielectric constant, or both, the solvent is preferably an ion conductivity, and a carbonate compound (ethylene carbonate) is exemplified. Ester, propylene carbonate, etc.), heterocyclic compound (3-methyl-2-oxazolidinone, etc.), ether compound (dioxane, diethyl ether, etc.), chain ether (ethylene glycol dialkyl ether) , propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, etc.), alcohols (methanol, ethanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, poly Propylene glycol monoalkyl ether, etc.), polyols (ethylene glycol, propylene glycol, polyethylene glycol, poly Propylene glycol, glycerin, etc., nitrile compounds (acetonitrile, pentane, methoxyacetonitrile, propionitrile, benzonitrile, dicyandiethyl ether, etc.), esters (carboxylates, phosphates, phosphonates, etc.), An aprotic polar solvent (dimethyl hydrazine, cyclobutyl hydrazine, etc.), water, an aqueous electrolyte solution described in JP-A-2002-110262, Japanese Patent Laid-Open Publication No. 2000-36332, and Japanese Patent Laid-Open No. 2000-243134 An electrolyte solvent or the like described in Japanese Laid-Open Patent Publication No. WO-00-54361. These solvents may be used in combination of two or more.

Further, as the electrolyte solvent, an electrochemically active salt which is liquid at room temperature and has a melting point lower than room temperature can be used, and examples thereof include 1-ethyl-3-methylimidazolium trifluoromethanesulfonate and 1-butyl. A nitrogen-containing heterocyclic quaternary chlorine compound such as an imidazolium salt or a pyridinium salt such as a 3-methylimidazolium trifluoromethanesulfonate or a tetraalkylammonium salt.

A polymer or an oil gelling agent may be added to the electrolyte composition used in the photoelectric conversion element of the present invention, or may be gelled by a polymerization of a polyfunctional monomer or a crosslinking reaction of a polymer (solidification). ).

When the electrolyte composition is gelated by adding a polymer, a compound described in Polymer Electrolyte Reviews-1 & 2 (JR MacCallum and CAVincent Co-authored, ELSEVIER APPLIED SCIENCE) can be added, and in this case, polypropylene is preferably used. Nitrile or polyvinylidene fluoride.

When the electrolyte composition is gelled by the addition of an oil gelling agent, the oil gelling agent can be used by J. Chem. Soc. Japan, Ind. Chem. Soc., 46779 (1943), J. Am. Chem. Soc., 111, 5542 (1989), J. Chem. Soc., Chem. Commun., 390 (1993), Angew. Chem. Int. Ed. Engl., 35, 1949 (1996), Chem. Lett., The compound described in 885 (1996), J. Chem. Soc., Chem. Commun., 545 (1997), etc., preferably A compound having a guanamine structure is used.

When the electrolyte composition is gelated by polymerization of a polyfunctional monomer, it is preferably a method of preparing a solution from a polyfunctional monomer, a polymerization initiator, an electrolyte, and a solvent, by casting, coating, or immersion. A method such as a method or an impregnation method forms a sol-like electrolyte layer on an electrode carrying a pigment, and gels by radical polymerization of a polyfunctional monomer. The polyfunctional monomer is preferably a compound having two or more ethylenically unsaturated groups, preferably divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, and diethylene glycol II. Acrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, and the like.

The gel electrolyte can be formed by polymerization of a mixture containing a monofunctional monomer in addition to the above polyfunctional monomer. Monofunctional monomers can be used: acrylic acid or alpha -alkyl acrylic acid (acrylic acid, methacrylic acid, itaconic acid, etc.) or esters or guanamine or vinyl esters (vinyl acetate, etc.), maleic acid Or fumaric acid or esters derived therefrom (dimethyl maleate, dibutyl maleate, diethyl fumarate, etc.), p-styrenesulfonic acid Sodium salt, acrylonitrile, methacrylonitrile, diene (butadiene, cyclopentadiene, isoprene, etc.), aromatic vinyl compound (styrene, p-chlorostyrene, tert-butylbenzene) Ethylene, α -methylstyrene, sodium styrene sulfonate, etc.), N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl -N-methylacetamide, vinyl sulfonic acid, sodium vinyl sulfonate, sodium allyl sulfonate, sodium methacrylate sulfonate, vinylidene fluoride, vinylidene chloride, vinyl alkyl ether (methyl vinyl ether or the like), ethylene, propylene, butylene, isobutylene, N-phenyl maleimide or the like.

The compounding amount of the polyfunctional monomer is preferably from 0.5 to 70% by weight, more preferably from 1.0 to 50% by weight, based on the total amount of the monomers. The above-mentioned monomers can be described by the "Experimental Method of Polymer Synthesis" (Chemical Fellow) or Otsu Takayuki "Lecture Polymerization Theory 1-Free Radical Polymerization (I)" (Chemical Fellow). The polymer synthesis method is a radical polymerization to polymerize. The monomer for gel electrolyte used in the present invention may be subjected to radical polymerization or electrochemical radical polymerization by heating, light or electron beam, and particularly preferably by free radical polymerization by heating. The polymerization initiators which can be preferably used at this time are: 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'- Azo-based initiators such as azobis(2-methylpropionic acid) dimethyl ester and 2,2'-azobisisobutyric acid dimethyl ester, lauryl peroxide, benzammonium peroxide, peroxidation A peroxide-based initiator such as butyl octanoate. The amount of the polymerization initiator to be added is preferably from 0.01 to 20% by weight, more preferably from 0.1 to 10% by weight, based on the total amount of the monomers.

The weight composition of the monomer in the gel electrolyte is preferably in the range of 0.5 to 70% by weight, more preferably 1.0 to 50% by weight. When the electrolyte composition is gelated by a polymer crosslinking reaction, it is preferred to add a polymer having a crosslinkable reactive group and a crosslinking agent to the composition. Preferred reactive groups are pyridine ring, imidazole ring, thiazole ring, oxazole ring, triazole ring, morpholin ring, piperidine ring, piperazine ring and the like, and a preferred crosslinking agent is A compound (electrophilic agent) having two or more functional groups which can be nucleophilically attacked by a nitrogen atom is, for example, a halogen functional alkane having 2 or more functional groups, an alkyl halide, a sulfonate, an acid anhydride, an anthracene chloride or an isocyanate.

The electrolyte composition of the present invention may be added with metal iodide (LiI, NaI, KI, CsI, CaI _2, etc.), metal bromide (LiBr, NaBr, KBr, CsBr, CaBr _{2 ,} etc.), and quaternary ammonium bromide (bromination). Tetraalkylammonium, pyridinium bromide, etc.), metal complex (ferrocyanide-iron cyanide, ferrocene-ferrocene ion, etc.), sulfur compound (polysulfide, alkylthiol) - an alkyl disulfide or the like), a violet pigment, hydroquinone-hydrazine or the like. These compounds can also be used in combination.

Further, in the present invention, a base such as tributylpyridine or 2-methylpyridine or 2,6-dimethylpyridine described in J. Am. Ceram. Soc., 80 (12), 3157-3171 (1997) may be added. For the compound, the preferred concentration range is 0.05~2M.

Further, the electrolyte of the present invention may use a charge transport layer containing a hole conductor substance. As the hole conductor material, a 9,9'-spiropyrene derivative or the like can be used.

