JP2011026534A - Dye, photoelectric conversion element and photoelectrochemical cell each comprising the dye - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dye-sensitized cell having high conversion efficiency by using an inexpensive organic dye. <P>SOLUTION: The dye has a structure represented by general formula (1) [wherein X is a non-metallic atom group necessary for forming 7-membered nitrogen-containing heterocyclic ring by bonding with a benzene ring; Y is a dye residue; n is an integer of ≥1; Z is a substituent; m is 0 or a positive integer; when m is ≥2, Z may be the same or different; and R<SP>1</SP>is a hydrogen atom, aliphatic group, aromatic group or heterocyclic group bonded through a carbon atom]. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a dye, a photoelectric conversion element sensitized with the dye, and a photoelectrochemical cell (a dye-sensitized solar cell) using the same.

  Photoelectric conversion elements are used in various optical sensors, copying machines, solar cells, and the like. Various types of photoelectric conversion elements have been put to practical use, such as those using metals, semiconductors, organic pigments and dyes, or combinations thereof. Above all, solar cells using non-depleting solar energy do not require fuel, and full-scale practical use is expected as inexhaustible clean energy. In this respect, silicon solar cells have been researched and developed for a long time. Popularization is progressing in consideration of the policy of each country. However, silicon is an inorganic material, and its throughput and molecular modification are naturally limited.

  Research on dye-sensitized solar cells has been vigorously conducted as a next-generation technology for solving the above-described problems. In particular, Greatzel et al. Of Lausanne University of Technology in Switzerland developed a dye-sensitized solar cell in which a dye composed of a ruthenium complex was fixed on the surface of a porous titanium oxide thin film, and realized a conversion efficiency comparable to that of amorphous silicon. Attracted attention from researchers.

  Patent Documents 1 to 3 describe dye-sensitized photoelectric conversion elements using semiconductor fine particles sensitized with a dye, to which this technique is applied. This has the advantage that the device can be manufactured in a relatively simple process. However, ruthenium complex dyes used as sensitizing dyes are extremely expensive. Ruthenium is also concerned about availability, and it is still not enough to respond in earnest as a technology to support the next generation of clean energy. R & D for practical use has just begun. For these reasons, it is desired to develop photoelectric conversion elements that are sensitized by inexpensive organic materials with low resource constraints and have sufficient conversion efficiency, and reports using organic dyes as sensitizers have been reported. (See Patent Document 4).

US Pat. No. 5,463,057 US Pat. No. 5,525,440 JP 7-249790 A JP 2008-135197 A

  An object of the present invention is to provide a photoelectrochemical cell having high conversion efficiency using an inexpensive dye.

As a result of intensive studies, the inventor has either a capability of absorbing sunlight in a wide wavelength region, which is a factor that affects conversion efficiency, and a high electron injection efficiency into the light receiving electrode, or It has been found that a photoelectrochemical cell with high conversion efficiency can be provided by satisfying both of these conditions and using this as a sensitizing dye. The present invention has been made based on this finding.
The object of the present invention has been achieved by the following means.

［一般式（１）中Ｘはベンゼン環と連結して七員環の含窒素複素環を形成するのに必要な非金属原子群を表す。Ｙは色素残基を表し、ｎは１以上の整数を表す。Ｚは置換基を表し、ｍは０又は正の整数を表す。ｍが２以上の場合、Ｚは同一でも異なっていてもよい。Ｒ^１は水素原子、脂肪族基、芳香族基又は炭素原子で結合する複素環基を表す。］
＜２＞前記一般式（１）で表される色素が、下記一般式（２）で表される構造を有することを特徴とする＜１＞記載の色素、

［一般式（２）において、Ｘはベンゼン環と連結して七員環の含窒素複素環を形成するのに必要な非金属原子群を表す。Ｒ^１は水素原子、脂肪族基、芳香族基又は炭素原子で結合する複素環基を表す。Ｒ^２〜Ｒ^９は水素原子、又は置換基を表し、置換基のうち少なくとも一つは一般式（３）で示される色素残基を表す。
一般式（３）においてＲ^１０、Ｒ^１１、及びＲ^１３は、それぞれ独立して、水素原子、脂肪族基、芳香族基、又は複素環基を表す。ｒは０以上の整数を示す。一般式（３）における炭素−炭素二重結合は、Ｅ型、又はＺ型のいずれであってもよい。Ｒ^１２は、酸性基を少なくとも一つ有する基または酸性核を表す。］
＜３＞前記一般式（１）又は一般式（２）で表される構造を有する色素が、下記一般式（４）で表されることを特徴とする＜１＞又は＜２＞記載の色素、

［一般式（４）において、Ｒ^１〜Ｒ^３、Ｒ^５〜Ｒ^１３は、それぞれ一般式（２）及び一般式（３）におけるＲ^１〜Ｒ^３、Ｒ^５〜Ｒ^１３と同義である。］
＜４＞前記一般式（１）又は一般式（２）で表される構造を有する色素が、下記一般式（５）で表されることを特徴とする＜１＞又は＜２＞記載の色素、

［一般式（５）において、Ｒ^１〜Ｒ^１３は、それぞれ一般式（２）及び一般式（３）におけるＲ^１〜Ｒ^１３と同義である。
一般式（５）において、Ｒ^１４は水素原子、アルキル基、アルコキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、又は複素環基を表す。］
＜５＞前記一般式（１）又は（２）で表される構造を有する色素が、下記一般式（６）で表されることを特徴とする＜１＞又は＜２＞記載の色素、

［一般式（６）において、Ｒ^１〜Ｒ^３、Ｒ^５、Ｒ^６、Ｒ^８〜Ｒ^１３は、それぞれ一般式（２）及び一般式（３）におけるＲ^１〜Ｒ^３、Ｒ^５、Ｒ^６、Ｒ^８〜Ｒ^１３と同義である。］
＜６＞Ｒ^１２が下記一般式（７）または一般式（８）で表されることを特徴とする＜２＞〜＜５＞のいずれか１項記載の色素、

一般式（７）においてＲ^１５、Ｒ^１６は、それぞれ独立に、脂肪族基、芳香族基または複素環基である（少なくとも１つの官能基は酸性基を有していてもよい）。ｌは０又は１を示す。一般式（７）における炭素−炭素二重結合は、Ｅ型又はＺ型のいずれであってもよい。一般式（７）中のＲ^１７は硫黄原子または一般式（９）を表し、一般式（９）における炭素−炭素二重結合は、Ｅ型又はＺ型のいずれであってもよい。
一般式（８）におけるＲ^１８、Ｒ^１９は、それぞれ独立に、シアノ基又は酸性基を表し、互いに同一でも異なっていてもよい。一般式（８）における炭素−炭素二重結合は、Ｅ型又はＺ型のいずれであってもよい。
一般式（９）におけるＲ^２０、Ｒ^２１は、それぞれ独立に、シアノ基又は酸性基を表し、互いに同一でも異なっていてもよい。一般式（９）における炭素−炭素二重結合は、Ｅ型Ｚ型のいずれであってもよい。
＜７＞前記一般式（７）が下記一般式（１０）で表されることを特徴とする＜６＞記載の色素、

一般式（１０）においてＲ^１６は、脂肪族基、芳香族基または複素環基である（酸性基を有していてもよい）。
＜８＞前記Ｒ^１２が下記一般式（１１）で表されることを特徴とする＜２＞〜＜５＞のいずれか１項記載の色素、

一般式（１１）においてＲ^１５は、脂肪族基、芳香族基または複素環基である（酸性基を有していてもよい）。
＜９＞前記Ｒ^１２が下記一般式（１２）で表されることを特徴とする＜２＞〜＜５＞のいずれか１項記載の色素、

＜１０＞受光電極が、＜１＞〜＜９＞のいずれか１項に記載の色素によって増感される半導体微粒子を含有することを特徴とする光電変換素子、
＜１１＞受光電極と対極との間に絶縁性の多孔体を有することを特徴とする＜１０＞記載の光電変換素子、
＜１２＞＜１０＞〜＜１１＞のいずれか１項に記載の光電変換素子を備えることを特徴とする光電気化学電池。 <1> A dye having a structure represented by the following general formula (1):

[In the general formula (1), X represents a nonmetallic atom group necessary for forming a seven-membered nitrogen-containing heterocycle by linking with a benzene ring. Y represents a dye residue, and n represents an integer of 1 or more. Z represents a substituent, and m represents 0 or a positive integer. When m is 2 or more, Z may be the same or different. R ¹ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group bonded with a carbon atom. ]
<2> The dye according to <1>, wherein the dye represented by the general formula (1) has a structure represented by the following general formula (2):

[In General Formula (2), X represents a nonmetallic atom group required in order to connect with a benzene ring and to form a seven-membered nitrogen-containing heterocyclic ring. R ¹ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group bonded with a carbon atom. R ^{2 to} R ⁹ represent a hydrogen atom or a substituent, and at least one of the substituents represents a dye residue represented by the general formula (3).
In General Formula (3), R ¹⁰ , R ¹¹ , and R ¹³ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. r represents an integer of 0 or more. The carbon-carbon double bond in general formula (3) may be either E-type or Z-type. R ¹² represents a group having at least one acidic group or an acidic nucleus. ]
<3> The dye according to <1> or <2>, wherein the dye having a structure represented by the general formula (1) or (2) is represented by the following general formula (4): ,

[In the general formula ^{(4), R 1 ~R 3} , R 5 ~R 13 are each synonymous with ^{R 1 ~R 3, R 5 ~R} 13 in the general formula (2) and the general formula (3). ]
<4> The dye according to <1> or <2>, wherein the dye having the structure represented by the general formula (1) or (2) is represented by the following general formula (5): ,

[In the general formula ^(5), R 1 ^{to R 13} are the same meanings as ^R 1 ^{to R 13} in the general formula (2) and the general formula (3).
In the general formula (5), R ¹⁴ represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, or a heterocyclic group. ]
<5> The dye according to <1> or <2>, wherein the dye having a structure represented by the general formula (1) or (2) is represented by the following general formula (6):

[In the general formula ^{(6), R 1 ~R 3} , R 5, R 6, R 8 ~R 13 is, ^R 1 ^{to R} 3, respectively, in the general formula (2) and the general formula ^{(3), R 5, R 6} , which is synonymous with R ^{8 to} R ¹³ . ]
<6> The dye according to any one of <2> to <5>, wherein R ¹² is represented by the following general formula (7) or general formula (8):

In the general formula (7), R ¹⁵ and R ¹⁶ are each independently an aliphatic group, an aromatic group, or a heterocyclic group (at least one functional group may have an acidic group). l represents 0 or 1; The carbon-carbon double bond in the general formula (7) may be either E-type or Z-type. R ¹⁷ in general formula (7) represents a sulfur atom or general formula (9), and the carbon-carbon double bond in general formula (9) may be either E-type or Z-type.
R ¹⁸ and R ¹⁹ in the general formula (8) each independently represent a cyano group or an acidic group, and may be the same as or different from each other. The carbon-carbon double bond in the general formula (8) may be either E type or Z type.
R ²⁰ and R ²¹ in the general formula (9) each independently represent a cyano group or an acidic group, and may be the same or different from each other. The carbon-carbon double bond in the general formula (9) may be any of E type and Z type.
<7> The dye according to <6>, wherein the general formula (7) is represented by the following general formula (10):

In the general formula (10), R ¹⁶ is an aliphatic group, an aromatic group or a heterocyclic group (which may have an acidic group).
<8> The dye according to any one of <2> to <5>, wherein R ¹² is represented by the following general formula (11):

In the general formula (11), R ¹⁵ is an aliphatic group, an aromatic group, or a heterocyclic group (which may have an acidic group).
<9> The dye according to any one of <2> to <5>, wherein R ¹² is represented by the following general formula (12):

<10> A photoelectric conversion element, wherein the light receiving electrode contains semiconductor fine particles sensitized by the dye according to any one of <1> to <9>,
<11> The photoelectric conversion element according to <10>, which has an insulating porous body between the light receiving electrode and the counter electrode,
<12> A photoelectrochemical cell comprising the photoelectric conversion element according to any one of <10> to <11>.

  The dye of the present invention has high photoelectric conversion efficiency when used as a sensitizing dye for a photoelectric conversion element or a photoelectrochemical cell, and has good characteristics. Moreover, since it is not necessary to use ruthenium as a sensitizing dye, a photoelectric conversion element and a photoelectrochemical cell using the same can be provided at a low price.

It is sectional drawing shown typically about one embodiment of the photoelectric conversion element of this invention.

As a result of intensive studies, the present inventors have found that a dye (dye compound) having high photoelectric conversion efficiency and excellent durability can be obtained by introducing the following four design concepts. Moreover, it discovered that the photoelectric conversion element containing the semiconductor fine particle sensitized by the pigment | dye and the photoelectrochemical cell comprised with the photoelectric conversion element had high photoelectric conversion efficiency.
<Design concept 1> In order to promote delocalization of the cation radical, a one-electron oxidation state of the dye was stabilized by introducing a donor site having a wide conjugated system.
<Design concept 2> It is considered that high conversion efficiency can be obtained by expanding the absorption range of the dye and improving the efficiency of electron injection from the dye into titanium oxide. Therefore, an acceptor structure having a high absorption range expansion effect, an acceptor structure having a high electron injection efficiency, or a combination of both structures was used.
<Design concept 3> The conventional dye may cover only about 1/3 of the total surface area of titanium oxide, and the amount of adsorption can be improved by controlling the dye arrangement in the adsorption state. It is done. Therefore, the present inventors introduced a structure that actively promotes the J-association of the dye. The structure that actively promotes J-association is a molecular structure in which a hydrophobic high-affinity group such as a long-chain alkyl group or an aryl group is arranged at a position opposite to the anchor portion such as a COOH group. In addition, the dye molecule has high planarity and has a substituent that protrudes three-dimensionally from the plane in the center of the molecular conjugate plane, or by having the same effect by twisting the molecule, Brickstone. It means a structure that promotes the arrangement of a structure, a staircase structure, or a Ladder structure.

In general formula (1), X represents a nonmetallic atom group necessary for linking with a benzene ring to form a nitrogen-containing seven-membered ring. Here, the nonmetallic atom group refers to an atomic group in which at least one selected from the group consisting of a carbon atom, an oxygen atom, a nitrogen atom and a sulfur atom is bonded.
Y represents a pigment residue. The dye residue refers to an atomic group necessary for constituting the dye compound as a whole together with the structure other than Y in the general formula (1). For example, dye compounds formed by Y include polymethine dyes such as merocyanine, hemicyanine, styryl, oxonol, and cyanine, diarylmethines including acridine, xanthene, thioxanthene, triarylmethine, coumarin, indoaniline, indophenol, diazine Oxazine, thiazine, diketopyrrolopyrrole, indigo, anthraquinone, perylene, quinacridone, naphthoquinone, bipyridyl, terpyridyl, tetrapyridyl, phenanthroline and the like. Preferable examples include polymethine dyes and polyaryl dyes. n represents an integer of 1 or more. The preferable value of n is 1-2.

Z represents a substituent, and examples thereof include an aliphatic group, an aromatic group, and a heterocyclic group. Specific examples of the substituent include alkyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, and heterocyclic rings. Preferred examples include alkyl groups (eg, methyl, ethyl, n-butyl, n-hexyl, isobutyl, sec-butyl, t-butyl, n-dodecyl, cyclohexyl, benzyl, etc.), substituted aryl groups (eg, phenyl, tolyl, Naphthyl and the like) and alkoxy groups (for example, methoxy, ethoxy, isopropoxy, butoxy and the like).
m represents 0 or a positive integer. The substituents represented by Z may be the same or different when m is 2 or more.