Further, an electrode layer, a photoreceptor layer (photoelectric conversion layer), a charge transport layer (hole transport layer), a conductive layer, and a counter electrode layer may be laminated in this order. The hole transport layer can be made using a hole transport material that functions as a p-type semiconductor. A preferred hole transport layer can be, for example, an inorganic or organic hole transport material. The inorganic hole transporting material may, for example, be CuI, CuO, NiO or the like. Further, the organic hole transporting material may be a polymer-based and low-molecular-weight hole transporting material, and the polymer-based hole transporting material may, for example, be a polyvinyl carbazole, a polyamine or an organic polydecane. Further, the low molecular weight hole transporting material may, for example, be a triphenylamine derivative, an anthracene derivative, an anthracene derivative or a phenylpropylamine derivative. Among them, the organic polydecane is different from the previous carbon-based polymer, and the 矽-electron along the main chain, rather than the localized σ electron, contributes to light conduction and has high hole mobility, so it is preferable (Phys.Rev .B, 35, 2818 (1987)).

The conductive layer is not particularly limited as long as it has good conductivity, and examples thereof include an inorganic conductive material, an organic conductive material, a conductive polymer, and an intermolecular charge transport complex. Among them, the donor material and the acceptor material are preferably The intermolecular charge transport complex formed by the material. Among them, an intermolecular charge transport complex formed of an organic donor and an organic acceptor can be preferably used.

The thickness of the conductive layer is not particularly limited, and it is preferably such that the porous material can be completely buried.

The above donor material is preferably a material in which electrons are concentrated in the molecular structure. For example, the organic donor material may, for example, be a material having an amine group, a hydroxyl group, an ether group, a selenium or a sulfur atom in a π- electron system of a molecule, and specific examples thereof include a phenylamine system, a triphenylmethane system, an oxazole system, and a phenol. A tetrathiafulvalene-based material. The acceptor material is preferably a material that is deficient in electrons within the molecular structure. For example, the organic acceptor material may, for example, be a material having a substituent such as a nitro group, a cyano group, a carboxyl group or a halogen group in a fullerene or a π-electron system of a molecule, and specifically, a PCBM ([6,6]-phenyl -C61-butyric acid methyl ester), benzoquinone, naphthoquinone, etc., anthraquinone, anthrone, tetrachlorophenylhydrazine, tetrabromophenylhydrazine, tetracyanoquinodimethane, tetracyanoethylene Wait.

(E) Conductive support

As shown in Fig. 1, in the photoelectric conversion element of the present invention, a photoreceptor layer 2 is formed on a conductive support 1, and the photoreceptor layer 2 is formed by adsorbing a sensitizing dye 21 on the porous semiconductor fine particles 22. As described later, for example, a dispersion of semiconductor fine particles can be applied onto a conductive support and dried, and then immersed in the dye solution of the present invention to produce a photoreceptor layer 2.

As the conductive support 1, a support which is electrically conductive like a metal or a glass or a polymer material having a conductive film layer on its surface can be used. The conductive support 1 is preferably substantially transparent, that is, the light transmittance is 10% or more, preferably 50% or more, and more preferably 80% or more. As the conductive support 1, a support in which a conductive metal oxide is coated on a glass or a polymer material can be used. The amount of the conductive metal oxide applied at this time is preferably 0.1 to 100 g per 1 m ^{2 of the} glass or polymer material support. When a transparent conductive support is used, it is preferred that light is incident from the side of the support. The polymer material to be preferably used may, for example, be tetraethylidene cellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), or syndiotactic polystyrene ( SPS), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate (PAR), polyfluorene (PSF), polyester fluorene (PES), polyether phthalimide (PEI), cyclic polymerization Olefin, brominated phenoxy resin, and the like. In the conductive support 1 , a light management function can be applied to the surface, and an antireflection film in which a high refractive film and a low refractive index oxide film are alternately laminated in Japanese Patent Laid-Open Publication No. 2003-123859, The light guiding function described in JP-A-2002-260746.

Further, a metal support is also preferable, and examples thereof include titanium, aluminum, copper, nickel, iron, stainless steel, and copper. These metals can also form alloys. More preferably, it is titanium, aluminum, copper, and particularly preferably titanium or aluminum.

The conductive support 1 preferably has an ultraviolet light blocking function. For example, a method in which a fluorescent material capable of converting ultraviolet light into visible light is present in a transparent support or a surface thereof, or a method using an ultraviolet absorber may be exemplified.

The function described in Japanese Laid-Open Patent Publication No. Hei 11-250944, and the like can also be applied to the conductive support 1 .

Preferred conductive films may be exemplified by metals (e.g., platinum, gold, silver, copper, aluminum, antimony, indium, etc.), carbon or conductive metal oxides (indium-tin composite oxides, doped with fluorine in tin oxide) a conductive metal oxide, etc.).

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

The lower the surface resistance of the conductive support 1 is, the better, preferably 50 Ω/cm ² or less, more preferably 10 Ω/cm ² or less. The lower limit is not particularly limited and is usually about 0.1 Ω/cm ² .

When the cell area is increased, the resistance value of the conductive film is increased, so that the collector electrode can also be disposed. Either or both of the gas barrier film and the ion diffusion preventing film may be disposed between the conductive support 1 and the transparent conductive film. A resin film or an inorganic film can be used for the gas barrier layer.

Further, a layer containing a transparent electrode and a porous semiconductor electrode photocatalyst may be provided. The transparent conductive film may also be a laminated structure, and a preferred method is, for example, laminating fluorine-doped tin oxide (FTO) on indium tin oxide (ITO).

(F) semiconductor particles

As shown in FIG. 1, in the photoelectric conversion element 10 of the present invention, a photoreceptor layer 2 is formed on a conductive support 1, and the photoreceptor layer 2 is formed by adsorbing the sensitizing dye 21 on the porous semiconductor fine particles 22. As described later, for example, the dispersion of the semiconductor fine particles 22 can be applied onto the conductive support 1 and dried, and then immersed in the dye solution to produce the photoreceptor layer 2.

As the semiconductor fine particles 22, a chalcogenide of a metal (for example, an oxide, a sulfide, a selenide or the like) or a fine particle of a perovskite is preferably used. The chalcogenide of the metal is preferably exemplified by oxides of titanium, tin, zinc, tungsten, zirconium, hafnium, yttrium, indium, lanthanum, cerium, lanthanum, vanadium, niobium or tantalum, cadmium sulfide, cadmium selenide, etc. . The perovskite is preferably exemplified by barium titanate or calcium titanate. Among these, the best ones are titanium oxide, zinc oxide, tin oxide, and tungsten oxide.

The semiconductor has a n-type in which the carrier related to the conduction is electrons and a p-type in which the carrier is a hole. In the element of the present invention, the n-type is preferably used from the viewpoint of conversion efficiency. The n-type semiconductor has an n-type semiconductor having a high electron carrier concentration in addition to an intrinsic semiconductor having a carrier concentration equal to a carrier concentration of a valence electron-charged hole (for example, an intrinsic semiconductor), without an impurity level. The n-type inorganic semiconductors which can be preferably used in the present invention are: TiO ₂ , TiSrO ₃ , ZnO, Nb ₂ O ₃ , SnO ₂ , WO ₃ , Si, CdS, CdSe, V ₂ O ₅ , ZnS, ZnSe, SnSe, KTaO. ₃ , FeS ₂ , PbS, InP, GaAs, CuInS ₂ , CuInSe ₂ and the like. The most preferred n-type semiconductors are TiO ₂ , ZnO, SnO ₂ , WO ₃ and Nb ₂ O ₃ . Further, a semiconductor material obtained by compounding a plurality of these semiconductors can also be preferably used.

The method for producing the semiconductor fine particles 22 is preferably a gel-sol method described by Agne-Shofu Co., Ltd. (1998), which is the "Science of Sol-Gel Method" by I. In addition, a method developed by Degussa to produce an oxide by hydrolyzing a chloride in an acid hydrogen salt is also preferable. When the semiconductor fine particles 22 are titanium oxide, the sol-gel method, the gel-sol method, and the high-temperature hydrolysis method of the chloride in the acid hydrogen salt are all preferable, and the "titanium oxide property and application technique" of Kiyono may be used. The sulfuric acid method and the chlorine method described in the Technical Bulletin, 1997). Another sol-gel method - preferably: Barbe is equivalent to the method described in Journal of the American Ceramic Society, Vol. 80, No. 12, 3157 to 3171 (1997), or Burnside is equal to Chemistry of Materials, Vol. 10, No. .9, 2419~2425.

Further, as a method for producing the semiconductor fine particles, for example, a method for producing titanium dioxide nanoparticles is preferably a method of flame hydrolysis of titanium tetrachloride, a combustion method of titanium tetrachloride, and hydrolysis of a stable chalcogenide complex. Orthotitanic acid Hydrolysis, a method of dissolving and removing a soluble portion after forming a semiconductor fine particle from a soluble portion and an insoluble portion, hydrothermal synthesis of a peroxide aqueous solution, or a method of producing a core/shell structured titanium oxide fine particle by a sol-gel method .

The crystal structure of titanium dioxide may, for example, be an anatase type, a brookite type or a rutile type, preferably an anatase type or a brookite type.

A titanium dioxide nanotube, a nanowire, or a nanorod may also be mixed in the titanium dioxide fine particles.

Titanium dioxide can be doped with non-metallic elements and the like. Additives in Titanium Dioxide In addition to the dopant, it is also possible to use an adhesive for improving necking or to use an additive on the surface to prevent reverse electron migration. Preferred examples of the additive include ITO, SnO particles, whiskers, fibrous graphite-carbon nanotubes, zinc oxide bonded binders, fibrous substances such as cellulose, metals, organic germanium, and dodecylbenzenesulfonic acid. a charge transporting binding molecule such as a decane compound, and a potential tilting dendrimer.

In order to remove surface defects and the like on the titanium oxide, the titanium oxide may be subjected to acid-base or redox treatment before the adsorption of the pigment. It can also be etched, oxidized, treated with hydrogen peroxide, dehydrogenated, UV-ozone, oxygen plasma, and the like.

(G) semiconductor particle dispersion

In the present invention, a porous semiconductor fine particle coating layer can be obtained by applying a semiconductor fine particle dispersion liquid onto the conductive support 1 and heating it moderately, and the content of solid components other than the semiconductor fine particles in the semiconductor fine particle dispersion is semiconductor fine particles. The entire dispersion is 10% by weight or less.

The method for producing the semiconductor fine particle dispersion liquid may be, in addition to the sol-gel method described above, in the form of fine particles in a solvent when synthesizing a semiconductor. A method of directly using, a method of pulverizing ultrafine particles by irradiating ultrasonic waves or the like, or a method of mechanically pulverizing and grinding using a grinder or a mortar. As the dispersing solvent, one or more of water and various organic solvents can be used. The organic solvent may, for example, be an alcohol such as methanol, ethanol, isopropanol, citronellol or terpineol, a ketone such as acetone, an ester such as ethyl acetate, dichloromethane or acetonitrile.

When dispersing, a small amount of a polymer such as polyethylene glycol, hydroxyethyl cellulose, carboxymethyl cellulose, a surfactant, an acid, or a chelating agent may be used as a dispersing aid. However, before the film forming step is performed on the conductive support, it is preferred to remove most of the dispersing aids in advance by a filtration method or a method using a separation membrane or a centrifugal separation method. The content of the solid component other than the semiconductor fine particles in the semiconductor fine particle dispersion liquid may be 10% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less, particularly preferably 1% by weight or less, and particularly preferably 0.5% by weight or less. Good 0.2wt%. In other words, the solid content of the solvent and the semiconductor fine particles in the semiconductor fine particle dispersion may be 10% by weight or less based on the total amount of the dispersion liquid, and preferably contains only the semiconductor fine particles and the dispersion solvent.

When the viscosity of the semiconductor fine particle dispersion is too high, the dispersion is aggregated and film formation is impossible. Conversely, if the viscosity of the dispersion is too low, the liquid flows and the film cannot be formed. Therefore, the viscosity of the dispersion is preferably 10 to 300 N at 25 ° C. s / m ² , more preferably 50 ~ 200N at 25 ° C. s/m ² .

Regarding the method of applying the semiconductor fine particle dispersion, a method of applying the system can be carried out by a roll method, a dipping method, or the like. As another method of metering, an air knife method, a blade method, or the like can be used. Moreover, the common method of the application method and the metrology method is preferably: Japanese Patent Publication No. Sho 58-4589 The sliding bar method, the extrusion coating method, the curtain method, and the like described in the specification of the wire bar method and the specification of U.S. Patent No. 2,681,294. Further, a method of applying a general-purpose machine by a spin method or a spray method is also preferable. The wet printing method is preferably a gravure plate, a rubber plate, a screen printing or the like typified by three major printing methods of relief, lithography and gravure. Among them, a preferred film forming method is selected depending on the liquid viscosity or the wet thickness. Further, since the semiconductor fine particle dispersion of the present invention has high viscosity and is viscous, it has a strong cohesive force and may not be sufficiently fused with the support at the time of coating. In this case, the surface can be cleaned and hydrophilized by UV ozone treatment, and the adhesion of the applied semiconductor fine particle dispersion to the surface of the conductive support 1 is increased, so that the application of the semiconductor fine particle dispersion is facilitated.

The thickness of the semiconductor fine particle layer as a whole is preferably 0.1 to 100 μm , more preferably 1 to 30 μm , and particularly preferably 2 to 25 μm . The carrying amount of the semiconductor fine particles per 1 m ^{2 of the} support is preferably from 0.5 to 400 g, more preferably from 5 to 100 g.

In order to enhance the electronic contact between the semiconductor fine particles and improve the adhesion to the support, and to dry the applied semiconductor fine particle dispersion, the coating layer may be subjected to heat treatment to form a porous semiconductor fine particle layer.

In addition, light energy can be used in addition to heat treatment. For example, when titanium oxide is used as the semiconductor fine particles 22, light absorbed by the semiconductor fine particles 22 such as ultraviolet light can be supplied to activate the surface, and only the surface of the semiconductor fine particles 22 can be activated by laser light or the like. The semiconductor fine particles 22 are irradiated with light that can be absorbed, and the impurities adsorbed on the surface thereof are decomposed by activation of the surface thereof, which is a preferable state for achieving the above object. When the heat treatment and the ultraviolet light are combined, it is preferred to irradiate the semiconductor fine particles 22 with the light absorbed thereby, and to heat at 100 ° C or more and 250 ° C or less, or preferably 100 ° C or more and 150 ° C or less. So, borrow By photoexcitation of the semiconductor fine particles 22, impurities mixed in the fine particle layer can be cleaned by photolysis, and physical bonding between the fine particles can be enhanced.