R ¹ represents a heterocyclic group bonded by a hydrogen atom, an aliphatic group, an aromatic group, or a carbon atom. Preferable specific examples of R ¹ include substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms (for example, methyl, ethyl, n-butyl, n-hexyl, isobutyl, sec-butyl, t-butyl, n-dodecyl, Cyclohexyl, benzyl, etc.), substituted or unsubstituted aryl groups (eg, phenyl, tolyl, naphthyl, etc.), substituted or unsubstituted heterocyclic residues (eg, pyridyl, imidazolyl, furyl, thienyl, oxazolyl, thiazolyl, benzimidazolyl, quinolyl) More preferably, it is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n-butyl, n-hexyl, isobutyl, sec-butyl, t-butyl, n-dodecyl). Cyclohexyl, benzyl, etc.).

In the general formula (2), X represents a nonmetallic atom group necessary for forming a benzene ring to be linked and a nitrogen-containing seven-membered ring. Here, the nonmetallic atom group refers to an atomic group in which at least one selected from the group consisting of a carbon atom, an oxygen atom, a nitrogen atom and a sulfur atom is bonded. R ¹ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group bonded with a carbon atom. Preferable specific examples of R ¹ include substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms (for example, methyl, ethyl, n-butyl, n-hexyl, isobutyl, sec-butyl, t-butyl, n-dodecyl, Cyclohexyl, benzyl, etc.), substituted or unsubstituted aryl groups (eg, phenyl, tolyl, naphthyl, etc.), substituted or unsubstituted heterocyclic residues (eg, pyridyl, imidazolyl, furyl, thienyl, oxazolyl, thiazolyl, benzimidazolyl, quinolyl) More preferably, it is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n-butyl, n-hexyl, isobutyl, sec-butyl, t-butyl, n-dodecyl). Cyclohexyl, benzyl, etc.). R ^{2 to} R ⁹ represent a hydrogen atom or a substituent, and at least one of the substituents represents a dye residue represented by the general formula (3). Specific examples of the substituent are an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a heterocyclic group, and the like. Preferred examples include alkyl groups (eg methyl, ethyl, n-butyl, n-hexyl, isobutyl, sec-butyl, t-butyl, n-dodecyl, cyclohexyl, benzyl, etc.), substituted aryl groups (eg phenyl, tolyl, naphthyl). Etc.) and alkoxy groups (for example, methoxy, ethoxy, isopropoxy, butoxy, etc.).

In the general formula (3), R ¹² represents a group having at least one acidic group or an acidic nucleus substituted with at least one acidic group.
T. as an acidic nucleus H. "The Theory of the photographic process. Forth edition." By James, published in 1977, published by Macmillan publishing, Inc.
When R ¹² has at least one acidic group, it is preferable that R ¹² has an electron withdrawing group at the same time, and the electron withdrawing group includes a substituent having the effects described below (-I effect, -M effect). Can be mentioned. When R ¹² has an acidic group and an electron-withdrawing group at the same time, the type and bonding position of the electron-withdrawing group are appropriately selected so that the effect of increasing the overlap between the molecular orbitals in the excited state of the dye and the light-receiving electrode is exhibited. Selected.
In general, an electron withdrawing group attenuates the electron density at a specific position of the molecule. The electron withdrawing property or electron donating property cannot be explained only by the difference in electronegativity. In other words, the induction effect and the mesomery effect act in a complex manner, and the appearance changes depending on the presence of aromaticity, conjugated system, and topological positional relationship. Hammett's rule is known as an empirical rule for quantitatively evaluating and predicting these effects based on the acid dissociation constants of para- and meta-substituted benzoic acids. In the case of the inductive effect, the electron withdrawing property is represented as the -I effect, and the electron donating property is represented as the + I effect. An atom having a higher electronegativity than carbon exhibits the -I effect. An anion shows a + I effect, and a cation shows a -I effect. In the case of the mesomery effect, the electron withdrawing property is represented as -M effect, and the electron donating property is represented as + M effect. Examples of electron withdrawing groups are shown below.
Induced effect (-I effect)
_{^{· -O + R 2> -N +}} R 3
_{^{· -N + R 3> -P +}} R 3> ...
_{^{· -O + R 2> -S +}} R 2> ...
_{^{· -N + R 3> -NO 2}} > -SO 2 R> -SOR
· _-SO 2 R> _-SO 3 R
· ^-N + _R 3> -NR ₂
· ^-O + _R 2> -OR
· ^-S + _R 2> -SR
-F>-Cl>-Br> -I
・ = O> = NR> = CR ₂
・ = O> -OR
・ ≡N> ≡CR
· ≡N> = NR> -NR _{2
· -C≡CR> -CR = CR 2>} -CR 2 CR 3
Mesomery effect (-M effect)
_{^{· = N + R 3> =}} NR
・ = O> = NR> = CR ₂
・ = S> = O> ≡N

Preferred examples of the acidic nucleus include rhodanine nucleus, hindantin, thiohydantoin, barbituric acid, pyrazolidinedione, pyrazolone, indandione and the like. These may include those in which two or more acidic nuclei dehydrated and condensed at the carbonyl moiety are linked. Preferably. Rhodanine, hindantin, thiohydantoin, barbituric acid, and pyrazolidinedione are preferable, and rhodanine is particularly preferable.
The acidic group contained in R ¹² represents a proton dissociable group having a pKa of 13 or less. Preferable specific examples of the acidic group include carboxylic acid, sulfonic acid, phosphoric acid, phosphate ester and the like. More preferred examples of the acidic group include carboxylic acid. The carbon-carbon double bond may be either E-type or Z-type.

In General Formula (3), R ¹⁰ , R ¹¹ , and R ¹³ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. r represents an integer of 0 or more. The carbon-carbon double bond in general formula (3) may be either E-type or Z-type. R ¹⁰ , R ¹¹ , and R ¹³ are preferably a hydrogen atom, an aliphatic group, or an aromatic group. More preferred examples include an aliphatic group and an aromatic group.

General formula (4) is a case where X in general formula (1) is an ethylene group, whereby a nitrogen-containing seven-membered ring structure is formed. It also has one dye residue at the para position of one benzene ring that is substituted with a nitrogen atom.

General formula (5) has a carbon-carbon double bond in a nitrogen-containing seven-membered ring, and has a pigment residue on the nitrogen-containing seven-membered ring. In the general formula (5), R ¹⁴ represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, or a heterocyclic group. Preferably, an alkyl group (for example, methyl, ethyl, n-butyl, n-hexyl, isobutyl, sec-butyl, t-butyl, n-dodecyl, cyclohexyl, benzyl, etc.), a substituted aryl group (for example, phenyl, tolyl, naphthyl, etc.) ) And alkoxy groups (for example, methoxy, ethoxy, isopropoxy, butoxy, etc.).

  General formula (6) is a case where X in general formula (1) is an ethylene group, whereby a nitrogen-containing seven-membered ring structure is formed. Each of the two benzene rings substituted with a nitrogen atom has one dye residue at each para position.

In General Formulas (3) to (6), R ¹² can be set to the following General Formula (7) or General Formula (8).

In the general formula (7), R ¹⁵ and R ¹⁶ are each independently an aliphatic group, an aromatic group, or a heterocyclic group (at least one functional group may have an acidic group). l represents 0 or 1; The carbon-carbon double bond in the general formula (7) may be either E-type or Z-type. R ¹⁷ in the general formula (7) represents a sulfur atom or the general formula (9).
When R ¹⁷ represents a sulfur atom, at least one of R ¹⁵ and R ¹⁶ is preferably an aliphatic group having an acidic group, an aromatic group, or a heterocyclic group, and they may be different. Preferable specific examples of the acidic group include carboxylic acid, sulfonic acid, phosphoric acid, phosphate ester and the like. More preferred examples of the acidic group include carboxylic acid. The carbon-carbon double bond may be either E-type or Z-type.

In the general formula (9), R ²⁰ and R ²¹ represent a cyano group or an acidic group, and may be the same or different from each other. Preferable specific examples of the acidic group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phosphoric ester group. More preferred examples of the acidic group include a carboxylic acid group. The carbon-carbon double bond in general formula (9) may be either E-type or Z-type.

R ¹⁸ and R ¹⁹ in the general formula (8) each independently represent a cyano group or an acidic group, and may be the same as or different from each other. Preferable specific examples of the acidic group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phosphoric ester group. More preferred examples of the acidic group include a carboxylic acid group. The carbon-carbon double bond in the general formula (8) may be either E type or Z type.

In the general formula (7), those represented by the following general formula (10) can be used. Here, R ¹⁶ is an aliphatic group, an aromatic group, or a heterocyclic group, and may have an acidic group.

In general formula (3) to ^(6), it is possible ^{to R 12} are the following general formula (11).

In the general formula (11), R ¹⁵ is an aliphatic group, an aromatic group, or a heterocyclic group (which may have an acidic group).
In general formula (3) to ^(6), it is possible ^{to R 12} are the following general formula (12).

  Although the preferable specific example of the pigment | dye (dye compound) of this invention is shown below, this invention is not limited to these.

The dye of the present invention has a maximum absorption wavelength in a solution of preferably 350 to 1000 nm, more preferably 370 to 700 nm, and particularly preferably 390 to 650 nm.
Specific examples of the photoelectric conversion element of the present invention include an optical sensor, a copying machine, and a photoelectrochemical cell, preferably a photoelectrochemical cell. In the photoelectrochemical cell, the dye of the present invention functions as a sensitizing dye.

  A preferred embodiment of the photoelectric conversion element of the present invention will be described with reference to the drawings. As shown in FIG. 1, the photoelectric conversion element 10 includes a conductive support 1, a photosensitive layer 2 having porous semiconductor fine particles adsorbed on a conductive support 1, a charge transfer layer 3, and a counter electrode. It consists of four. The conductive support 1 provided with the photosensitive layer 2 functions as a working electrode in the photoelectric conversion element 10. The photoelectric conversion element 10 can be used as a battery for working in the external circuit 6 and can be operated as a photoelectrochemical cell (not shown).

The light-receiving electrode 5 is an electrode composed of the conductive support 1 and the photosensitive layer (semiconductor film layer) 2 of the semiconductor fine particles 22 adsorbed by the dye 21 coated on the conductive support. Light incident on the photosensitive layer 2 excites the dye. The excited dye has electrons with high energy, and these electrons are passed from the dye 21 to the conduction band of the semiconductor fine particles 22 and reach the conductive support 1 by diffusion. At this time, the molecule of the dye 21 is an oxidant, but the electrons on the electrode return to the dye oxidant while working in the external circuit, and the light receiving electrode 5 serves as the negative electrode of the battery. work.
In the present invention, the materials used for the photoelectric conversion element and the photoelectrochemical cell and the method for producing each member may be the usual ones of this type. For example, US Pat. No. 5,463,057, US Pat. No. 5,525,440, JP-A-7-249790, JP-A-2004-220974, and JP-A-2008-135197 can be referred to. Hereinafter, main members will be described with reference to the drawings as appropriate.

(A) Conductive Support As shown in FIG. 1, a conductive support 1 is used in the photoelectric conversion element of the present invention. As the conductive support, there can be used a glass or a polymer material having a conductive film layer on the surface, such as a metal that is conductive in the support itself. It is preferable that the conductive support is substantially transparent. Substantially transparent means that the light transmittance is 10% or more, preferably 50% or more, particularly preferably 80% or more. As the conductive support, a glass or polymer material coated with a conductive metal oxide can be used. The coating amount of the conductive metal oxide at this time is preferably 0.1 to 100 g per 1 m ² of the support of glass or polymer material. When a transparent conductive support is used, light is preferably incident from the support side. Examples of polymer materials that are preferably used include tetraacetyl cellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), Examples include polyarylate (PAR), polysulfone (PSF), polyester sulfone (PES), polyetherimide (PEI), cyclic polyolefin, and brominated phenoxy. On the conductive support, the surface may be provided with a light management function. For example, an antireflection film in which high refractive films and low refractive index oxide films described in JP-A-2003-123859 are alternately laminated, The light guide function described in Open 2002-260746 is raised.
In addition to this, a metal support can also be preferably used. Examples thereof include titanium, aluminum, copper, nickel, iron, stainless steel, and copper. These metals may be alloys. More preferably, titanium, aluminum, and copper are preferable, and titanium and aluminum are particularly preferable.

It is preferable that the conductive support has a function of blocking ultraviolet light. For example, the method of making the fluorescent material which can change the ultraviolet light of Unexamined-Japanese-Patent No. 2001-185242 into visible light exist in a transparent support body or the surface of a transparent support body is mentioned. Another preferred method is a method using an ultraviolet absorber. Preferred embodiments include, for example, JP-A-11-345991, JP-A-2002-25634, JP-A-2003-21769, JP-A-2004-227843, JP-A-2004-349129, JP-A-2002-134178. And those disclosed in Japanese Patent Application Laid-Open No. 2003-100388.
The functions described in JP-A-11-250944, JP-A-2003-308892, and JP-A-2003-282163 may be provided on the conductive support.

Preferred conductive films include metals (eg, platinum, gold, silver, copper, aluminum, rhodium, indium, etc.), carbon, or conductive metal oxides (indium-tin composite oxide, tin oxide doped with fluorine, etc.) ). Preferred embodiments of the conductive film and the production method thereof are disclosed in JP2003-151355A, JP2004-31174A, JP2004-31175A, JP2004-31176A, JP2005-85699A, Examples thereof include those described in JP-A-2005-85670, JP-A-2005-116391, JP-A-2003-323818, JP-A-2004-165080, and JP-A-2005141981.
The thickness of the conductive film layer 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, the better. The range of the surface resistance is preferably 50 Ω / cm ² or less, more preferably 10 Ω / cm ² or less. This lower limit is not particularly limited, but is usually about 0.1 Ω / cm ² .

  Since the resistance value of the conductive film increases as the cell area increases, a collecting electrode may be disposed. Preferable shapes and materials of the current collecting electrode include JP-A-11-266028, JP-A-2005-108467, JP-A-2003-203681, JP-A-2004-146425, and JP-A-2004-128267. JP, 2004-164970, JP, 2004-327226, JP, 2004-164950, JP, 2005-78857, JP, 2005-197176, JP, 2004-164950, JP 2000-285777 A, JP 2002-314108 A, and JP 2003-123858 A.

As described in JP-A-2000-285974, a gas barrier film and / or an ion diffusion preventing film may be disposed between the support and the transparent conductive film. The gas barrier layer may be either a resin film (for example, Japanese Patent Application Laid-Open No. 2000-282163, Japanese Patent Application Laid-Open No. 2005-14086) or an inorganic film (Japanese Patent Application Laid-Open No. 2005-14086).
Moreover, you may provide a transparent electrode and a porous semiconductor electrode photocatalyst content layer like Unexamined-Japanese-Patent No. 2005-142084 or 2005-14085.

  The transparent conductive layer may have a laminated structure. As a preferable method, for example, in addition to the method described in JP-A No. 2003-323818, FTO is laminated on ITO, JP-A No. 2005-44544 and JP-A No. 2005-142888. JP-A-2005-19205, JP-A-2004-241228, and JP-A-2004-319872.

(B) Semiconductor Fine Particles As shown in FIG. 1, in the photoelectric conversion element of the present invention, a photosensitive layer 2 in which a dye 21 is adsorbed on porous semiconductor fine particles 22 is formed on a conductive support 1. . As described later, for example, a photosensitive layer can be produced by immersing the dispersion of semiconductor fine particles in the dye solution of the present invention after coating and drying the conductive support.
As the semiconductor fine particles, metal chalcogenides (for example, oxides, sulfides, selenides, etc.) or perovskite fine particles are preferably used. Preferred examples of the metal chalcogenide include titanium, tin, zinc, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, tantalum oxide, cadmium sulfide, cadmium selenide, and the like. . Preferred perovskites include strontium titanate and calcium titanate. Of these, titanium oxide, zinc oxide, tin oxide, and tungsten oxide are particularly preferable.

In semiconductors, there are an n-type in which carriers involved in conduction are electrons and a p-type in which carriers are holes. In the element of the present invention, n-type is preferable in terms of conversion efficiency. In an n-type semiconductor, in addition to an intrinsic semiconductor (or an intrinsic semiconductor) having no impurity level and having the same carrier concentration due to conduction band electrons and valence band holes, the electron carrier concentration is reduced by structural defects derived from impurities. There are high n-type semiconductors. The n-type inorganic semiconductor preferably used in the present invention is 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. Of these, the most preferred n-type semiconductors are TiO ₂ , ZnO, SnO ₂ , WO ₃ , and Nb ₂ O ₃ . A semiconductor material in which a plurality of these semiconductors are combined is also preferably used.

  For the purpose of keeping the viscosity of the semiconductor fine particle dispersion high, the average particle size of the primary particles is preferably 2 nm to 50 nm, and the average primary particle size is more than 2 nm to 30 nm. More preferably, it is a fine particle. Two or more kinds of fine particles having different particle size distributions may be mixed. In this case, the average size of the small particles is preferably 5 nm or less. In addition, for the purpose of improving the light capture rate by scattering incident light, large particles having an average particle size exceeding 50 nm can be added to the above ultrafine particles at a low content. In this case, the content of the large particles is preferably 50% or less, more preferably 20% or less of the mass of particles having an average particle size of 50 nm or less. The average particle size of the large particles added and mixed for the above purpose is preferably 100 nm or more, and more preferably 250 nm or more.

  Semiconductor fine particles can be produced by Sakuo Sakuo's “Science of Sol / Gel Method” Agne Jofu Co., Ltd. (1998), “Thin Film Coating Technology by Sol / Gel Method” (1995) of the Technical Information Association, etc. The sol-gel method described, Tadao Sugimoto, “Synthesis and size control of monodisperse particles by a new synthesis gel-sol method”, Materia, Vol. 35, No. 9, 1012-1018 (1996) The gel-sol method described in 1 is preferred. Also preferred is a method of producing an oxide by high-temperature hydrolysis of chloride developed by Degussa in an oxyhydrogen salt. When the semiconductor fine particles are titanium oxide, the above sol-gel method, gel-sol method, and high-temperature hydrolysis method in oxyhydrogen salt of chloride are preferred, but Kiyoshi Manabu's “Titanium oxide properties and applied technology” The sulfuric acid method and the chlorine method described in Gihodo Publishing (1997) can also be used. Further, as the sol-gel method, the method described in Journal of American Ceramic Society, Vol. 80, No. 12, 3157-3171 (1997), or the chemistry of Burnside et al. The method described in Materials, Vol. 10, No. 9, pages 2419-2425 is also preferable.

  In addition, as a method for producing semiconductor fine particles, for example, a method for producing titania nanoparticles is preferably a method by flame hydrolysis of titanium tetrachloride (Japanese Patent Publication No. 06-511113), a method of combustion of titanium tetrachloride (special No. 2003-327432), hydrolysis of a stable chalcogenide complex (JP 2001-85076 A), hydrolysis of orthotitanic acid (JP 2004-161589 A, JP 2004-238213 A), possible Method of dissolving and removing soluble part after forming semiconductor fine particles from soluble part and insoluble part (Japanese Patent Laid-Open No. 2002-246620), hydrothermal synthesis of aqueous peroxide solution (Japanese Patent Laid-Open No. 2003-92154), or sol-gel method And the production method of titanium oxide fine particles having a core / shell structure by JP-A-2004-10403.

  Examples of the crystal structure of titania include anatase type, brookite type, and rutile type, and anatase type and brookite type are preferable. Preferred examples include those described in JP-A-11-339867, JP-A-2001-43907, and JP-A-2001-43907. Further, as preferable physical properties of titanium oxide, EP 1338563 (A2), U.S. Patent 2004-0161380, U.S. Pat. No. 6,075,203, U.S. Pat. No. 6,444,189, U.S. Pat. No. 6,720,202 are described. Examples described in Chinese Patent No. 1540772 (A), Japanese Patent Application Laid-Open No. 2001-283942, and Japanese Patent Application Laid-Open No. 2001-212457.

  Titania nanotubes, nanowires, and nanorods may be mixed with titania fine particles. Preferred examples include JP-A No. 2003-168495, JP-A No. 2003-251194, JP-A No. 2004-175586, JP-A No. 2004-175588, JP-A No. 2004-175588, and JP-A No. 2004-31354. And JP-A-2004-31355, JP-A-2004-319661, and JP-A-2005-162584.

  Titania may be doped with a nonmetallic element or the like. Preferred examples include JP-A No. 2000-235874, JP-A No. 2003-252624, JP-A No. 2002-25637, JP-A No. 2003-187881, JP-A No. 2003-187882, JP-A No. 2003-179244. JP, JP-A-2004-87148, JP-A-2004-119279, JP-A-2005-93944, JP-A-2005-64493, JP-A-2003-257507, and JP-A-2003-323920. Examples described in the publication are listed. In addition to the dopant, an additive to the titania may be used as a binder for improving necking or an additive on the surface for preventing reverse electron transfer. Examples of preferable additives include ITO, SnO particles (Japanese Patent Laid-Open Nos. 11-283682 and 2001-345125), whiskers (Japanese Patent Laid-Open No. 2003-163037), and fibrous graphite / carbon nanotubes (Japanese Patent Laid-Open No. 2003-163037). 2003-163037), zinc oxide necking binder (Japanese Patent Laid-Open No. 2003-273181), fibrous materials such as cellulose (Japanese Patent Laid-Open No. 2003-123861), metal (Japanese Patent Laid-Open No. 2000-285975, Japanese Patent Laid-Open No. 2000-285975) 2001-35551), organic silicon (Japanese Patent Laid-Open No. 2000-294304), dodecylbenzenesulfonic acid (Japanese Patent Laid-Open No. 2000-260493), charge transfer binding molecules such as silane compounds (Japanese Patent Laid-Open No. 2000-323192, JP, 2001-102103, A) and potential Like swash dendrimer (JP 2004-213908).

  For the purpose of removing surface defects on titania, titania may be acid-base or redox treated before dye adsorption. Examples of the acid-base treatment include, for example, JP 2000-101106 A, JP 2002-293541 A, JP 2003-297441 A, JP 2003-297442 A, JP 2004-235240 A, and the like. can give. Further, as described in JP-A-08-81222, JP-A-2000-285980, JP-A-2004-158243, and JP-A-2004-247104, etc., etching, oxidation treatment, hydrogen peroxide treatment, You may process by a dehydrogenation process, UV-ozone, oxygen plasma, etc.

(C) Semiconductor fine particle dispersion In the present invention, a semiconductor fine particle dispersion in which the solid content other than the semiconductor fine particles is 10% by mass or less of the entire semiconductor fine particle dispersion is applied to the conductive support. A porous semiconductor fine particle coating layer can be obtained by heating to a high temperature.
In addition to the sol-gel method described above, a method of preparing a semiconductor fine particle dispersion is a method of depositing fine particles in a solvent and using them as they are when synthesizing a semiconductor. Ultrafine particles are irradiated with ultrasonic waves. Or a method of mechanically pulverizing and grinding using a mill or a mortar. As the dispersion solvent, water and / or various organic solvents can be used. Examples of the organic solvent include alcohols such as methanol, ethanol, isopropyl alcohol, citronellol and terpineol, ketones such as acetone, esters such as ethyl acetate, dichloromethane, acetonitrile and the like.
At the time of dispersion, a small amount of, for example, a polymer such as polyethylene glycol, hydroxyethyl cellulose, carboxymethyl cellulose, a surfactant, an acid, or a chelating agent may be used as a dispersion aid. However, most of these dispersing aids are preferably removed by a filtration method, a method using a separation membrane, a centrifugal method or the like before the step of forming a film on a conductive support. In the semiconductor fine particle dispersion, the solid content other than the semiconductor fine particles can be 10% by mass or less of the total dispersion. This concentration is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less. More preferably, it is 0.5% or less, and particularly preferably 0.2%. That is, in the semiconductor fine particle dispersion, the solid content other than the solvent and the semiconductor fine particles can be 10% by mass or less of the entire semiconductor fine dispersion. It is preferable to consist essentially of semiconductor fine particles and a dispersion solvent.
If the viscosity of the semiconductor fine particle dispersion is too high, the dispersion will aggregate and cannot be formed into a film. Conversely, if the viscosity of the semiconductor fine particle dispersion is too low, the liquid will flow and cannot be formed into a film. is there. Therefore, the viscosity of the dispersion is preferably 10 to 300 N · s / m ² at 25 ° C. More preferably, it is 50 to 200 N · s / m ² at 25 ° C.

As a method for applying the semiconductor fine particle dispersion, a roller method, a dip method, or the like can be used as an application method. Moreover, an air knife method, a blade method, etc. can be used as a metering method. Further, as an application method and a metering method can be made the same part, the wire bar method disclosed in Japanese Patent Publication No. 58-4589, US Pat. No. 2,681,294, US Pat. No. 2,761,419, US Pat. The slide hopper method, the extrusion method, the curtain method and the like described in the specification and the like are preferable. It is also preferable to apply by a spin method or a spray method using a general-purpose machine. As the wet printing method, intaglio, rubber plate, screen printing and the like are preferred, including the three major printing methods of letterpress, offset and gravure. From these, a preferred film forming method is selected according to the liquid viscosity and the wet thickness. Further, since the semiconductor fine particle dispersion of the present invention has a high viscosity and has a viscous property, it may have a strong cohesive force and may not be well adapted to the support during coating. In such a case, by performing cleaning and hydrophilization of the surface by UV ozone treatment, the binding force between the applied semiconductor fine particle dispersion and the surface of the conductive support increases, and the semiconductor fine particle dispersion can be easily applied.
The preferred thickness of the entire semiconductor fine particle layer is 0.1 to 100 μm. The thickness of the semiconductor fine particle layer is further preferably 1 to 30 μm, and more preferably 2 to 25 μm. The amount of the semiconductor fine particles supported per 1 m ² of the support is preferably 0.5 g to 400 g, and more preferably 5 to 100 g.

The applied semiconductor fine particle layer is subjected to heat treatment to enhance the electronic contact between the semiconductor fine particles and to improve the adhesion to the support, and to dry the applied semiconductor fine particle dispersion. . By this heat treatment, a porous semiconductor fine particle layer can be formed.
In addition to heat treatment, light energy can also be used. For example, when titanium oxide is used as the semiconductor fine particles, the surface may be activated by applying light absorbed by the semiconductor fine particles such as ultraviolet light, or only the surface of the semiconductor fine particles may be activated by laser light or the like. Can do. By irradiating the semiconductor fine particles with light absorbed by the fine particles, the impurities adsorbed on the particle surface are decomposed by the activation of the particle surface, and can be brought into a preferable state for the above purpose. When heat treatment and ultraviolet light are combined, it is preferable that heating be performed at 100 ° C. or higher and 250 ° C. or lower, or preferably 100 ° C. or higher and 150 ° C. or lower, while irradiating the semiconductor fine particles with light absorbed by the fine particles. Thus, by photoexciting the semiconductor fine particles, impurities mixed in the fine particle layer can be washed by photolysis, and physical bonding between the fine particles can be strengthened.

In addition, the semiconductor fine particle dispersion may be applied to the conductive support, and other treatments may be performed in addition to heating and light irradiation. Examples of preferred methods include energization and chemical treatment.
The pressure may be applied after coating, and examples of the method of applying pressure include JP-T-2003-500857, JP-A-2002-93475, JP-A-2003-282160, and JP-A-2004-214129. It is done. Examples of light irradiation include JP-A No. 2001-357896, JP-A No. 11-219734, JP-A No. 2004-314313, JP-A No. 2005-142446, and JP-A No. 2001-247314. Examples of plasma, microwave, and energization include JP 2002-353453 A, JP 2003-308893 A, JP 2004-265562 A, JP 2004-327369 A, and JP 2004-342319 A. JP 2005-116415 A, JP 2005-139498 A, and JP 2004-273770 A. Examples of the chemical treatment include JP 2001-357896 A, JP 2002-280327 A, JP 2003-281947 A, JP 2005-520314 A, and JP 2003-297442 A.

  The above-mentioned method of coating the semiconductor fine particles on the conductive support includes a method of applying a semiconductor fine particle dispersion on the conductive support, and a semiconductor fine particle precursor described in Japanese Patent No. 2664194 as a conductive support. It is included in (1) a wet method such as a method of applying a semiconductor and hydrolyzing with moisture in the air to obtain a semiconductor fine particle film. In addition to the methods described above, as a method for producing a wet method, as a method of preparing a dispersion of semiconductor fine particles, a method of grinding with a mortar, a method of dispersing while grinding using a mill, or a semiconductor synthesis Examples of the method include a method of precipitating as fine particles in a solvent and using them as they are, but preferably, JP-A-11-144772, JP-A-2005-1000079, EP-A-1300897 (A1), JP-A-2002-324591. JP-A-2002-145615, JP-A-2003-176130, and JP-A-2004-79610. (1) As a dispersion medium of the coating liquid of the wet method, water or various organic solvents (for example, methanol, ethanol, t-butanol, dichloromethane, acetone, acetonitrile, ethyl acetate, etc.) can be mentioned. No. 06-511113, Chinese Patent No. 144292, Japanese Unexamined Patent Publication No. 11-11912, Japanese Unexamined Patent Publication No. 2000-294814, Japanese Unexamined Patent Publication No. 2000-319018, Japanese Unexamined Patent Publication No. 2000-319018, Japanese Unexamined Patent Publication No. 2000-319018. JP, JP 2002-145614, JP 2002-75477, JP 2004-193321, WO 02/067357, JP 2004-207205, JP 2004-111348, JP JP 2004-186144 A, JP 2003-28 A 162, JP 2005-142011, JP 2005-174695, JP 2005-85500, JP 11-343118, JP 11-354169, JP 2000-106222. JP-A-2003-246621, JP-A-2003-51345, JP-A-2004-158551, JP-A-2001-358348, JP-A-2003-217893, and the like. . At the time of dispersion, a polymer, a surfactant, an acid, a chelating agent, or the like may be used as a dispersion aid if necessary.

As a method of coating the semiconductor fine particles on the conductive support, (2) dry method and (3) other methods may be used in combination with the above (1) wet method.
(2) Preferably, the dry method is disclosed in JP 2000-231943, JP 2002-170602, JP 2001-345124, JP 2003-197280, JP 2003-123854, JP, JP 2003-123852 A, JP 2003-123853 A, JP 2005-39013 A, JP 2004-39286 A, JP 2005-104760 A, and the like.
(3) As other methods, preferably, JP 2002-134435 A, US 2004/0123896 A, JP 2004-327265 A, JP 342397 A, JP 2003-500857 A, JP 2005-85491 A, JP 2003-98777 A, JP 2002-299665 A, JP 2003-243053 A, JP 2004-253331 A, JP 11-310898 A, JP 2003 2003 A. No. -257507, JP 2003-323920, US 2004/0084080, US 2004/0121068, JP 2004-319873, JP 10-112337, JP 11-6098. No. 2000-178 91, JP 2000-178792, JP 2004-103420 and JP 2003-301283 JP are mentioned JP.

  The semiconductor fine particles preferably have a large surface area so that many dyes can be adsorbed. For example, in a state where the semiconductor fine particles are coated on the support, the surface area is preferably 10 times or more, more preferably 100 times or more the projected area. Although there is no restriction | limiting in particular in this upper limit, Usually, it is about 5000 times. Examples of preferable semiconductor fine particle structures include JP-A No. 2001-93591, JP-A No. 2001-257010, JP-A No. 2001-196106, JP-A No. 2001-273936, and European Patent No. 1207572 (A1). It is done.