Further, after the semiconductor fine particle dispersion is applied onto the conductive support 1, the other treatment may be performed in addition to heating or illumination. A preferred method is exemplified by energization, chemical treatment, and the like.

The pressure may be applied after the application, and the method may, for example, be Japanese Patent Laid-Open Publication No. 2003-500857. Examples of the illumination include Japanese Patent Laid-Open Publication No. 2001-357896. Examples of the plasma, the microwave, and the electric current are exemplified by Japanese Laid-Open Patent Publication No. 2002-353453. For example, JP-A-2001-357896 can be cited as a chemical treatment.

In the method of applying the semiconductor fine particles 22 to the conductive support 1, in addition to the above method of applying the semiconductor fine particle dispersion onto the conductive support 1, the method described in Japanese Patent No. 2664194 (the semiconductor fine particles 22 can be used). A method in which the precursor is applied to the conductive support 1 and hydrolyzed by moisture in the air to obtain a semiconductor fine particle film).

The precursor may, for example, be (NH ₄ ) ₂ TiF ₆ , titanium peroxide, a metal alkoxide-metal complex-metal organic acid salt or the like.

In addition, a method of forming a semiconductor film by a slurry of a metal organic oxide (such as an alkoxide) and forming a semiconductor film by heat treatment or light treatment, and a slurry or slurry in which an inorganic precursor is present may be used. The pH value and the properties of the dispersed titanium oxide particles are specifically set. Among these slurries, a binder may be added in a small amount, and examples of the binder include cellulose, fluoropolymer, crosslinked rubber, polybutyl titanate, and carboxymethylcellulose.

Techniques related to the formation of semiconductor particles 22 or their precursor layers For example, a method of hydrophilization by a physical method such as corona discharge, plasma, or ultraviolet light; chemical treatment by alkali or polyethylene dioxythiophene and polystyrenesulfonic acid; and intermediate bonding of polyaniline or the like Formation of a film, etc.

The method of applying the semiconductor fine particles 22 to the conductive support 1 may be carried out in combination with the above (1) wet method (2) dry method or (3) other methods. (2) The dry method is preferably exemplified by Japanese Laid-Open Patent Publication No. 2000-231943. (3) Other methods are preferably Japanese Patent Laid-Open Publication No. 2002-134435.

The dry method can be exemplified by evaporation or sputtering, gas deposition, and the like. Alternatively, an electrophoresis-electrolysis method can also be used.

Alternatively, a method of temporarily producing a coating film on a heat-resistant substrate and transferring it to a film such as plastic may be used. Preferably, the method of transferring by ethylene-vinyl acetate (EVA) described in JP-A-2002-184475, and the ultraviolet-ray, water-based system are described in JP-A-2003-98977. A method in which a semiconductor layer-conductive layer is formed on a sacrificial substrate of a solvent-removed inorganic salt, and then transferred to an organic substrate to remove a sacrificial substrate.

The semiconductor fine particles 22 are capable of adsorbing a large amount of the sensitizing dye 21, and preferably have a large surface area. For example, in the case where the semiconductor fine particles 22 are coated on the conductive support 1, 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. A preferred structure of the semiconductor fine particles 22 is, for example, Japanese Laid-Open Patent Publication No. 2001-93591.

Generally, the larger the thickness of the semiconductor fine particle layer, the more the amount of the sensitizing dye 21 that can be carried per unit area, so the higher the light absorption efficiency, but the diffusion distance of the generated electrons increases, and thus the charge recombination is caused. The loss has also increased. The preferred thickness of the semiconductor fine particle layer varies depending on the use of the element, and is typically 0.1 to 100 μm . When used in a photoelectrochemical cell, it is preferably 1 to 50 μm , more preferably 3 to 30 μm . After the semiconductor fine particles are applied to the support, the particles may be heated at a temperature of 100 to 800 ° C for 10 minutes to 10 hours in order to adhere them to each other. When glass is used as the support, the film formation temperature is preferably 400 to 600 °C.

When a polymer material is used as the support, it is preferred to heat the film after forming at 250 ° C or lower. The film forming method at this time may be any one of (1) wet method, (2) dry method, and (3) electrophoresis method (including electrodeposition method), and preferably (1) wet method or (2) dry type. The method is more preferably (1) wet method.

Further, the coating amount of the semiconductor fine particles 22 per 1 m ^{2 of the} support is 0.5 to 500 g, preferably 5 to 100 g.

In order to adsorb the sensitizing dye 21 to the semiconductor fine particles 22, it is preferred to immerse the sufficiently dried semiconductor fine particles 22 for a long time in the dye solution for dye adsorption containing the solvent and the dye of the present invention. The solvent used for the dye solution for dye adsorption is not particularly limited as long as it can dissolve the sensitizing dye 21 of the present invention. As described above, the solvent for dissolving the metal complex dye composition in the present invention is an organic solvent, and examples thereof include a nonpolar solvent, a polar aprotic solvent, a polar protic solvent, an ionic liquid, and the like. A polar solvent, a polar aprotic solvent, or a polar protic solvent is preferred, and for example, ethanol, methanol, isopropanol, toluene, tertiary butanol, acetonitrile, acetone, n-butanol, N, N-di can be used. Methylformamide, N,N-dimethylacetamide, and the like. Among them, ethanol and toluene can be preferably used.

The solubility of the metal complex dye composition in the above solvent in the present invention is preferably 100 mg/L or more, more preferably 105 mg/L or more, and particularly preferably 110 mg/L or more at 25 °C.

The dye solution for dye adsorption containing the solvent and the dye of the present invention may be heated to 50 to 100 ° C as needed. The adsorption of the sensitizing dye 21 can be carried out before the application of the semiconductor fine particles 22, or after the coating. Further, the semiconductor fine particles 22 and the sensitizing dye 21 may be simultaneously coated and adsorbed. The unadsorbed sensitizing dye 21 is removed by washing. When the coating film is to be calcined, the adsorption of the sensitizing dye 21 is preferably carried out after calcination, and it is particularly preferable to rapidly adsorb the sensitizing dye 21 after the calcination and before the water is adsorbed on the surface of the coating film. The adsorbed sensitizing dye 21 may be one type of the above-mentioned dye A1, and may be further mixed with other dyes. In order to maximize the wavelength region of the photoelectric conversion, a mixed pigment can be selected. When the coloring matter is mixed, it is preferred to dissolve all the pigments to prepare a dye solution for dye adsorption.

The amount of the sensitizing dye 21 is generally 0.01 to 100 mmol, preferably 0.1 to 50 mmol, and preferably 0.1 to 10 mmol, per 1 m ^{2 of the} support. At this time, the amount of the sensitizing dye 21 of the present invention is preferably set to 5 mol% or more.

Further, the amount of adsorption of the sensitizing dye 21 on the semiconductor fine particles 22 is preferably 0.001 to 1 mmol, and more preferably 0.1 to 0.5 mmol, relative to the semiconductor fine particles 1 g.

By setting the amount of the dye in this manner, the sensitizing effect of the semiconductor can be sufficiently obtained. On the other hand, when the amount of the pigment is small, the sensitizing effect is insufficient, and when the amount of the dye is too large, the dye that does not adhere to the semiconductor floats and the sensitizing effect is lowered.

Further, in order to reduce the interaction between the dyes such as association, the colorless compound may be co-adsorbed. The co-adsorbed hydrophobic compound may, for example, be a steroid compound having a carboxyl group (for example, cholic acid or pivaloyl acid).

After the sensitizing dye 21 is adsorbed, the surface of the semiconductor fine particles 22 may be treated with an amine. Preferred examples of the amines include 4-tris-butylpyridine and polyvinylpyridine. These may be used as a liquid or as an organic solvent.

The counter electrode 4 serves as the positive electrode of the photoelectrochemical cell. The counter electrode 4 is generally synonymous with the above-described conductive support 1, and in the configuration in which the strength is sufficiently maintained, the support for the counter electrode is not necessarily required, but when the support is provided, it is advantageous in terms of hermeticity. The material of the counter electrode 4 may, for example, be platinum, carbon, a conductive polymer or the like. Preferable examples include platinum, carbon, and a conductive polymer.

The structure of the counter electrode 4 is preferably a structure having a high current collecting effect, and a preferred example thereof is disclosed in Japanese Laid-Open Patent Publication No. Hei 10-505192.

As the light-receiving electrode 5, a composite electrode of titanium oxide and tin oxide (TiO ₂ /SnO ₂ ) or the like can be used, and a mixed electrode of titanium dioxide can be exemplified by JP-A-2000-113913. The mixed electrode other than titanium dioxide can be exemplified by Japanese Patent Laid-Open Publication No. 2001-185243, No. 2003-282164, and the like.

Further, the photoelectric conversion element may have a configuration in which the first electrode layer, the first photoelectric conversion layer, the conductive layer, the second photoelectric conversion layer, and the second electrode layer are laminated in this order. In this case, the dyes used for the first and second photoelectric conversion layers may be the same or different, and when the dyes used are different, the absorption spectra are preferably different.

The light receiving electrode 5 can also be formed in series in order to increase the utilization rate of incident light or the like. The preferred embodiment of the tandem type is exemplified by Japanese Patent Laid-Open No. 2000-90989, Japanese Patent Laid-Open No. 2002-90989, and the like.

A light management function for efficiently performing light scattering and reflection may be provided inside the layer of the light-receiving electrode 5, and a function described in Japanese Laid-Open Patent Publication No. 2002-93476 is preferably exemplified.

In order to prevent a reverse current caused by the direct contact between the electrolyte and the electrode, a short-circuit prevention layer is preferably formed between the conductive support 1 and the porous semiconductor fine particle layer, and a preferred example thereof is a Japanese Patent Publication No. 06-507999. Wait.

In order to prevent the light-receiving electrode 5 from coming into contact with the counter electrode 4, a spacer or a spacer is preferably used. A preferred example is JP-A-2001-283941.

The sealing method of the unit and the module is preferably: using a polyisobutylene thermosetting resin, a varnish resin, a photocurable (meth) acrylate resin, an epoxy resin, an ionic polymer resin, a glass powder, and an alkane in the alumina. A method of alumina; a method of laser melting a low-melting glass paste, and the like. When glass frit is used, the powder glass can be mixed into an acrylic resin as a binder.

[Example]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto.

1. Preparation of crude purified product of metal complex pigment

The crude purified product of the metal complex was prepared by the following method (1) by external heating and (2) by microwave heating, and then purified by 2.

(1) Preparation of crude purified product using externally heated metal complex pigment (a) Preparation of crude purified product of metal complex dye D-20

The crude purified product of D-20 in the metal complex dye of the general formula (1) shown in the above specific example was prepared by the method shown below.

<coordination synthesis>

<complexation>

<coordination synthesis> (i) Preparation of compound d-1-2

25 g of d-1-1, 3.8 g of Pd ₂ (dba) ₃ , 8.6 g of triphenylphosphine, 2.5 g of copper iodide, 25.2 g of 1-heptyne in 70 mL of triethylamine, 50 mL of tetrahydrofuran in the chamber The mixture was stirred at a temperature and further stirred at 80 ° C for 4.5 hours. After concentration, it was purified by column chromatography to give 26.4 g of Compound d-1-2.

(ii) Preparation of d-1-4

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

(iii) Preparation of Compound d-1-5

13.2 g of d-1-4, 1.7 g of PPTS (pyridinium p-toluenesulfonate) was added to 1000 mL of toluene, and the mixture was heated under reflux for 5 hours under a nitrogen atmosphere. After concentrating, the organic layer was concentrated with EtOAc EtOAc m.

<complexation>

The metal complex dye D-20 was prepared by external heating and complexation. 3.0 g of d-1-5 and 1.64 g of d-1-6 synthesized above were added to 35 mL of DMF (dimethylformamide), and stirred at 70 ° C for 90 minutes in a dark room. At this time, it is heated from the outside by an oil bath. Then, 1.3 g of d-1-7 was added, and 270 mL of DMF was added, and the mixture was stirred under heating at 160 ° C for 150 minutes. At this time, it is heated from the outside by an oil bath. Then 14.25 g of ammonium thiocyanate was added and stirred at 130 ° C for 5 hours. At this time, it is heated from the outside by an oil bath. After concentration, 300 mL of water was added for filtration, and the mixture was washed with diethyl ether to give a crude purified product.

(b) Preparation of crude purified product of metal complex dye D-10

A crude purified product of D-10 in the metal complex dye of the above formula (1) shown in the above specific examples was prepared by the method shown below.

<coordination synthesis>

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

(i) Preparation of compound d-2-2

25 g of d-2-1 was dissolved in 500 mL of THF and cooled in an ice bath, and 1.05 equivalent of n-butyllithium (1.6 mol/L hexane solution) was added dropwise. Then, 1.5 equivalent of dimethylformamide was added dropwise, and the mixture was stirred at room temperature for 1 hour. Saturated aqueous ammonium chloride solution was added dropwise, and liquid separation and extraction were carried out. After concentration, it was purified by distillation under reduced pressure to give 25.6 g of Compound d-2-2.

(ii) Preparation of d-2-4

In the preparation of the metal complex dye D-20 of (a), d-1-2 used for the preparation of d-1-4 is replaced by d-2-2, and d-2-3 is used in the same manner to prepare d- 2-4.

(iii) Preparation of compound d-2-5

In the preparation of the metal complex dye D-20 of (a), the d-1-4 used for the preparation of d-1-5 was changed to d-2-4, and further, d-2-5 was prepared in the same manner. .

<complexation>

A crude purified product of the metal complex dye D-10 was prepared by external heating and complexation.

The crude purified product of D-10 was prepared in the same manner except that d-1-5 used in the preparation of D-20 in (a) was replaced by d-2-5.

(2) Preparation of crude purified product of metal complex dye heated by microwave (a) Preparation of crude purified product of metal complex dye D-20

3.0 g of compound d-1-5 and 1.64 g of d-1-6 were added to 35 mL of DMF, and microwaved (frequency 2.45 GHz) in a dark room and stirred at 70 ° C for 10 minutes. Then, 1.3 g of d-1-7 was added, and 270 mL of DMF was added, and the mixture was heated and stirred at 160 ° C for 10 minutes by the above microwave. Then, 14.25 g of ammonium thiocyanate was added, and the mixture was stirred at 130 ° C for 10 minutes by the above microwave. After concentration, 300 mL of water was added and filtered, and the mixture was washed with diethyl ether to give crude purified D-20.