In general, as the thickness of the semiconductor fine particle layer increases, the amount of dye that can be supported per unit area increases, so that the light absorption efficiency increases. The preferred thickness of the semiconductor fine particle layer varies depending on the use of the device, but is typically 0.1 to 100 μm. When using as a photoelectrochemical cell, it is preferable that it is 1-50 micrometers, and it is more preferable that it is 3-30 micrometers. The semiconductor fine particles may be heated at a temperature of 100 to 800 ° C. for 10 minutes to 10 hours in order to adhere the particles to each other after being applied to the support. When glass is used as the support, the film forming temperature is preferably 400 to 600 ° C.
When a polymer material is used as the support, it is preferably heated after film formation at 250 ° C. or lower. In this case, the film forming method may be any of (1) a wet method, (2) a dry method, and (3) an electrophoresis method (including an electrodeposition method), and preferably (1) a wet method or ( 2) Dry method, more preferably (1) Wet method.

The wet method is a method of forming a film on a plastic film by applying the semiconductor layer or its precursor wet, etc., and further activating it. For example, as described in JP-A-10-290018 A method of heating a mixture of a semiconductor and a conductive compound at a low temperature, a method using a precursor (for example, (NH ₄ ) ₂ TiF ₆ described in Japanese Patent Application Laid-Open No. 2001-110462, Japanese Patent Application Laid-Open No. 2001-247314 And a metal organic oxide (such as an alkoxide) described in JP-T-2005-520314. A method of forming a semiconductor film by applying a slurry and applying a heat treatment, a light treatment, etc .; Slurry allowed to coexist precursor, and include a method that identifies a property of pH titania particles dispersed in the slurry of JP 2005-056627 JP.
A small amount of a binder may be added to these slurries. Examples of the binder include cellulose described in JP-A No. 2003-109678 or JP-A No. 2003-123861, and JP-A No. 2003-272722. And a crosslinked rubber described in JP 2004-47261 A, polybutyl titanate described in JP 2005-516365 A, and carboxymethyl cellulose described in JP 2005-135798 A.

  As a technique relating to the formation of a semiconductor or a precursor layer thereof, a method of hydrophilizing by a physical method such as corona discharge, plasma, UV described in JP-A No. 2003-308890, an alkali (JP-A No. 2004-119120) And chemical treatment with polyethylenedioxythiophene and polystyrene sulfonic acid (Japanese Patent Laid-Open No. 2005-169228), and formation of an interlayer film for bonding such as polyaniline described in Japanese Patent Laid-Open No. 2003-297443.

Examples of the dry method include vapor deposition, sputtering, and aerosol deposition method. Preferably, JP 2005-39013 A, JP 2004-074609 A, JP 3265481 A, JP 2003-1000035 A, And the method of Unexamined-Japanese-Patent No. 2004-39286 is mentioned.
Moreover, you may use the electrophoresis method and electrodeposition method of Unexamined-Japanese-Patent No. 2002-100146 and Unexamined-Japanese-Patent No. 2004-311354.

Moreover, after producing a coating film once on a heat-resistant board | substrate, you may use the method of transcribe | transferring to films, such as a plastics. Preferably, a method of transferring via EVA described in JP-A No. 2002-184475, a semiconductor layer / conductive layer on a sacrificial substrate containing an inorganic salt that can be removed with ultraviolet rays and an aqueous solvent described in JP-A No. 2003-98977 And a method of removing the sacrificial substrate after transfer to an organic substrate.
The coating amount of the semiconductor fine particles per 1 m ² of the support is preferably 0.5 to 500 g, more preferably 5 to 100 g.

(D) Photosensitive layer The photoelectric conversion element is obtained by adsorbing the dye of the present invention to the porous semiconductor fine particle layer obtained by applying the above-mentioned semiconductor fine particle dispersion on the conductive support and heating. A photosensitive layer can be obtained. The photosensitive layer is designed according to the purpose, and may be a single layer structure or a multilayer structure. The dyes in one photosensitive layer may be one kind or a mixture of various kinds, but at least one of them uses the dye of the present invention. The photosensitive layer of the photoelectric conversion element produced by the method of the present invention contains semiconductor fine particles adsorbed with the dye, has high sensitivity, and can be used as a photoelectrochemical cell, and high conversion efficiency can be obtained.

  Examples of the dye (dye compound) of the present invention include F.I. M.M. It is described in Harmer's "Heterocyclic Compounds-Cyane Dies and Related Compounds" John Willey & Sons, New York and London, published in 1994, etc., or can be synthesized by a similar method.

In order to adsorb the dye to the semiconductor fine particles, it is preferable to immerse the well-dried semiconductor fine particles for a long time in the dye adsorbing dye solution comprising the solution and the dye of the present invention. The solution used for the dye solution for dye adsorption can be used without particular limitation as long as it can dissolve the dye of the present invention. For example, ethanol, methanol, isopropanol, toluene, t-butanol, acetonitrile, acetone, n-butanol and the like can be used. Among these, ethanol and toluene can be preferably used.
The dye solution for dye adsorption comprising the solution and the dye of the present invention may be heated to 50 ° C. to 100 ° C. as necessary. The adsorption of the dye may be performed before or after application of the semiconductor fine particles. Further, the semiconductor fine particles and the dye may be applied and adsorbed simultaneously. Unadsorbed dye is removed by washing. When baking a coating film, it is preferable to adsorb | suck a pigment | dye after baking. It is particularly preferable that the dye is quickly adsorbed after the baking and before water adsorbs on the coating film surface. One kind of adsorbing dye may be used, or several kinds may be mixed and used. In the case of mixing, two or more of the dyes of the present invention may be mixed, the specifications of U.S. Pat. Nos. 4,927,721, 4,684,537, 5,084,365, 5,350,644, 5,463,057, 5,525,440, and The complex dye described in Kaihei 7-249790 may be mixed with the dye of the present invention. The dye to be mixed is selected so as to make the wavelength range of photoelectric conversion as wide as possible. When mixing the dyes, it is necessary to prepare a dye solution for dye adsorption by dissolving all the dyes.

The total amount of the dye used is preferably 0.01 to 100 mmol, more preferably 0.1 to 50 mmol, particularly preferably 0.1 to 10 mmol, per 1 m ² of the support. In this case, the amount of the dye of the present invention is preferably 5 mol% or more.
Further, the adsorption amount of the dye to the semiconductor fine particles is preferably 0.001 to 1 mmol, more preferably 0.1 to 0.5 mmol, with respect to 1 g of the semiconductor fine particles.
By using such a dye amount, a sensitizing effect in a semiconductor can be sufficiently obtained. On the other hand, when the amount of the dye is small, the sensitizing effect becomes insufficient, and when the amount of the dye is too large, the dye not attached to the semiconductor floats and causes the sensitizing effect to be reduced.

Further, a colorless compound may be co-adsorbed for the purpose of reducing the interaction between dyes such as association. Examples of the hydrophobic compound to be co-adsorbed include steroid compounds having a carboxyl group (for example, cholic acid and pivaloyl acid).
After adsorbing the dye, the surface of the semiconductor fine particles may be treated with amines. Preferred amines include 4-tert-butyl pyridine, polyvinyl pyridine and the like. These may be used as they are in the case of a liquid, or may be used by dissolving in an organic solvent.

  Hereinafter, the charge transfer layer and the counter electrode will be described in detail. The charge transfer layer is a layer having a function of replenishing electrons to the oxidant of the dye, and is provided between the light receiving electrode and the counter electrode. Typical examples include a liquid in which a redox couple is dissolved in an organic solvent, a so-called gel electrolyte in which a polymer matrix is impregnated with a liquid in which a redox pair is dissolved in an organic solvent, and a molten salt containing the redox couple. .

  Examples of the redox pair include a combination of iodine and iodide (eg, lithium iodide, tetrabutylammonium iodide, tetrapropylammonium iodide, etc.), alkyl viologen (eg, methyl viologen chloride, hexyl viologen bromide, benzyl viologen tetrafluoro). Borate) and its reduced form, a combination of polyhydroxybenzenes (for example, hydroquinone, naphthohydroquinone, etc.) and its oxidized form, a combination of divalent and trivalent iron complexes (for example, red blood salt and yellow blood salt) Etc. Of these, a combination of iodine and iodide is preferred. Examples of organic solvents for dissolving them include aprotic polar solvents (for example, acetonitrile, propylene carbonate, ethylene carbonate, dimethylformamide, dimethyl sulfoxide, sulfolane, 1,3-dimethylimidazolinone, 3-methyloxazolidinone, etc.) -110262, the electrolyte solution described in JP 2000-36332 A, JP 2000-243134 A, and republished WO / 00-54361, etc., and acetonitrile, methoxypropionitrile , Propylene carbonate, and γ-butyrolactone are preferable.

  As an additive to the electrolyte, in addition to the above-mentioned 4-tert-butylpyridine, pyridine and pyridine compounds described in JP-A-2003-331986, JP-A-2004-47229, JP-A-2004-171821, etc. Aminopyridine compounds described in JP-A-2004-273272, benzimidazole compounds described in JP-A-2005-38711, aminotriazole-based compounds and aminothiazole-based compounds described in JP-A-2005-108663, and imidazole-based compounds described in JP-A-2005-108663 Compounds, quinoline compounds (JP-A 2005-135782), aminotriazine compounds (JP 2005-183166), urea derivatives (JP 2003-168493), amide compounds (JP 2004-103404) Gazette) Jin compounds (JP 2004-247158), and nitrogen heterocycles containing no (JP 2005-166612, JP 2005-166613 and JP Patent 2005-16615 JP) and the like.

  In order to improve efficiency, a method of controlling the water content of the electrolytic solution may be used. As a preferable method for controlling moisture, a method for controlling the concentration (JP 2000-323189 A, JP 2001-76774 A), a method in which a dehydrating agent coexists (JP 2002-237335 A, JP 2002 2002). -237335).

  In order to reduce the toxicity of iodine as described in JP-A No. 2004-235011, an inclusion compound of iodine and cyclodextrin may be used, and on the contrary, moisture is constantly replenished as described in JP-A No. 2003-25709. You may use the method to do. Cyclic amidine may be used as described in Japanese Patent No. 3462115, an antioxidant (Japanese Patent Laid-Open No. 2004-39292), a hydrolysis inhibitor (Japanese Patent Laid-Open No. 2004-111276), and a decomposition inhibitor (Japanese Patent Laid-Open No. 2004-2004). -111277) and zinc iodide (Japanese Patent Laid-Open No. 2004-152613) may be added.

  A molten salt may be used as the electrolyte, and preferred molten salts include ionic liquids containing imidazolium or triazolium type cations (Japanese Patent Publication Nos. 09-507334, 08-259543, 2003-2003). No. 031270, JP-A No. 2005-112733, JP-A No. 2005-116367, JP-A No. 2005-112733, JP-A No. 2003-68374, JP-A No. 2003-92153, JP-A No. 2004-241378 JP, 2005-85587, JP 2004-87387), oxazolium (JP 2000-53662), pyridinium (JP 2000-58891, JP 2001-23705, JP 2001-167630 A, JP 2001-2 6828, JP 2001-266962 JP), guanidium based (JP 2001-35253 JP), and combinations thereof (JP 2000-90991, JP-JP 2001-35552) can be mentioned. These cationic systems may be combined with specific anions. For example, JP 2002-75442 A, JP 2001-75443 A, JP 2002-170426 A, JP 2002-298913 A, JP 2002-367426 A, JP 2003-171148 A, and the like. Additives may be added to these molten salts. Preferred additives include JP-A-2001-67931, JP-A-2001-160427, JP-A-2002-289267, and JP-A-2002. 289268, JP-A 2000-90991, JP-A 2000-1000048, JP-A 2001-283943) and the like. You may have a liquid crystalline substituent like Unexamined-Japanese-Patent No. 2002-319314 or 2002-343440. Moreover, you may use the quaternary ammonium salt type molten salt as described in Unexamined-Japanese-Patent No. 2005-104845, Unexamined-Japanese-Patent No. 2005-104844, Unexamined-Japanese-Patent No. 2005-179254, etc.

  Examples of molten salts other than these include, for example, JP-A-2005-139100, JP-A-2005-145927, and lithium iodide and at least one other lithium salt (for example, lithium acetate, lithium perchlorate). The thing etc. which gave the fluidity | liquidity at room temperature by mixing a polyethylene oxide are mentioned. In this case, the amount of the polymer added is 1 to 50% by mass. Moreover, (gamma) -butyrolactone may be contained in electrolyte solution, and thereby the diffusion efficiency of iodide ion becomes high and conversion efficiency improves.

  The electrolyte may be quasi-solidified by adding a gelling agent to an electrolyte solution composed of an electrolyte and a solvent for gelation. Examples of the gelling agent include organic compounds having a molecular weight of 1000 or less (Japanese Patent Laid-Open Nos. 11-185836, 2000-36608, 2000-58140), Si-containing compounds having a molecular weight of 500-5000 (special No. 2003-203520), organic salts made from specific acidic compounds and basic compounds (Japanese Patent Laid-Open No. 2003-203520), sorbitol derivatives (Japanese Patent Laid-Open No. 2003-346828), polyvinyl pyridine (Japanese Patent Laid-Open No. 2004-227920) And Japanese Patent Application Laid-Open No. 2005-093370).

Alternatively, a method of trapping a matrix polymer, a crosslinkable polymer compound or monomer, a crosslinking agent, an electrolyte, and a solvent in the polymer may be used.
The matrix polymer is preferably a polymer having a nitrogen-containing heterocycle in the repeating unit of the main chain or side chain, and a crosslinked product obtained by reacting these with an electrophilic compound (Japanese Patent Application Laid-Open Nos. 11-126917 and 2002). 2000-86724), polymers having a triazine structure, polymers having a ureido structure (Japanese Patent Laid-Open No. 2000-251532), and liquid crystal compounds (Japanese Patent Laid-Open No. 2000-319260, 2002-2002). 246066), a polymer having an ether bond (JP 2000-150006 A, JP 2002-63813 A, JP 2001-338700 A, JP 2002-75480 A), polyvinylidene fluoride ( JP-A-2003-303628), methacrylate-acrylate system (JP-A-2001-2001) No. 8276, JP-A No. 2001-210390), thermosetting resin (JP-A No. 2002-363414, JP-A No. 2002-305041), cross-linked polysiloxane (JP-A No. 2002-216661), PVA ( JP-A No. 2002-175841), inclusion systems such as polyalkylene glycol and dextrin (JP-A No. 2004-327271), oxygen-containing or sulfur-containing polymers (JP-A No. 2005-108845), Natural polymers (Japanese Patent Laid-Open No. 2005-71688) and the like can be mentioned. These include alkali-swelling polymers (Japanese Patent Laid-Open No. 2002-175482), and polymers having a compound capable of forming a charge transfer complex between a cation moiety and iodine in one polymer (Japanese Patent Laid-Open No. 2005-63791). Etc. may be added.
As the matrix polymer, a system including a cross-linked polymer obtained by reacting a functional group such as a hydroxyl group, an amino group, or a carboxyl group with a bifunctional or higher functional isocyanate as one component may be used. Examples thereof include JP 2000-228234 A, JP 2002-184478 A, JP 2002-289271 A, and JP 2003-303630 A). Further, a crosslinking method (JP 2003-86258 A) in which a cross-linked polymer (Japanese Patent Laid-Open No. 2003-59548), polysulfonic acid, polycarboxylic acid, or the like is reacted with a divalent or higher metal ion compound by a hydrosilyl group and a double bond compound. Etc.) may also be used.