(b) Preparation of crude purified product of metal complex dye D-10

The external heating of (1) (b) was changed to microwave heating (conditions were the same as (2) (a)), and further, 2.5 g of a crude purified product of D-10 was obtained in the same manner.

2. A metal complex dye containing the formula (5) and/or a metal complex of the formula (6) Preparation of pigment metal complex dye composition and metal complex pigment (1) Preparation of a metal complex dye composition using external heating

1. The crude purified product of the metal complex dye D-20 obtained in (1) (a) was dissolved in a methanol solution together with tetrabutylammonium hydroxide (TBAOH) to Sephadex LH-20 (product of GE Healthcare). Name) Column purification. The fraction of the main layer was recovered and concentrated, and then 0.2 M of nitric acid was added to obtain a precipitate. After filtration, it is washed with water and diethyl ether, and at least one metal containing the metal complex dye of the formula (5) and the metal complex dye of the formula (6) having D-17 as a main component is misaligned. Pigment composition. When the column is purified, 50 g of the carrier liquid is used for 200 mg of the crude purified product, and the number of times of performing the column purification is changed to 1 to 4 times, thereby obtaining the metal complex dye of the general formula (5) and the general formula (6). At least one metal complex pigment composition of the metal complex dye (Examples 1-4).

The crude purified product of the metal complex dye D-10 obtained in (1)(b) is purified in the same manner, and the metal complex dye containing the general formula (5) and the general formula (D-11) are used as the main component. 6) A metal complex dye composition of at least one of the metal complex dyes (Examples 5 to 8). In addition, the obtained metal complex dye composition is further dissolved in a methanol solution together with tetrabutylammonium hydroxide, and a 0.1 N methanol solution of nitric acid is added dropwise to pH=0 to obtain a general formula of D-10 as a main component ( At least one metal complex dye composition of the metal complex dye of 5) and the metal complex dye of the formula (6) (Examples 9 to 12).

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

For comparison with (1), the crude purified product of the metal complex dye D-20 prepared by microwave heating obtained in 1. (2) (a) was purified in the same manner as (1), and D-17 was obtained. a metal complex dye containing the general formula (5) as a main component At least one metal complex dye composition of the metal complex dye of the formula (6) (Comparative Examples 1 to 3). Further, the crude purified product of the metal complex dye D-10 obtained in 1. (2) (b) was purified in the same manner, and the metal complex dye containing the general formula (5) having D-11 as a main component was purified. And at least one metal complex dye composition of the metal complex dye of the formula (6) (Comparative Examples 5 to 7). Further, the obtained metal complex dye composition was further dissolved in a methanol solution together with tetrabutylammonium hydroxide, and a 0.1 N methanol solution of nitric acid was added dropwise until pH=0, and the general formula of D-10 was contained. At least one metal complex dye composition of the metal complex dye of (5) and the metal complex dye of the formula (6) (Comparative Examples 9 to 11).

(3) Preparation of metal complex pigment by HPLC separation

The crude purified product of 1.(1)(a) was purified by HPLC, and the crude purified product was first dissolved in a solution of tetrabutylammonium hydroxide in methanol, and then Caps Pak UG120 was made by Shiseido. The 30 mm × 250 mm LC fractionation column was purified, and the composition of the eluent was set to methanol/water = 85/15 to 95/5. The fraction of the main layer was recovered and concentrated, and 0.2 M nitric acid was added to obtain a precipitate. After filtration, it was washed with water and diethyl ether to obtain 3.2 g of a metal complex dye D-17 of the formula (1) (Comparative Example 4).

The structure of the obtained metal complex dye D-17 was confirmed by nuclear magnetic resonance (NMR) measurement and liquid chromatography-mass spectrometry (LC-MS).

¹ H-NMR (DMSO-d ₆ , 400 MHz): Aromatic region δ (ppm): 9.37 (1H, d), 9.11 (1H, d), 9.04 (1H, s), 8.89 (2H), 8.74 (1H) , s), 8.26 (1H, d), 8.10-7.98 (2H), 7.85-7.73 (2H), 7.60 (1H, d), 7.45-7.33 (2H), 7.33-7.12 (5H, m), 6.92 ( 1H,d)

MS-ESI m/z: 1023.143 (M+H) ⁺

The obtained metal complex dye D-17 (Comparative Example 8) was dissolved in tetrahydrofuran:water = 63:37 (0.1% trifluoroacetic acid) to prepare a solution having a concentration of 8.5 μmol/L, using U-4100 spectrophotometer (Hitachi Corporation). The product was subjected to spectral absorption measurement, and the absorption maximum wavelength was 568 nm.

Similarly, the metal complex dye D-11 (Comparative Example 8) was also purified by HPLC using the crude purified product obtained in 1. (1) (b).

MS-ESI m/z: 1003.2 (M+H) ⁺

Then, it was dissolved in THF:water = 63:37 (0.1% trifluoroacetic acid) to prepare a solution having a concentration of 8.5 μmol/L, and subjected to spectral absorption measurement using a U-4100 spectrophotometer (manufactured by Hitachi, Ltd.), and the absorption maximum wavelength was 566 nm.

The obtained metal complex dye D-11 was dissolved in a methanol solution together with tetrabutylammonium hydroxide, and a 0.1 N methanolic solution of nitric acid was added dropwise until pH = 0 to obtain D-10 (Comparative Example 12).

MS-ESI m/z: 1003.2 (M+H) ⁺

Then, it was dissolved in THF:water = 63:37 (0.1% trifluoroacetic acid) to prepare a solution having a concentration of 8.5 μmol/L, and subjected to spectral absorption measurement using a U-4100 spectrophotometer (manufactured by Hitachi, Ltd.), and the absorption maximum wavelength was 571 nm.

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

The metal complex dye contained in the obtained metal complex dye composition was identified by the following (a) to (b), and the content thereof was determined. The values are shown in Table 1.

(a) Measurement of high performance liquid chromatography

The obtained metal complex pigment composition was subjected to HPLC measurement under the following conditions. Metal complex dye of the formula (5) and/or metal of the formula (6) The content ratio of the dye is determined by identifying a metal complex having a CN ligand together with the LC-MS measurement results described later.

(Measurement conditions for high performance liquid chromatography (HPLC))

Use equipment: system controller SCL-10AVP

Column oven CTO-10ASVP

Detector SPD-10AVVP

Deaerator DGU-14AM

Liquid supply unit LC-10ADVP (trade name of Shimadzu Corporation)

Column: YMC-Pack ODS-AM, model AM-312

Dimensions 150×6.0 mm I.D. (manufactured by YMC Co., Ltd. Japan)

Flow rate: 0.75mL/min

Dissolution: THF/water = 63/37 containing 0.1% trifluoroacetic acid

Temperature: 40 ° C

Detection wavelength: 254nm

(b) Identification of metal complex pigments in metal complex pigment compositions

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

(Measurement conditions of LC-MS)

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

Ionization method: ESI-posi

Detection method: TOF-MS

Column: YMC-Pack ODS-AM, model AM-312

Dimensions 150 × 6.0 mm I.D. (manufactured by YMC Co., Ltd. Japan)

Flow rate: 0.75mL/min

Dissolution: THF/water = 63/37 containing 0.1% trifluoroacetic acid

Temperature: 40 ° C

The metal complex dye of the formula (5) contained in the metal complex dye composition containing D-17 as a main component and the formula (6) were detected as follows. Further, the acidic group of counter ions was detected as a proton by the trifluoroacetic acid contained in the elution solution. In the metal complex composition, the counter ion may be proton or tetrabutylammonium.