As a solvent that can be preferably used in combination with the above quasi-solid electrolyte, a specific phosphoric acid ester (JP 2000-1000048, JP 2003-16833), and a mixed solvent containing ethylene carbonate (JP 2004-87202), a solvent having a specific dielectric constant (Japanese Patent Laid-Open No. 2004-335366), and solvents described in Japanese Patent Laid-Open Nos. 2003-16833 and 2003-264011.
The liquid electrolyte solution may be held in a solid electrolyte membrane or pores, and preferably as a method therefor, a conductive polymer membrane (Japanese Patent Laid-Open No. 11-339866), a fibrous solid (Japanese Patent Laid-Open No. 2000-357544). And solid on cloth such as a filter (Japanese Patent Laid-Open No. 2001-345125). A specific combination of a gel electrolyte and a conductive resin counter electrode described in JP-A No. 2003-157914 may be used.

  A solid charge transport system such as a p-type semiconductor or a hole transport material may be used instead of the liquid electrolyte and the quasi-solid electrolyte. As the P-type semiconductor, CuI (Japanese Patent Laid-Open No. 2001-156314, Japanese Patent Laid-Open No. 2001-185743, Japanese Patent Laid-Open No. 2001-185743, Japanese Patent Laid-Open No. 2001-230434, Japanese Patent Laid-Open No. 2003-273181, JP 2003-234485 A, JP 2003-243681 A, JP 2003-234486 A), CuSCN, and p-SbAl (Japanese Patent Laid-Open No. 2003-258284). As a manufacturing method of these hole transport materials, JP-A-2003-331938, JP-A-2001-168359, JP-A-2001-196612, JP-A-2001-257370, JP-A-2002-2002 are preferred. No. 246623, JP-A 2002-246624, and JP-A 2003-289151.

  A photoelectrochemical cell having high conversion efficiency can be obtained by using a laminate in which a hole transporter is provided adjacent to a photosensitive layer of semiconductor fine particles adsorbed with the dye of the present invention. The hole transporter is not particularly limited, but an organic hole transport material can be used. As the hole transporter, polythiophene (Japanese Patent Laid-Open No. 2000-106223, Japanese Patent Laid-Open No. 2003-364304), polyaniline (Japanese Patent Laid-Open No. 2003-264304), polypyrrole (Japanese Patent Laid-Open No. 2000-106224, Japanese Patent Laid-Open No. 2000-106224) are preferable. 2003-264304) and polysilane (Japanese Patent Laid-Open No. 2001-53555, Japanese Patent Laid-Open No. 2001-203377), and a central element in which two rings have a tetrahedral structure such as C and Si. Spiro compounds (JP-A-11-513522, JP-A-2001-525108), aromatic amine derivatives such as triarylamine (JP-A-11-144773, JP-A-11-339868, JP 2003-123856 A, JP 2003-197942 A JP 2004-356281 A), triphenylene derivatives (JP 11-176489 A), nitrogen-containing heterocyclic derivatives (JP 2001-85077 A, JP 2001-85713 A), liquid crystalline cyano derivatives (patents) No. 3505381).

  Since the redox couple becomes an electron carrier, a certain concentration is required. The preferred concentration is 0.01 mol / l or more in total, more preferably 0.1 mol / l, and particularly preferably 0.3 mol / l or more. The upper limit in this case is not particularly limited, but is usually about 5 mol / l.

  The counter electrode functions as a positive electrode of the photoelectrochemical cell. The counter electrode is usually synonymous with the conductive support described above, but the support is not necessarily required in a configuration in which the strength is sufficiently maintained. However, having a support is advantageous in terms of hermeticity. Examples of the material for the counter electrode include platinum, carbon, conductive polymer, and the like. Preferred examples include platinum (JP 2001-102102 A), carbon (JP 2002-298936 A, JP 2003-297446 A, JP 2004-127849 A, JP 2004-152747 A, JP-A-2004-165015, JP-A-2004-111216, JP-A-2004-241228, JP-A-2004-319872), conductive polymer (JP-A-2003-317814, JP-A-2004-319131) And JP-A-2005-116301), and examples of JP-A-2001-43908, JP-A-2003-142168, JP-A-2004-127849, and JP-A-2004-152747. You may use what is shown.

  As the structure of the counter electrode, a structure having a high current collecting effect is preferable. Preferred examples include JP-A-10-505192, JP-A-2004-296669, JP-A-2005-11609, JP-A-2005-141996, JP-A-2005-142090, JP-A-2005-158470. JP, 2000-348784, JP 2005-158379, JP 2000-294305, JP 2001-243955, JP 2004-241228, JP 2004-296203. Examples of JP-A-2004-319872, JP-A-2005-197097, and the like.

As the light receiving electrode, a composite electrode such as titanium oxide and tin oxide (TiO ₂ / SnO ₂ ) may be used. As a mixed electrode of titania, for example, JP 2000-111393 A, JP 2004-95387 A, JP 2001-155791, JP2003-272723, JP05-504023, JP2000-114563, JP2002-75476, JP20028741, China 1350334 ( A), JP 2003-272724 A, JP 2003-308991 A, JP 2005-174934 A, JP 2001-358348 A, JP 2003-123862 A, JP 2004-103420 A. JP, 2005-39013, and 2003- No. 317815. As mixed electrodes other than titania, for example, JP 2001-185243, JP 2003-282164, JP 2003-289151, JP 2003-321299, JP 2002-93471, JP 2002-141115, JP 2002-184476, JP 2002-356400, JP 2002-246623, JP 2002-246624, JP 2002-261303, JP 2003 No. 243053, JP-A No. 2004-6235, JP-A No. 2003-323920, JP-A No. 2004-277197, JP-A No. 2004-210605, JP-A No. 2005-135798, JP-A No. 2005-135799. Publication, JP 2001-19610 JP, JP 100-100418, JP 2002-100419, JP 2002-280084, JP 2003-272724, JP 2004-124124, JP 09-237641. JP-A-11-273755 and JP-A-2004-247105.

  The light receiving electrode may be a tandem type in order to increase the utilization rate of incident light. Examples of preferable tandem type configurations include Japanese Patent Laid-Open No. 2002-90989, Japanese Patent Laid-Open No. 2002-222971, Japanese Patent Laid-Open No. 2003-168296, Japanese Patent Laid-Open No. 2003-249275, Japanese Patent Laid-Open No. 2005-166313, Japanese Laid-Open Patent Publication No. 11-273753, Japanese Unexamined Patent Application Publication No. 2002-167808, Japanese Unexamined Patent Application Publication No. 2005-129259, Japanese Unexamined Patent Application Publication No. 2002-231324, Japanese Unexamined Patent Application Publication No. 2005-158620, Japanese Unexamined Patent Application Publication No. 2005-158621, Japanese Unexamined Patent Application Publication No. 2005. Examples described in JP-A No. 191137 and JP-A No. 2003-333757 are given.

  A light management function for efficiently performing light scattering and reflection inside the light receiving electrode layer may be provided. Preferably, JP 2002-93476 A, JP 2004-296373 A, JP 2002-352868 A, JP 2003-142170 A, JP 2003-59549 A, JP 2002-289274 A. JP-A-2002-222968, JP-A-2003-217688, JP-A-2004-172110, JP-A-2003-303629, JP-A-2004-343071, JP-A-2005-116302, Examples include JP-A 09-259943, JP-A 10-255863, JP-A 2003-142171, JP-A 2002-110261, and JP-A 2004-311197.

  It is preferable to form a short-circuit prevention layer between the conductive support and the porous semiconductor fine particle layer in order to prevent reverse current due to direct contact between the electrolyte and the electrode. Preferable examples include JP 06-507999 A, JP 06-51113 A, JP 2000-178792 A, JP 11-312541 A, JP 2000-285974 A, JP 2000-285999 A. JP, 2001-143771, JP 2001156314, JP 2001-307785, JP 2002-151168, JP 2002-75471, JP 2003-163359, JP 2003-163360 A, JP 2003-123856 A, WO 03/038909, JP 2002-289270 A, JP 2002-319439 A, JP 2003-297443 A, JP 2004-87622 A. Publication, JP2003-33A No. 934, JP 2003-243054, JP 2004-319130, JP 2004-363069, JP 2005-71956, JP 2005-108807, JP 2005-108836. Gazette and JP-A-2005-142087.

  In order to prevent contact between the light receiving electrode and the counter electrode, it is preferable to use a spacer or a separator. Preferred examples include Japanese Patent Application Laid-Open Nos. 2001-283941, 2003-18783, 2000-294306, 2002-175844, 2002-367686, and 2004-253333. No. gazette.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these.

(Synthesis example)
<Preparation of Exemplified Dye A-1>
Illustrative dye A-1 was prepared by the following method.

(1) Preparation of Compound A-1a 10,11-Dihydro-5H-dibenz [b, f] azepine 15.0 g and 1-iodohexane 21.0 g were added to 60 ml of DMF and stirred at room temperature to dissolve them. It was ice-cooled later. Next, 7.5 g of 50-70% sodium hydride was added in portions, and the mixture was stirred for 1.5 hours at an internal temperature of 10 ° C or lower. After completion of the reaction, water was added dropwise to the reaction solution to inactivate the remaining sodium hydride, hexane was added for liquid separation, the organic layer was concentrated and purified by column chromatography to obtain Compound A-1a 18. 3 g was obtained.

(2) Preparation of Compound A-1b 20 ml of phosphorus oxychloride was added to 60 ml of DMF under ice-cooling and stirred for 30 minutes, 9.5 g of Compound A-1a was added thereto, heated to 60 ° C., and stirred for 3 hours. After allowing to cool to room temperature, water was added to the reaction mixture and stirred, and a 10% aqueous sodium hydroxide solution was further added and stirred for 1 hour. After extraction and concentration with ethyl acetate, column purification was performed to obtain 9.4 g of compound A-1b.

(3) Preparation of Compound A-1c After adding 2.0 g of Compound A-1b and 3.2 g of methyltriphenylphosphonium iodide to 20 ml of DMF, stirring and dissolving at room temperature, methanol solution of 28% sodium methoxide 1 0.5 g was added dropwise. Then, it heated at 60 degreeC and stirred for 2 hours. Thereafter, the mixture was allowed to cool to room temperature, water was added to the reaction solution, hexane was further added to carry out liquid separation, and the organic layer was concentrated and purified by column chromatography to obtain 1.9 g of Compound A-1c.

(4) Preparation of compound A-1d
To 10 ml of DMF, 5 ml of phosphorus oxychloride was added under ice-cooling and stirred for 30 minutes. Then, 1.9 g of compound A-1c was added thereto, heated to 60 ° C. and stirred for 3 hours. Thereafter, the mixture was allowed to cool to room temperature, and water was added to the reaction mixture and stirred. Further, a 10% aqueous sodium hydroxide solution was added, and the mixture was stirred for 1 hour. Extraction with ethyl acetate and concentration followed by column purification gave 2.0 g of compound A-1d.

(5) Synthesis of Compound A-1 After adding 1.0 g of A-1d and 0.25 g of cyanoacetic acid to 20 ml of acetic acid and stirring for 30 minutes, 0.5 g of ammonium acetate was added, heated to 90 ° C. and stirred for 3 hours. . After allowing to cool to room temperature, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate and concentrated. The obtained crystal was purified by recrystallization to obtain 0.6 g of A-1.

<Preparation of Exemplified Dye A-4>
Exemplified dye A-4 was prepared by the following method.

(1) Preparation of compound A-4a 15 ml of phosphorus oxychloride was added to 30 ml of DMF under ice-cooling and stirred for 30 minutes, and 5.8 g of compound A-1b was added thereto, heated to 60 ° C. and stirred for 4 hours. After allowing to cool to room temperature, water was added to the reaction mixture and stirred. The reaction solution was added dropwise to a 10% aqueous sodium hydroxide solution under ice cooling and stirred for 1 hour. After extraction and concentration with ethyl acetate, column purification was performed to obtain 3.3 g of Compound A-1b.

(3) Preparation of Compound A-4b 1.7 g of Compound A-4a and 4.9 g of methyltriphenylphosphonium iodide were added to 20 ml of DMF and stirred at room temperature to dissolve them, and then 28% sodium methoxide in methanol. 2.3 g of the solution was added dropwise. Then, it heated at 60 degreeC and stirred for 2 hours. After allowing to cool to room temperature, water was added to the reaction mixture, and hexane was further added for extraction. The organic layer was concentrated and purified by column chromatography to obtain 1.4 g of compound A-4b.

(4) Preparation of Compound A-4c 10 ml of phosphorus oxychloride was added to 20 ml of DMF under ice-cooling and stirred for 30 minutes, 1.3 g of Compound A-4b was added thereto, heated to 60 ° C. and stirred for 2 hours. After allowing to cool to room temperature, water was added to the reaction mixture and stirred. The reaction solution was added dropwise to a 10% aqueous sodium hydroxide solution under ice cooling and stirred for 1 hour. After extraction and concentration with ethyl acetate, column purification was performed to obtain 1.5 g of Compound A-4c.

(5) Synthesis of Compound A-4 After adding 1.4 g of A-4c and 0.6 g of cyanoacetic acid to 20 ml of acetic acid and stirring for 30 minutes, 1.1 g of ammonium acetate was added, heated to 90 ° C. and stirred for 4 hours. . After allowing to cool to room temperature, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate and concentrated. The obtained crystal was purified by recrystallization to obtain 1.5 g of A-4.

<Preparation of Exemplified Dye A-5>
As shown below, exemplary dye A-5 was prepared by reacting separately prepared intermediate B-1 with A-1d.

(1) Preparation of intermediate B-1 (i) Preparation of compound B-1a To 30 ml of DMF, 8.5 g of t-butyl cyanoacetate and 10.0 g of 4-methoxyphenyl isothiocyanate were added and stirred in an ice bath. 9.7 g of DBU was added dropwise. After stirring for 4 hours, 10.1 g of ethyl bromoacetate was added, and the mixture was heated to 65 ° C. After stirring for 4 hours, the mixture was allowed to cool to room temperature. Water was added, and the precipitated crystals were filtered to obtain 19.7 g of B-1a.
(Ii) Preparation of Intermediate B-1 After adding 1.1 g of B-1a to 10 ml of TFA and stirring at room temperature for 1 hour, water was added to the reaction solution and the precipitated crystals were filtered. This was purified by recrystallization to obtain 0.8 g of Intermediate B-1.

(2) Preparation of Illustrative Dye A-5 After adding 1.7 g of A-1d and 1.5 g of Intermediate B-1 to 20 ml of acetic acid and stirring for 30 minutes, 0.7 g of ammonium acetate was added and heated to 90 ° C. And stirred for 4 hours. After allowing to cool to room temperature, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate and concentrated. The obtained crystal was purified by recrystallization to obtain 1.5 g of A-5.

<Preparation of Exemplified Dye A-8>
Exemplified dye A-8 was prepared by the following method.

1.0 g of compound A-1b and 0.6 g of 3-carboxymethylrhodanine were dissolved in 20 ml of acetic acid by stirring at room temperature. To this was added 0.5 g of ammonium acetate and the mixture was heated and stirred at 90 ° C. for 4 hours. After cooling, water was added, and the precipitated crystals were collected by filtration and recrystallized with MeOH / CH ₂ Cl ₂ system to obtain 1.0 g of A-1.

<Preparation of Exemplified Dye A-26>
Exemplified dye A-26 was prepared by the following method.

(1) Preparation of Compound A-26a 5.0 g of 10,11-dihydro-5H-dibenz [b, f] azepine and 10.3 g of 1-iododecane were stirred and dissolved in 20 ml of DMF at room temperature and then ice-cooled. 50-70% sodium hydride (2.5 g) was added in portions, and the mixture was stirred at an internal temperature of 10 ° C or lower for 3.0 hours. After completion of the reaction, water was added dropwise to the reaction solution to inactivate the remaining sodium hydride, hexane was added for liquid separation, and the organic layer was concentrated and purified by column chromatography to give compound A-26a 8. 6 g was obtained.