MS-ESI m/z: 991.163 (M+H) ⁺ 959.194 (M+H) ⁺

Absorption maximum wavelength: 542nm 515nm

a metal complex dye composition containing D-11 as a main component and a metal complex dye of the formula (5) contained in a metal complex dye composition containing D-10 as a main component and a general formula ( All of 6) were detected as the following structures. Further, the acidic group counter ion is detected as a proton by the trifluoroacetic acid in the eluate, but the counter ion in the metal complex composition may be a proton or tetrabutylammonium.

MS-ESI m/z: 971.194 (M+H) ⁺ 939.223 (M+H) ⁺

Maximum absorption wavelength: 540nm 513nm

4. Evaluation of the solubility of pigment in solution

12 mg of each of the metal complex dye compositions shown in Table 1 was dissolved in a mixed solvent of 50 mL of toluene and 50 mL of methanol in a dark room, and the mixture was stirred at 25 ° C for 15 minutes with a stirring blade to obtain a dye solution. The amount of the metal complex dye represented by the formula (1) in the solution was quantified using the HPLC apparatus used in the above method. The dissolved amount is 11.0 mg or more and 12.0 mg or less is marked as A, 10.0 mg or more and less than 11.0 mg is marked as B, 9.0 mg or more and less than 10.0 mg is marked as C, and less than 9.0 mg is marked as D, wherein A and B are qualified.

5. Adsorption evaluation of pigment on semiconductor particle electrode (Production of semiconductor microparticle electrode)

A fluorine-doped tin oxide is formed on the glass substrate by a sputtering method as a transparent conductive film, and the transparent conductive film is divided into two portions by laser cutting.

Next, 32 g of anatase-type titanium oxide (P-25 (trade name) manufactured by Nippon Aerosil Co., Ltd.) was blended in a 100 mL mixed solvent containing water and acetonitrile in a volume ratio of 4:1, and a mixing regulator was used for the rotation/revolution type. Disperse and mix uniformly to obtain a semiconductor fine particle dispersion. Applying this dispersion to a transparent guide On the electric film, a semiconductor fine particle electrode was produced by heating at 500 °C.

A dispersion containing SiO ₂ particles and rutile-type titanium oxide having a mass ratio of 40:60 was produced in the same manner, and the dispersion was applied onto the above-mentioned light-receiving electrode, and heated at 500 ° C to form an insulating porous body, and then a carbon electrode was formed. Electrode.

Next, the glass substrate on which the above-mentioned insulating porous body was formed was immersed in an ethanol solution of the metal complex dye composition of Table 1 for 12 hours. The sensitized dyed glass was immersed in a solution of 4-tris-butylpyridine in 10% ethanol for 30 minutes, washed with ethanol and naturally dried. The thickness of the photosensitive layer thus obtained was 10 μm , and the coating amount of the semiconductor fine particles was 20 g/m ² .

(Adsorption evaluation)

2.3 cm ² of the semiconductor fine particle electrode produced by the above method was bubbled in each dye solution at 40 ° C for 30 minutes in a dark room. The semiconductor microparticle electrode after the dye adsorption was subjected to pigment desorption using a 10% TBAOH methanol solution, and the initial adsorption amount of each pigment was quantified by HPLC. The amount of dissolution in the solution was determined in the same manner as the HPLC used in the method of the above 3. When the adsorption amount is 1.0 mg or more, the label is A, 0.9 mg or more and less than 1.0 mg is B, 0.7 mg or more and less than 0.9 mg is C, and less than 0.7 mg is D, wherein A and B are acceptable.

6. Evaluation of photoelectric conversion efficiency of photoelectric conversion elements (Production of semiconductor microparticle electrode)

A fluorine-doped tin oxide is formed on the glass substrate by a sputtering method as a transparent conductive film, which is laser-cut, and the transparent conductive film is divided into two portions.

Next, 32 g of anatase-type titanium oxide (P-25 (trade name) manufactured by Nippon Aerosil Co., Ltd.) was blended in a 100 mL mixed solvent containing water and acetonitrile in a volume ratio of 4:1, and a mixing regulator was used for the rotation/revolution type. Evenly dispersed, Mixing to obtain a semiconductor fine particle dispersion. This dispersion liquid was applied onto a transparent conductive film, and heated at 500 ° C to prepare a semiconductor fine particle electrode.

A dispersion containing SiO ₂ particles and rutile-type titanium oxide having a mass ratio of 40:60 was produced in the same manner, and the dispersion was applied onto the above-mentioned light-receiving electrode, and heated at 500 ° C to form an insulating porous body, and then a carbon electrode was formed. Electrode.

Next, the glass substrate on which the above-mentioned insulating porous body was formed was immersed in the dye solution shown in Table 1 prepared for 4 hours. The sensitized dyed glass was immersed in a solution of 4-tris-butylpyridine in 10% ethanol for 30 minutes, washed with ethanol and naturally dried. The thickness of the photosensitive layer thus obtained was 10 μm , and the coating amount of the semiconductor fine particles was 20 g/m ² .

Then, the semiconductor fine electrode was placed opposite to the platinum sputtered FTO substrate via a 50 μm-thick thermoplastic polyolefin resin sheet, and the resin sheet portion was thermally melted to fix the two plates.

In addition, the electrolyte is injected from the liquid injection port opened in advance on the platinum sputtering electrode side, and the electrode is filled, and the peripheral portion and the electrolyte injection port are completely sealed with the epoxy sealing resin, and silver is applied to the current collecting terminal portion. A photoelectric conversion element is produced by glue.

The electrolytic solution was a methoxypropionitrile solution using dimethylpropylimidazolium iodide (0.5 mol/L) and iodine (0.1 mol/L).

(Evaluation of photoelectric conversion elements)

The light of a 500 W xenon lamp (manufactured by Ushio Electric Co., Ltd.) was passed through an AM 1.5 filter (manufactured by Oriel Co., Ltd.) and a sharp cut filter (Kenko L-42) to prepare a simulated sunlight containing no ultraviolet rays. The light intensity was 89 mW/cm ² .

The crocodile clip is respectively connected to the conductive glass plate and the platinum vapor-deposited glass plate of the photoelectrochemical cell, so that the crocodile clips are connected to the current and voltage measuring device. (Keithley SMU238 (trade name)). The simulated sunlight is irradiated from the side of the conductive glass plate, and the generated electricity is measured by a current-voltage measuring device. The photoelectrochemical cell conversion efficiency determined thereby is 9.0% or more and is marked as A, 8.0% or more and less than 9.0% is marked as B, 7.0% or more and less than 8.0% is marked as C, and less than 7.0% is marked as D, wherein A and B are To be qualified.

As is clear from Table 1, when the metal complex dye represented by the formula (5) or (6) is too large, there is a problem in photoelectric conversion efficiency; when the metal complex dye is too small, The amount of the pigment dissolved, the amount of adsorption, and the photoelectric conversion efficiency also have problems.