(2) Preparation of Compound A-26b 10 ml of phosphorus oxychloride was added to 20 ml of DMF under ice-cooling and stirred for 30 minutes, 3.5 g of Compound A-24a was added thereto, heated to 60 ° C., and stirred for 2.5 hours. After allowing to cool to room temperature, water was added to the reaction mixture and stirred, and a 10% aqueous sodium hydroxide solution was further added and stirred for 1 hour. After extraction and concentration with ethyl acetate, column purification was performed to obtain 2.0 g of Compound A-26b.

(3) Preparation of Compound A-26c Compound A-26b (2.2 g) and methyltriphenylphosphonium iodide (2.9 g) were stirred in DMF (20 ml) at room temperature to dissolve them, and then 28% sodium methoxide M in methanol. 1.4 g was added dropwise. Then, it heated at 60 degreeC and stirred for 3 hours. After allowing to cool to room temperature, water was added to the reaction solution, and hexane was further added for extraction. The organic layer was concentrated and purified by column chromatography to obtain 2.0 g of compound A-26c.

(4) Preparation of compound A-26d
Under ice cooling, 10 ml of phosphorus oxychloride was added to 20 ml of DMF and stirred for 30 minutes. To this, 2.0 g of compound A-26c was added, and the mixture was heated to 60 ° C. and stirred for 0.5 hours. After allowing to cool to room temperature, water was added to the reaction mixture and stirred, and a 10% aqueous sodium hydroxide solution was further added and stirred for 1 hour. After extraction and concentration with ethyl acetate, column purification was performed to obtain 2.1 g of Compound A-26d.

(5) Synthesis of Exemplified Dye A-26 1.5 g of A-24d and 0.3 g of cyanoacetic acid were added to 20 ml of AcOH, stirred for 30 minutes, 0.6 g of ammonium acetate was added, and the mixture was heated to 90 ° C. and stirred for 5 hours. did. After allowing to cool to room temperature, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate and concentrated. The obtained crystal was purified by recrystallization to obtain 0.6 g of A-26.

<Preparation of Exemplified Dye A-3>
Illustrative dye A-3 was prepared by the following method.

(1) Preparation of Compound A-3a After 5.0 g of 10,11-dihydro-5H-dibenz [b, f] azepine and 12.7 g of 1-iodooctadecane were stirred in 20 ml of DMF at room temperature, these were dissolved. Ice-cooled. After 2.5 g of 50-70% sodium hydride was added in portions and stirred at an internal temperature of 10 ° C. or lower for 0.5 hours, the mixture was further stirred at room temperature for 3 hours. After completion of the reaction, water was added dropwise to the reaction solution to inactivate the remaining sodium hydride, hexane was added for liquid separation, the organic layer was concentrated, and purified by column chromatography to obtain Compound A-3a. 7 was obtained.

(2) Preparation of Compound A-3b 10 ml of phosphorus oxychloride was added to 20 ml of DMF under ice-cooling and stirred for 30 minutes, 5.0 g of Compound A-3a was added thereto, heated to 60 ° C. and stirred for 7 hours. After allowing to cool to room temperature, water was added to the reaction mixture and stirred, and a 10% aqueous sodium hydroxide solution was further added and stirred for 1 hour. After extraction and concentration with ethyl acetate, column purification was performed to obtain 4.6 g of Compound A-3b.

(3) Preparation of Compound A-3c After 4.5 g of Compound A-3b and 4.6 g of methyltriphenylphosphonium iodide were dissolved in 20 ml of DMF with stirring at room temperature, 2.2 g of 28% sodium methoxide in methanol was added dropwise. . Then, it heated at 60 degreeC and stirred for 5 hours. After allowing to cool to room temperature, water was added to the reaction solution, and hexane was further added for extraction. The organic layer was concentrated and purified by column chromatography to obtain 4.3 g of Compound A-3c.

(4) Preparation of compound A-3d
Under ice-cooling, 15 ml of phosphorus oxychloride was added to 30 ml of DMF, and the mixture was stirred for 30 minutes. Then, 4.3 g of compound A-3c was added thereto, heated to 60 ° C., and stirred for 5 hours. After allowing to cool to room temperature, water was added to the reaction mixture and stirred, and a 10% aqueous sodium hydroxide solution was further added and stirred for 1 hour. Extraction with ethyl acetate and concentration followed by column purification gave 1.8 g of compound A-3d.

(5) Synthesis of Illustrative Dye A-3 After adding 1.4 g of A-3d and 0.2 g of cyanoacetic acid to 20 ml of acetic acid and stirring for 30 minutes, 0.4 g of ammonium acetate was added, heated to 90 ° C. and stirred for 4 hours. did. After allowing to cool to room temperature, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate and concentrated. The obtained crystal was purified by recrystallization to obtain 1.3 g of A-3.

<Preparation of Exemplified Dye A-2>
As shown below, exemplary dye A-2 was prepared by reacting separately prepared intermediate B-2 with A-2d.

(1) Preparation of intermediate B-2 (i) Preparation of compound B-2a To 40 ml of DMF, 5.6 g of 3-ethylrhodanine and 5.0 g of ethyl isothiocyanate were added, stirred in an ice bath, and then 5.5 g of DBU. Was dripped. After stirring for 2 hours, 5.7 g of ethyl bromoacetate was added, heated to 80 ° C. and stirred for 4 hours, then allowed to cool to room temperature. Water was added, extracted with ethyl acetate, concentrated and purified by column chromatography to obtain 7.2 g of B-2a.

(Ii) Preparation of Intermediate B-2 After adding 7.2 g of B-2a and 30 ml of concentrated hydrochloric acid to 60 ml of acetic acid and heating to 90 ° C. and stirring for 4 hours, water was added to the reaction solution and the precipitated crystals were filtered. This was purified by recrystallization to obtain 5.5 g of intermediate B-2.

(2) Preparation of Illustrative Dye A-2 (i) Preparation of Compound A-2c 2.0 g of Compound A-1b and 2.8 g of benzyltriphenylphosphonium bromide were stirred in 20 ml of DMF at room temperature. 1.5% methanol solution of sodium methoxide was added dropwise. Then, it heated at 60 degreeC and stirred for 3 hours. After allowing to cool to room temperature, water was added to the reaction solution, and hexane was further added for extraction. The organic layer was concentrated and purified by column chromatography to obtain 1.6 g of compound A-3c.

(Ii) Preparation of compound A-2d
Under ice-cooling, 15 ml of phosphorus oxychloride was added to 30 ml of DMF, and the mixture was stirred for 30 minutes. Then, 2.9 g of compound A-2c was added thereto, heated to 50 ° C., and stirred for 4 hours. After allowing to cool to room temperature, water was added to the reaction mixture and stirred, and a 10% aqueous sodium hydroxide solution was further added and stirred for 1 hour. After extraction and concentration with ethyl acetate, column purification was performed to obtain 2.5 g of Compound A-2d.

(Iii) Synthesis of Exemplified Dye A-2 To 20 ml of acetic acid, 0.62 g of A-2d and 0.57 g of Intermediate B-2 were added and stirred for 30 minutes. Then, 0.2 g of ammonium acetate was added and heated to 90 ° C. Stir for 4 hours. After allowing to cool to room temperature, water was added to the reaction solution, and the precipitated crystals were filtered. The obtained crystal was purified by recrystallization to obtain 0.9 g of A-2.

<Preparation of Exemplified Dye A-46>
Exemplified dye A-46 was prepared by the following method.

(1) Preparation of Compound A-46a 5.0 g of 10-methoxy-5H-dibenzo [b, f] azepine and 9.3 g of 1-iododecane were added to 20 ml of DMF, and stirred at room temperature to dissolve them. Chilled. 50 g to 70% sodium hydride (2.0 g) was added in portions and stirred at an internal temperature of 10 ° C. or lower for 5.0 hours. After completion of the reaction, water was added dropwise to the reaction solution to inactivate the remaining sodium hydride, hexane was added for liquid separation, and the organic layer was concentrated and purified by column chromatography to give Compound A-46a 8. 4 g was obtained.

(2) Preparation of compound A-46b 10 ml of phosphorus oxychloride was added to 20 ml of DMF under ice-cooling and stirred for 30 minutes, and 3.5 g of compound A-46a was added thereto, heated to 60 ° C. and stirred for 2.5 hours. After allowing to cool to room temperature, water was added to the reaction mixture and stirred, and a 10% aqueous sodium hydroxide solution was further added and stirred for 1 hour. After extraction and concentration with ethyl acetate, column purification was performed to obtain 3.7 g of Compound A-46b.

(3) Preparation of Compound A-46c 3.5 g of Compound A-46b and 4.3 g of methyltriphenylphosphonium iodide were dissolved in 20 ml of DMF with stirring at room temperature, and 2.0 g of 28% sodium methoxide MeOH solution was added dropwise. Then, it heated at 60 degreeC and stirred for 4 hours. After allowing to cool to room temperature, water was added to the reaction solution, hexane was further added to carry out liquid separation, and the organic layer was concentrated and purified by column chromatography to obtain 2.7 g of Compound A-46c.

(4) Preparation of compound A-46d
10 ml of phosphorus oxychloride was added to 20 ml of DMF and stirred for 30 minutes under ice-cooling, and 2.7 g of compound A-46c was added thereto, heated to 60 ° C. and stirred for 1 hour. After allowing to cool to room temperature, water was added to the reaction mixture and stirred, and a 10% aqueous sodium hydroxide solution was further added and stirred for 1 hour. After extraction and concentration with ethyl acetate, column purification was performed to obtain 2.5 g of Compound A-46d.

(5) Synthesis of Illustrative Dye A-46 After adding 0.6 g of A-46d and 0.5 g of Intermediate B-2 to 30 ml of acetic acid and stirring for 30 minutes, add 0.2 g of ammonium acetate and warm to 90 ° C. Stir for 4 hours. After allowing to cool to room temperature, water was added to the reaction solution, and the precipitated crystals were filtered. The obtained crystals were purified by column chromatography to obtain 0.2 g of A-46.

<Preparation of Exemplified Dye A-17>
Exemplified dye A-17 was prepared by the following method.

  To 20 ml of acetic acid, 0.50 g of A-1d and 0.48 g of intermediate B-2 were added and stirred for 30 minutes. Then, 0.23 g of ammonium acetate was added, heated to 90 ° C. and stirred for 4 hours. After allowing to cool to room temperature, water was added to the reaction solution, and the precipitated crystals were filtered. The obtained crystal was purified by recrystallization to obtain 0.9 g of A-17.

<Preparation of Exemplified Dye A-9>
Exemplified dye A-9 was prepared by the following method.

  To 20 ml of acetic acid, 0.58 g of A-1b and 0.6 g of intermediate B-2 were added and stirred for 30 minutes. Then, 0.33 g of ammonium acetate was added, heated to 90 ° C. and stirred for 2 hours. After allowing to cool to room temperature, water was added to the reaction solution, and the precipitated crystals were filtered. The obtained crystal was purified by recrystallization to obtain 0.94 g of A-9.

<Preparation of Exemplified Dye A-10>
Exemplified dye A-10 was prepared by the following method.

  To 20 ml of acetic acid, 1.8 g of A-1b and 0.5 g of intermediate B-2 were added and stirred for 30 minutes. Then 1.0 g of ammonium acetate was added, heated to 90 ° C. and stirred for 4 hours. After allowing to cool to room temperature, water was added to the reaction solution, and the precipitated crystals were filtered. The obtained crystal was purified by recrystallization to obtain 1.9 g of A-10.

<Preparation of Exemplified Dye A-16>
Exemplified dye A-16 was prepared by the following method.

(1) Preparation of Compound A-16c 3.1 g of Compound A-1b and 5.2 g of hexyltriphenylphosphonium bromide were stirred in 20 ml of DMF at room temperature to dissolve them, and then 28% sodium methoxide in methanol. 5 g was added dropwise. Then, it heated at 60 degreeC and stirred for 2 hours. After allowing to cool to room temperature, water was added to the reaction solution, hexane was further added to carry out liquid separation, and the organic layer was concentrated and purified by column chromatography to obtain 3.3 g of Compound A-16c.

(4) Preparation of compound A-16d
Under ice cooling, 10 ml of phosphorus oxychloride was added to 20 ml of DMF and stirred for 30 minutes. Then, 3.2 g of compound A-16c was added thereto, heated to 35 ° C. and stirred for 6 hours. After allowing to cool to room temperature, water was added to the reaction mixture and stirred, and a 10% aqueous sodium hydroxide solution was further added and stirred for 1 hour. After extraction and concentration with ethyl acetate, column purification was performed to obtain 2.5 g of Compound A-16d.

(5) Synthesis of Exemplified Dye A-16 Add 0.75 g of A-16d and 0.60 g of the above Intermediate B-2 to 20 ml of AcOH, stir for 30 minutes, add 0.44 g of ammonium acetate, and heat to 90 ° C. Warmed and stirred for 5 hours. After allowing to cool to room temperature, water was added to the reaction solution, and the precipitated crystals were filtered. The obtained crystal was purified by recrystallization to obtain 0.95 g of A-2.

<Preparation of Exemplified Dye A-29>
Exemplified dye A-29 was prepared by the following method.

(1) Preparation of compound A-29a To 30 ml of EtOH, 3.0 g of compound A-1b and 0.4 g of sodium borohydride were added under ice cooling and stirred for 2 hours. Water was added and the mixture was stirred, extracted with ethyl acetate, concentrated and purified by column chromatography to give 2.9 g of compound A-29a.

(2) Preparation of Compound A-29b 1.7 g of Compound A-29b and 1.9 g of triphenylphosphine-hydrobromide salt were stirred in 90 ml of THF at 90 ° C. for 4.5 hours and then allowed to cool to room temperature. To this, 0.9 g of 2,5-thiophenedicarboxaldehyde and 1.3 g of a 28% sodium methoxide methanol solution were added dropwise. Then, it heated at 40 degreeC and stirred for 3 hours. After allowing to cool to room temperature, water was added to the reaction mixture, extracted with ethyl acetate, concentrated and purified by column chromatography to give 1.9 g of compound A-29b.

(3) Synthesis of Compound A-29 0.60 g of A-29b and 0.14 g of cyanoacetic acid were added to 20 ml of acetic acid and stirred for 30 minutes, then 0.28 g of ammonium acetate was added, and the mixture was heated to 90 ° C. and stirred for 11 hours. . After allowing to cool to room temperature, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate and concentrated. The obtained crystals were purified by column chromatography to obtain 0.2 g of A-29.

<Preparation of Exemplified Dye A-47>
Exemplified dye A-47 was prepared by the following method.

(1) Preparation of Compound A-47a 3.0 g of Compound A-1b and 4.5 g of allyltriphenylphosphonium bromide were stirred in 30 ml of DMF at room temperature to dissolve them, and then a methanol solution of 28% sodium methoxide 2 .3 g was added dropwise. Then, it heated at 60 degreeC and stirred for 5 hours. After allowing to cool to room temperature, water was added to the reaction solution, hexane was further added to carry out liquid separation, and the organic layer was concentrated and purified by column chromatography to obtain 2.1 g of Compound A-47a.

(2) Preparation of compound A-47b
To 10 ml of DMF, 5 ml of phosphorus oxychloride was added under ice-cooling and stirred for 30 minutes, 2.1 g of compound A-47a was added thereto, heated to 60 ° C. and stirred for 1.5 hours. After allowing to cool to room temperature, water was added to the reaction mixture and stirred, and a 10% aqueous sodium hydroxide solution was further added and stirred for 1 hour. After extraction and concentration with ethyl acetate, column purification was performed to obtain 1.0 g of Compound A-47b.

(3) Synthesis of Illustrative Dye A-47 After adding 0.93 g of A-47b and 0.22 g of cyanoacetic acid to 15 ml of acetic acid and stirring for 30 minutes, 0.4 g of ammonium acetate is added, heated to 90 ° C. and stirred for 4 hours. did. After allowing to cool to room temperature, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate and concentrated. The obtained crystal was purified by recrystallization to obtain 0.70 g of A-47.

<Preparation of Exemplified Dye A-48>
As shown below, Exemplified dye A-48 was prepared using Intermediate B-3 separately prepared.
(1) Preparation of Intermediate B-3 First, Intermediate B-3 was prepared by the following method.

  To 100 ml of dimethylacetamide (DMAc), 22.7 g of iodophenol, 21.9 g of iodohexane and 21.3 g of potassium carbonate were added and stirred for 4 hours. Water was added, the mixture was extracted with ethyl acetate, concentrated, and purified by column chromatography to obtain 28 g of Intermediate B-3.

Next, as shown below, exemplary dye A-48 was prepared using the obtained intermediate B-3.

(2) Preparation of compound A-48a 10,11-dihydro-5H-dibenz [b, f] azepine 0.5 g and t-butoxy sodium 0.73 g, intermediate B-3 0.66 g, tri-t-butyl One drop of phosphine and a catalyst amount of trisdibenzylideneacetone palladium were put in 20 ml of toluene, heated to 110 ° C. and stirred for 4 hours. Thereafter, water was added to the reaction solution to terminate the reaction. Ethyl acetate was added for liquid separation, and the organic layer was concentrated and purified by column chromatography to obtain 0.67 g of Compound A-48a.

(3) Preparation of Compound A-48b 20 ml of phosphorus oxychloride was added to 90 ml of DMF under ice-cooling and stirred for 30 minutes, 11.1 g of Compound A-48b was added thereto, heated to 70 ° C. and stirred for 5 hours. After allowing to cool to room temperature, water was added to the reaction mixture and stirred, and a 10% aqueous sodium hydroxide solution was further added and stirred for 1 hour. After extraction and concentration with ethyl acetate, column purification was performed to obtain 6.0 g of Compound A-48b.

(4) Synthesis of Illustrative Dye A-48 After adding 0.71 g of A-48b and 0.57 g of Intermediate B-2 to 30 ml of acetic acid and stirring for 30 minutes, add 0.27 g of ammonium acetate and warm to 90 ° C. Stir for 4.5 hours. After allowing to cool to room temperature, water was added to the reaction solution, and the precipitated crystals were filtered. The obtained crystals were purified by recrystallization to obtain 1.1 g of A-48.

<Preparation of Exemplified Dye A-49>
As shown below, Exemplified dye A-49 was prepared using the intermediate B-2 prepared separately.

  To 50 ml of acetic acid, 0.51 g of A-4a and 0.97 g of intermediate B-2 were added and stirred for 30 minutes. Then, 0.47 g of ammonium acetate was added, heated to 90 ° C. and stirred for 6 hours. After allowing to cool to room temperature, water was added to the reaction solution, and the precipitated crystals were filtered. The obtained crystals were purified by recrystallization to obtain 1.1 g of A-49.

<Preparation of Exemplified Dye A-50>
As shown below, Exemplified dye A-50 was prepared using the intermediate B-2 prepared separately.

(1) Preparation of Compound A-50a After 2.0 g of Compound A-1b and 3.0 g of ethyltriphenylphosphonium iodide were stirred in 25 ml of DMF at room temperature to dissolve them, 28% sodium methoxide methanol 1.5 g of the solution was added dropwise. Then, it heated at 60 degreeC and stirred for 4 hours. After allowing to cool to room temperature, water was added to the reaction solution, hexane was further added to carry out liquid separation, and the organic layer was concentrated and purified by column chromatography to obtain 1.9 g of Compound A-50a.

(2) Preparation of compound A-50b
Under ice cooling, 10 ml of phosphorus oxychloride was added to 20 ml of DMF, and the mixture was stirred for 30 minutes. Then, 2.9 g of compound A-50b was added thereto, heated to 50 ° C., and stirred for 4 hours. After allowing to cool to room temperature, water was added to the reaction mixture and stirred, and a 10% aqueous sodium hydroxide solution was further added and stirred for 1 hour. After extraction and concentration with ethyl acetate, column purification was performed to obtain 1.3 g of Compound A-50b.

(3) Synthesis of Exemplified Dye A-50 To 50 ml of acetic acid, 0.70 g of A-50b and 0.67 g of the above intermediate B-2 were added and stirred for 30 minutes. Then, 0.32 g of ammonium acetate was added and the mixture was heated to 90 ° C. Warmed and stirred for 5 hours. After allowing to cool to room temperature, water was added to the reaction solution, and the precipitated crystals were filtered. The obtained crystal was purified by recrystallization to obtain 0.9 g of A-50.

<Preparation of Exemplified Dye A-51>
As shown below, Exemplified dye A-51 was prepared using the intermediate B-2 prepared separately.

  After adding 0.48 g of A-26d and 0.38 g of intermediate B-2 to 20 ml of acetic acid, the mixture was stirred for 30 minutes, then 0.19 g of ammonium acetate was added, heated to 90 ° C., and stirred for 4 hours. After allowing to cool to room temperature, water was added to the reaction solution, and the precipitated crystals were filtered. The obtained crystal was purified by recrystallization to obtain 0.7 g of A-51.

<Preparation of Exemplified Dye A-52>
Exemplified dye A-52 was prepared by the following method.

(1) Synthesis of Compound A-52a After 3.3 g of Compound A-4a and 8.7 g of hexyltriphenylphosphonium iodide were dissolved in 30 ml of DMF with stirring at room temperature, 3.9 g of a methanol solution of 28% sodium methoxide was added dropwise. . Then, it heated at 60 degreeC and stirred for 2 hours. After allowing to cool to room temperature, water was added to the reaction solution, and hexane was further added for liquid separation, and the organic layer was concentrated and purified by column chromatography to obtain 4.2 g of Compound A-52b.

(2) Synthesis of Compound A-52b 15 ml of phosphorus oxychloride was added to 30 ml of DMF under ice-cooling and stirred for 30 minutes, 4.2 g of Compound A-52a was added thereto, heated to 60 ° C. and stirred for 4 hours. After allowing to cool to room temperature, water was added to the reaction mixture and stirred. The reaction solution was added dropwise to a 10% aqueous sodium hydroxide solution under ice cooling and stirred for 1 hour. After extraction and concentration with ethyl acetate, column purification was performed to obtain 3.8 g of Compound A-52b.

(3) Synthesis of Illustrative Dye A-52 To 20 ml of acetic acid, 0.90 g of A-52b and 0.30 g of cyanoacetic acid were added and stirred for 30 minutes. Then 0.26 g of ammonium acetate was added, heated to 90 ° C. and stirred for 4 hours. did. After allowing to cool to room temperature, water was added to the reaction mixture, and the mixture was extracted with ethyl acetate and concentrated. The obtained crystal was purified by recrystallization to obtain 1.0 g of A-52.

<Preparation of Exemplified Dye A-53>
As shown below, Exemplified dye A-51 was prepared using the intermediate B-2 prepared separately.

  To 50 ml of acetic acid, 0.77 g of A-52b and 0.92 g of intermediate B-2 were added and stirred for 30 minutes. Then, 0.45 g of ammonium acetate was added, heated to 90 ° C. and stirred for 6 hours. After allowing to cool to room temperature, water was added to the reaction solution, and the precipitated crystals were filtered. The obtained crystal was purified by recrystallization to obtain 1.1 g of A-53.

Example 1
(Preparation of photoelectric conversion element)
The photoelectric conversion element shown in FIG. 1 was produced as follows.
On the glass substrate, tin oxide doped with fluorine was formed as a transparent conductive film by sputtering, and this was scribed with a laser to divide the transparent conductive film into two parts.
Next, 32 g of anatase-type titanium oxide (P-25 (trade name) manufactured by Nippon Aerosil Co., Ltd.) is mixed with 100 ml of a mixed solvent of water and acetonitrile having a volume ratio of 4: 1, and a rotating / revolving mixing conditioner is prepared. The resulting mixture was uniformly dispersed and mixed to obtain a semiconductor fine particle dispersion. This dispersion was applied to a transparent conductive film and heated at 500 ° C. to produce a light receiving electrode.
Thereafter, similarly, a dispersion containing 40:60 (mass ratio) of silica particles and rutile-type titanium oxide is prepared, and this dispersion is applied to the light receiving electrode and heated at 500 ° C. to form an insulating porous material. Formed body. Next, a carbon electrode was formed as a counter electrode.
Next, the glass substrate on which the insulating porous body was formed was immersed in an ethanol solution (3 × 10 ⁻⁴ mol / l) of a sensitizing dye described in Table 1 below for 48 hours. The glass dyed with the sensitizing dye was immersed in a 10% ethanol solution of 4-tert-butylpyridine for 30 minutes, then washed with ethanol and air dried. The thickness of the photosensitive layer thus obtained was 10 μm, and the coating amount of semiconductor fine particles was 20 g / m ² . As the electrolytic solution, a methoxypropionitrile solution of dimethylpropylimidazolium iodide (0.5 mol / l) and iodine (0.1 mol / l) was used.

(Measurement of maximum absorption wavelength of sensitizing dye)
The maximum absorption wavelength of the sensitizing dye used was measured. A spectrophotometer (U-4100, manufactured by Hitachi High-Tech) was used, and ethanol was used as the solution.

(Measurement of photoelectric conversion efficiency)
Simulated sunlight containing no ultraviolet rays was generated by passing the light of a 500 W xenon lamp (manufactured by Ushio) through an AM1.5G filter (manufactured by Oriel) and a sharp cut filter (KenkoL-42, trade name). The intensity of this light was 89 mW / cm ² . The produced photoelectric conversion element was irradiated with this light, and the generated electricity was measured with a current-voltage measuring device (Caseley 238 type, trade name). The results of measuring the conversion efficiency of the photoelectrochemical cell thus obtained are shown in Table 1 below. As a result, conversion efficiency of 5% or more was evaluated as ◎, 2% or more and less than 5% as ◯, 0.5% or more and less than 2% as △, and less than 0.5% as x. .

As sample number 54, the following sensitizing dye A described in JP-A No. 11-214730 was used.

As shown in Table 1, the electrochemical cell produced using the dye of the present invention has A1 to A7, A12 to A15, A-18, A-19, A-21, A- as dyes. 24, A-26 to A-31, A-33 to A-35, A-41, A-43, A-44, A-50, A-52, A-53, the conversion efficiency is The value was as high as 5% or more. Even when other dyes of the present invention were used, the conversion efficiency was 2% or more and less than 5%, which was a usable level.
On the other hand, the comparative example of sample number 54 had a conversion efficiency of 0.5% or more and less than 2%, which was insufficient for use in an electrochemical cell.

(Example 2)
An ITO film was produced on a glass substrate, and an FTO film was laminated thereon to produce a transparent conductive film. Then, a transparent electrode plate was obtained by forming an oxide semiconductor porous film on the transparent conductive film. And the photoelectrochemical cell was produced using the transparent electrode plate, and conversion efficiency was measured. The method is as follows (1)-(5).

(1) Preparation of raw material compound solution for ITO (indium / tin / oxide) film Indium (III) tetrahydrate 5.58 g and tin (II) chloride dihydrate 0.23 g were dissolved in 100 ml of ethanol. Thus, a raw material compound solution for ITO film was obtained.

(2) Preparation of FTO (Fluorine Doped Tin Oxide) Film Raw Material Compound Solution 0.701 g of tin (IV) chloride pentahydrate was dissolved in 10 ml of ethanol, and 0.592 g of a saturated aqueous solution of ammonium fluoride was added thereto. This mixture was subjected to an ultrasonic cleaning machine for about 20 minutes and completely dissolved to obtain a raw material compound solution for an FTO film.

(3) Preparation of ITO / FTO transparent conductive film The surface of a heat-resistant glass plate having a thickness of 2 mm was chemically washed and dried, and then this glass plate was placed in a reactor and heated with a heater. When the heating temperature of the heater reached 450 ° C., the raw material compound solution for ITO film obtained in (1) was adjusted from a nozzle having a diameter of 0.3 mm to a pressure of 0.06 MPa and a distance to the glass plate of 400 mm, 25 Sprayed for a minute.
After spraying the raw material compound solution for ITO film, 2 minutes passed (ethanol was sprayed on the glass substrate surface during this period to suppress the rise of the substrate surface temperature), and the heating temperature of the heater became 530 ° C. Occasionally, the FTO membrane raw material compound solution obtained in (2) was sprayed for 2 minutes 30 seconds under the same conditions. As a result, a transparent electrode plate was obtained in which an ITO film having a thickness of 530 nm and an FTO film having a thickness of 170 nm were sequentially formed on the heat-resistant glass plate.
For comparison, similarly, a transparent electrode plate in which only a 530 nm thick ITO film is formed on a heat resistant glass plate having a thickness of 2 mm and a transparent electrode plate in which only a 180 nm thick FTO film is similarly formed are formed. Each was produced.
These three kinds of transparent electrode plates were heated in a heating furnace at 450 ° C. for 2 hours.

(4) Production of photoelectrochemical cell Next, a photoelectrochemical cell having the structure shown in FIG. 2 of Japanese Patent No. 4260494 was produced using the above three types of transparent electrode plates. The oxide semiconductor porous film 15 is formed by dispersing fine particles of titanium oxide having an average particle size of about 230 nm in 100 ml of acetonitrile to form a paste, applying this to the transparent electrode 11 to a thickness of 15 μm by a bar coating method, and drying. The oxide semiconductor porous film 15 was loaded with the dyes listed in Table 2 by baking at 450 ° C. for 1 hour. The immersion conditions in the dye solution were the same as in Example 1.
Further, a conductive substrate in which an ITO film and an FTO film were laminated on a glass plate was used for the counter electrode 16, and an electrolytic solution made of a non-aqueous solution of iodine / iodide was used for the electrolyte layer 17. The planar dimension of the photoelectrochemical cell was 25 mm × 25 mm.

(5) Evaluation of photoelectrochemical cell About this photoelectrochemical cell, artificial sunlight (AM1.5) was irradiated and the electric power generation efficiency was calculated | required. The results are shown in Table 2. As a result, conversion efficiency of 5% or more is indicated as ◎, 2% or more and less than 5% as ◯, 0.5% or more and less than 2% as △, and less than 0.5% as x. .
Sample No. using sensitizing dye A In Samples 11 to 13, the conversion efficiency is low, whereas Sample No. using the exemplified dye of the present invention. It turned out that a favorable result is shown in 1-9. In a photoelectrochemical cell using a laminate of an ITO film and an FTO film as a transparent electrode plate, the conversion efficiency is particularly high as compared with the case where only an ITO film or only an FTO film is used. This dye was found to be highly effective.

(Example 3)
A collecting electrode was arranged on the FTO film to produce a photoelectrochemical cell, and the conversion efficiency was evaluated. Evaluation was made into two types, test cell (i) and test cell (iv) as follows.