On the other hand, the metal complex dye composition of the present invention can satisfy any of the characteristics. When the content of the metal complex dye represented by the formula (5) or (6) is large, the solubility tends to be improved. When the content of the metal complex is > 5.0%, the amount of adsorption tends to decrease. It is estimated that the low conversion efficiency metal complex pigment represented by the general formula (5) or (6) is preferentially adsorbed, resulting in a decrease in conversion efficiency.

The present invention is not limited to the details of the invention as set forth in the accompanying claims, unless otherwise specified.

The present application claims priority to Japanese Patent Application No. 2011-054802, filed on Jan. 11, 2011, the entire disclosure of which is hereby incorporated by reference.

1‧‧‧Electrical support

2‧‧‧Photoreceptor layer

3‧‧‧ Charge transport layer

4‧‧‧ opposite electrode

5‧‧‧Photoelectrode

6‧‧‧External circuit

10‧‧‧ photoelectric conversion components

21‧‧‧ Sensitizing pigment

22‧‧‧Semiconductor particles

100‧‧‧Photoelectrochemical battery

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

1‧‧‧Electrical support

2‧‧‧Photoreceptor layer

3‧‧‧ Charge transport layer

4‧‧‧ opposite electrode

5‧‧‧Photoelectrode

6‧‧‧External circuit

10‧‧‧ photoelectric conversion components

21‧‧‧ Sensitizing pigment

22‧‧‧Semiconductor particles

100‧‧‧Photoelectrochemical battery

Claims (10)

A metal complex dye composition comprising a metal complex dye represented by the following formula (1), a metal complex dye represented by the following formula (5), and the following formula (6) The metal complex dye shown in the formula; the metal complex dye represented by the formula (5) and the metal represented by the formula (6) by the area of 254 nm detected by HPLC (High Performance Liquid Chromatography) The content of the complex dye is 0.5 to 5% in total, M ¹ (LL ¹ ) _m1 (LL ² ) _m2 (Z ¹ ) ₂ ‧ (CI ¹ ) _m3 Formula (1) [in the formula (1), M ¹ represents a metal atom, LL ¹ is a bidentate ligand represented by the following formula (2), LL ² is a bidentate ligand represented by the following formula (3); m1 represents 1; m2 represents 1; Z ¹ represents a ligand, which is at least one selected from the group consisting of isothiocyanato, isocyanate, and isoselenocyano; CI ¹ represents a counter ion when ions are required to neutralize charges, and m3 is 0 or more. Integer] [In the formula (2), R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ independently represent an acidic group or a salt thereof or a hydrogen atom, and R ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ may be the same or different; wherein R At least one of ¹¹ to R ¹⁴ and R ²¹ to R ²⁴ is an acidic group or a salt thereof] [In the general formula (3), n1 and n2 independently represent an integer of 0 to 3, and Y ¹ and Y ² independently represent a hydrogen atom or a heteroaryl group represented by the following formula (4), but Ar ¹ and Ar ^{2 are} independently Indicates a heteroaryl group represented by the following formula (4)] [In the formula (4), R ³¹ to R ³³ independently represent a hydrogen atom, an alkyl group, an alkoxy group or an alkynyl group, and at least one of R ³¹ to R ³³ is an alkyl group, an alkoxy group or an alkynyl group; Is a sulfur atom, an oxygen atom, a selenium atom or NR ⁴ , and R ⁴ is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group] M ¹ (LL ¹ ) _m1 (LL ² ) _m2 (Z ¹ ) (CN) ‧ ( CI ¹ ) _m3 Formula (5) [In the formula (5), M ¹ , LL ¹ , LL ² , Z ¹ , CI ¹ , m1, m2 and m3 have the same meanings as in the formula (1)] M ¹ (LL ¹ ) _m1 (LL ² ) _m2 (CN) ₂ ‧(CI ¹ ) _m3 Formula (6) [In the formula (6), M ¹ , LL ¹ , LL ² , Z ¹ , CI ¹ , m1 The meanings of m2 and m3 are the same as those in the formula (1)]. The metal complex dye composition according to claim 1, wherein LL ^{2 in} the formula (1) is represented by the following formula (7): [In the formula (7), R ⁴¹ to R ⁴³ and R ⁵¹ to R ⁵³ independently represent a hydrogen atom, an alkyl group, an alkoxy group or an alkynyl group; and at least one of R ⁴¹ to R ⁴³ is an alkyl group or an alkoxy group; a group or an alkynyl group; at least one of R ⁵¹ to R ⁵³ is an alkyl group, an alkoxy group or an alkynyl group; and X ¹ and X ² are each independently a sulfur atom, an oxygen atom, a selenium atom or NR ⁷ , and R ⁷ is hydrogen. Atom, alkyl, aryl or heterocyclic group]. The metal complex dye composition according to claim 2, wherein X ¹ and X ² in the formula (7) are sulfur atoms. The metal complex dye composition according to any one of claims 1 to 3, wherein the metal complex dye represented by the formula (1) is represented by the following formula (8): In the formula (8), R ⁶¹ and R ^{62 each} independently represent an alkyl group, an alkoxy group or an alkynyl group, and A ¹ and A ² independently represent a carboxyl group or a salt thereof. The metal complex dye composition according to any one of claims 1 to 3, wherein the metal complex dye represented by the formula (5) is represented by the following formula (9): The metal complex dye shown in (6) is represented by the following formula (10): [In the formula (9), R ⁷¹ and R ⁷² independently represent an alkyl group, an alkoxy group or an alkynyl group, and A ⁵ and A ⁶ independently represent a carboxyl group or a salt thereof; in the formula (10), R ⁷³ and R ^{74 are} independently It represents an alkyl group, an alkoxy group or an alkynyl group, and A ⁷ and A ^{8 are each} independently a carboxyl group or a salt thereof]. The metal complex dye composition according to the fourth aspect of the invention, wherein the metal complex dye represented by the formula (5) is represented by the following formula (9), and is represented by the formula (6) The metal complex pigment is represented by the following formula (10): [In the formula (9), R ⁷¹ and R ^{72 each} independently represent an alkyl group, an alkoxy group or an alkynyl group, and A ⁵ and A ⁶ independently represent a carboxyl group or a salt thereof; in the formula (10), R ⁷³ and R ^{74 are} independently It represents an alkyl group, an alkoxy group or an alkynyl group, and A ⁷ and A ^{8 are each} independently a carboxyl group or a salt thereof]. The metal complex dye composition according to any one of claims 1 to 3, wherein the metal complex dye represented by the formula (5) is represented by the following formula (11): The metal complex dye shown in (6) is represented by the following formula (12): [In the general formulae (11) and (12), R ⁸¹ to R ⁸⁴ independently represent an alkynyl group; and A ¹³ to A ¹⁶ independently represent a carboxyl group or a salt thereof]. The metal complex dye composition according to the fourth aspect of the invention, wherein the metal complex dye represented by the formula (5) is represented by the following formula (11), and is represented by the formula (6) The metal complex pigment is represented by the following formula (12): [In the general formulae (11) and (12), R ⁸¹ to R ⁸⁴ independently represent an alkynyl group; and A ¹³ to A ¹⁶ independently represent a carboxyl group or a salt thereof]. A photoelectric conversion element using the metal complex dye composition according to any one of claims 1 to 8 as a sensitizing dye. A photoelectrochemical cell comprising the photoelectric conversion element according to any one of the claims.