(Test cell (i))
The surface of a heat-resistant glass plate of 100 mm × 100 mm × 2 mm was chemically washed and dried, and then this glass plate was placed in a reactor and heated with a heater, and then the FTO (fluorine-doped tin oxide) film used in Example 2 The raw material compound solution was sprayed from a nozzle having a diameter of 0.3 mm at a pressure of 0.06 MPa and a distance to the glass plate of 400 mm for 25 minutes to prepare a glass substrate with an FTO film. On the surface, grooves having a depth of 5 μm were formed in a lattice circuit pattern by an etching method. After pattern formation by photolithography, etching was performed using hydrofluoric acid. A metal conductive layer (seed layer) was formed thereon by sputtering to enable plating formation, and a metal wiring layer 3 was further formed by additive plating. The metal wiring layer 3 was formed in a convex lens shape from the surface of the transparent substrate 2 to a height of 3 μm. The circuit width was 60 μm. From this, an FTO film having a thickness of 400 nm was formed as the shielding layer 5 by the SPD method to obtain an electrode substrate (i). The cross-sectional shape of the electrode substrate (i) was as shown in FIG. 2 in JP-A No. 2004-146425.
On the electrode substrate (i), a dispersion obtained by dispersing titanium oxide having an average particle diameter of 25 nm in 100 ml of acetonitrile was applied and dried, and heated and sintered at 450 ° C. for 1 hour. This was immersed in an ethanol solution of the dye shown in Table 3 to adsorb the dye. The immersion conditions were the same as in Example 1. It arrange | positioned facing a platinum sputter | spatter FTO board | substrate through the 50-micrometer-thick thermoplastic polyolefin resin sheet, the resin sheet part was heat-melted, and the bipolar plate was fixed.
A methoxyacetonitrile solution containing 0.5M iodide and 0.05M iodine as the main components was injected from the electrolyte solution inlet previously opened on the platinum sputter electrode side, and filled between the electrodes. It was. Further, the peripheral part and the electrolyte solution injection port were finally sealed with an epoxy-based sealing resin, and a silver paste was applied to the current collecting terminal part to obtain a test cell (i). The photoelectric conversion characteristics of the test cell (i) were evaluated using pseudo sunlight of AM1.5. The results are shown in Table 3.

(Test cell (iv))
A glass substrate with a 100 × 100 mm FTO film was prepared in the same manner as in the test cell (i). A metal wiring layer 3 (gold circuit) was formed on the FTO glass substrate by additive plating. The metal wiring layer 3 (gold circuit) was formed in a lattice shape on the substrate surface, and had a circuit width of 50 μm and a circuit thickness of 5 μm. On this surface, an FTO film having a thickness of 300 nm was formed as a shielding layer 5 by the SPD method to obtain a test cell (iv). When the cross section of the electrode substrate (iv) was confirmed using SEM-EDX, there was a sneaking in which seems to be caused by the bottom of the plating resist at the bottom of the wiring, and the shadow portion was not covered with FTO.
A test cell (iv) was produced in the same manner as the test cell (i) using the electrode substrate (iv). The photoelectric conversion characteristics of the test cell (iv) were evaluated by AM1.5 artificial sunlight, and the results are shown in Table 3. As a result, conversion efficiency of 5% or more is indicated as ◎, 2% or more and less than 5% as ◯, 0.5% or more and less than 2% as △, and less than 0.5% as x. .

  From Table 3, when the pigment | dye of this invention was used, the conversion efficiency in the case of test cell (i) showed the high value with 5% or more. On the other hand, when the test cell (iv) was used, the conversion efficiency was higher when the dye of the present invention was used as compared with the case where the dye of the comparative example was used. For this reason, it was found that the degree of freedom of test cell selection was increased by using the dye of the present invention (comparison between sample number 11 and sample number 13).

Example 4
Tests were conducted on a method for producing peroxotitanic acid and titanium oxide fine particles and a method for producing an oxide semiconductor film using the peroxotitanic acid and titanium oxide fine particles, and a photoelectrochemical cell was produced and evaluated.

(Photovoltaic cell (A))
(1) Preparation of coating liquid (A) for forming an oxide semiconductor film 5 g of titanium hydride is suspended in 1 liter of pure water, 400 g of a 5 mass% hydrogen peroxide solution is added over 30 minutes, and then 80 A solution of peroxotitanic acid was prepared by heating to ° C and dissolution. 90% by volume was taken from the total amount of this solution, adjusted to pH 9 by adding concentrated aqueous ammonia, placed in an autoclave, hydrothermally treated at 250 ° C. for 5 hours under saturated vapor pressure, and titania colloidal particles (A) Was prepared. The obtained titania colloidal particles were anatase type titanium oxide having high crystallinity by X-ray diffraction.
Next, the obtained titania colloidal particles (A) was concentrated to 10 wt%, the peroxotitanic acid solution were mixed, the titanium of the mixed solution TiO ₂ terms, TiO ₂ mass of 30 mass% Then, hydroxypropylcellulose was added as a film formation aid so that a coating solution for forming a semiconductor film was prepared.

(2) Production of oxide semiconductor film (A) Next, the coating solution was applied on a transparent glass substrate on which fluorine-doped tin oxide was formed as an electrode layer, dried naturally, and subsequently 6000 mJ using a low-pressure mercury lamp. The peroxoacid was decomposed by irradiating with / cm ² of ultraviolet rays, and the coating film was cured. The coating film was heated at 300 ° C. for 30 minutes to decompose and anneal the hydroxypropyl cellulose to form an oxide semiconductor film (A) on the glass substrate.

(3) Adsorption of dye to oxide semiconductor film (A) Next, an ethanol solution having a concentration of 3 × 10 ⁻⁴ mol / liter of the dye of the present invention was prepared as a spectral sensitizing dye. This dye solution was applied onto the metal oxide semiconductor film (A) with a 100 rpm spinner and dried. This coating and drying process was performed five times.

(4) Preparation of electrolyte solution In a mixed solvent having a volume ratio of acetonitrile and ethylene carbonate of 1: 5, tetrapropylammonium iodide is adjusted to a concentration of 0.46 mol / liter and iodine to a concentration of 0.07 mol / liter. To prepare an electrolyte solution.

(5) Production of photoelectric cell (A) The glass substrate on which the oxide semiconductor film (A) adsorbed with the dye produced in (2) was formed was used as one electrode, and the other electrode was fluorine-doped. A transparent glass substrate carrying tin oxide as an electrode and carrying platinum on it is placed facing it, the sides are sealed with resin, the electrolyte solution (4) is sealed between the electrodes, and the electrodes are lead between them. Photoelectric cells (A) were prepared by connecting with wires.

(6) Evaluation of Photoelectric Cell (A) Photoelectric cell (A) was irradiated with light of 100 W / m ² with a solar simulator, measured η (conversion efficiency), and the results are shown in Table 4. Indicated.

(Photovoltaic cell (B))
Oxide semiconductor film (A) except that after irradiation with ultraviolet light, peroxo acid was decomposed and the film was cured, Ar gas ion irradiation (Nisshin Electric Co., Ltd .: ion implantation apparatus, irradiation at 200 eV for 10 hours) was performed. ), An oxide semiconductor film (B) was formed.
Similarly to the oxide semiconductor film (A), the dye was adsorbed to the oxide semiconductor film (B).
Thereafter, a photoelectric cell (B) was prepared in the same manner as in Example 1, and η was measured. The results are shown in Table 4.

(Photovoltaic cell (C))
18.3 g of titanium tetrachloride was diluted with pure water to obtain an aqueous solution containing 1.0% by mass in terms of TiO ₂ . While stirring this aqueous solution, 15% by mass of aqueous ammonia was added to obtain a white slurry having a pH of 9.5. This slurry was washed by filtration to obtain a 10.2% by mass hydrated titanium oxide gel cake in terms of TiO ₂ . This cake was mixed with 400 g of a 5 mass% hydrogen peroxide solution, and then heated to 80 ° C. to dissolve to prepare a peroxotitanic acid solution. 90% by volume is taken from the total amount of this solution, and concentrated ammonia water is added to adjust the pH to 9, and the mixture is placed in an autoclave, hydrothermally treated at 250 ° C. for 5 hours under saturated vapor pressure, and titania colloidal particles (C ) Was prepared.
Next, using the peroxotitanic acid solution obtained above and titania colloidal particles (C), an oxide semiconductor film (C) is formed in the same manner as the oxide semiconductor film (A), and the metal oxide semiconductor film In the same manner as (A), the dye of the present invention was adsorbed as a spectral sensitizing dye.
Thereafter, a photoelectric cell (C) was prepared by the same method as that for the photoelectric cell (A), and η was measured. The results are shown in Table 4.

(Photovoltaic cell (D))
18.3 g of titanium tetrachloride was diluted with pure water to obtain an aqueous solution containing 1.0% by mass in terms of TiO ₂ . While stirring this, 15% by mass of ammonia water was added to obtain a white slurry having a pH of 9.5. This slurry was filtered and washed, suspended in pure water to obtain a 0.6 mass% hydrated titanium oxide gel slurry as TiO ₂ , adjusted to pH 2 by adding hydrochloric acid thereto, put in an autoclave, and stirred at 180 ° C. for 5 hours. The titania colloidal particles (D) were prepared by performing hydrothermal treatment for a period of time under saturated vapor pressure.
Next, titania colloidal particles (D) are concentrated to 10% by mass, and hydroxypropyl cellulose is added as a film forming aid so as to be 30% by mass in terms of TiO ₂ to form a semiconductor film. A coating solution was prepared. Next, the coating solution is applied onto a transparent glass substrate on which fluorine-doped tin oxide is formed as an electrode layer, dried naturally, and subsequently irradiated with 6000 mJ / cm ² of ultraviolet rays using a low-pressure mercury lamp to form a film. Cured. Furthermore, it heated at 300 degreeC for 30 minute (s), decomposed | disassembled and annealed hydroxypropyl cellulose, and formed the oxide semiconductor film (D).
Next, the dye of the present invention was adsorbed as a spectral sensitizing dye in the same manner as the oxide semiconductor film (A).
Then, the photoelectric cell (D) was created by the method similar to a photoelectric cell (A), and (eta) was measured. The results are shown in Table 4. As a result, conversion efficiency of 5% or more is indicated as ◎, 2% or more and less than 5% as ◯, 0.5% or more and less than 2% as △, and less than 0.5% as x. .

  From Table 4, in the case of the pigment | dye of this invention, when test cell (A)-(C) was used, it turned out that conversion efficiency is especially high.

(Example 5)
Titanium oxide was prepared or synthesized by changing the method, an oxide semiconductor film was prepared from the obtained titanium oxide, and a photoelectrochemical cell was evaluated.

(1) Preparation of titanium oxide by heat treatment Using commercially available anatase-type titanium oxide (trade name ST-01, manufactured by Ishihara Sangyo Co., Ltd.), this is heated to about 900 ° C. and converted to blue kite-type titanium oxide. Further, it was heated to about 1,200 ° C. to obtain a rutile type titanium oxide. Respectively, comparative titanium oxide 1 (anatase type), titanium oxide 1 (blue kite type), and comparative titanium oxide 2 (rutile type) are used.

(2) Synthesis of titanium oxide by wet method (titanium oxide 2 (blue kite type))
954 ml of distilled water is charged into a reaction vessel equipped with a reflux condenser and heated to 95 ° C. While maintaining the stirring speed at about 200 rpm, 46 ml of an aqueous solution of titanium tetrachloride (Ti content: 16.3 mass%, specific gravity 1.59, purity 99.9%) was added to this distilled water at a speed of about 5.0 ml / min. It was dripped at the reaction tank. At this time, care was taken not to lower the temperature of the reaction solution. As a result, the titanium tetrachloride concentration was 0.25 mol / liter (2% by mass in terms of titanium oxide). In the reaction vessel, the reaction solution started to become cloudy immediately after dropping, but kept at the same temperature. After the dropping was completed, the temperature was further raised and heated to the vicinity of the boiling point (104 ° C.). The reaction was terminated.
The sol obtained by the reaction was filtered, and then powdered using a vacuum dryer at 60 ° C. As a result of quantitative analysis of this powder by X-ray diffractometry, the ratio of (peak intensity on the surface of blue kite type 121) / (peak intensity at the position where the three overlap) is 0.38, (rutile main peak intensity) / The ratio (peak intensity at the position where the three lines overlap) was 0.05. From these, the titanium oxide was crystallinity of about 70.0% by mass for the brookite type, about 1.2% by mass for the rutile type, and about 28.8% by mass for the anatase type. Further, when the fine particles were observed with a transmission electron microscope, the average particle diameter of the primary particles was 0.015 μm.

(Titanium oxide 3 (Blue Kite type))
An aqueous solution of titanium trichloride (Ti content: 28% by mass, specific gravity 1.5, purity 99.9%) was diluted with distilled water to obtain a solution having a concentration of 0.25 mol / L in terms of titanium concentration. At this time, it was ice-cooled so as not to increase the liquid temperature and kept at 50 ° C. or lower. Next, 500 ml of this solution was put into a reaction tank equipped with a reflux condenser, and ozone gas with a purity of 80% was bubbled from the ozone gas generator at 1 L / min while heating at 85 ° C. to carry out an oxidation reaction. This state was maintained for 2 hours to complete the reaction. The obtained sol was filtered and vacuum-dried to obtain a powder. As a result of quantitative analysis of this powder by X-ray diffractometry, the ratio of (peak intensity on the surface of blue kite type 121) / (peak intensity at the position where the three overlap) is 0.85, (rutile main peak intensity) / The ratio (peak intensity at the position where the three lines overlap) was 0. From these, the titanium dioxide was about 98% by mass for the blue kite type, 0% by mass for the rutile type, 0% by mass for the anatase type, and about 2% was amorphous. Further, when the fine particles were observed with a transmission electron microscope, the average particle diameter of the primary particles was 0.05 μm.

(Production and evaluation of dye-sensitized photoelectric conversion device)
A photoelectric conversion element having the configuration shown in FIG. 1 of JP-A No. 2000-340269 was produced as follows using titanium oxide prepared by the above titanium oxides 1 to 3 as a semiconductor.
A glass substrate was coated with fluorine-doped tin oxide to form a conductive transparent electrode. A paste using each titanium oxide particle as a raw material was formed on the electrode surface, applied to a thickness of 50 μm by a bar coating method, and then baked at 500 ° C. to form a thin layer having a thickness of about 20 μm. Next, a 3 × 10 ⁻⁴ molar ethanol solution of the dye was prepared, and the glass substrate on which the titanium oxide thin layer was formed was immersed therein and kept at room temperature for 12 hours.

  A photoelectric conversion element having a configuration shown in FIG. 1 of JP-A-2000-340269 was prepared using an iodine salt of tetrapropylammonium as an electrolytic solution and an acetonitrile solution of lithium iodide and using platinum as a counter electrode. For photoelectric conversion, light from a 160-w high-pressure mercury lamp (the infrared part was cut by a filter) was applied to the above-mentioned element, and the conversion efficiency at that time was measured. The results are shown in Table 5. As a result, conversion efficiency of 5% or more was indicated as ◎, 2% or more and less than 5% as ◯, 0.5% or more and less than 2% as △, and less than 0.5% as x. .

  From Table 5, it was found that the dye of the present invention has high conversion efficiency.

(Example 6)
Photoelectrochemical cells were fabricated as semiconductor electrodes using titanium oxides having different particle sizes, and the characteristics were evaluated.
[Preparation of paste]
First, a paste for forming a semiconductor layer or a light scattering layer of a semiconductor electrode constituting the photoelectrode was prepared by the following procedure.

(Paste 1)
A titania slurry was prepared by placing spherical TiO ₂ particles (anatase type, average particle size: 25 nm, hereinafter referred to as spherical TiO ₂ particles 1) in a nitric acid solution and stirring. Next, a cellulose binder as a thickener was added to the titania slurry and kneaded to prepare a paste.

(Paste 2)
A titania slurry was prepared by placing spherical TiO ₂ particles 1 and spherical TiO ₂ particles (anatase type, average particle size: 200 nm, hereinafter referred to as spherical TiO ₂ particles 2) in a nitric acid solution and stirring. Next, a cellulose binder as a thickener was added to the titania slurry and kneaded to prepare a paste (mass of TiO ₂ particles 1: mass of TiO ₂ particles 2 = 30:70).

(Paste 3)
The paste 1 is mixed with rod-like TiO ₂ particles (anatase type, diameter: 100 nm, aspect ratio: 5, hereinafter referred to as rod-like TiO ₂ particles 1), the mass of the rod-like TiO ₂ particles 1: the mass of the paste 1 = 10: Ninety pastes were prepared.

(Paste 4)
The paste 1, a rod-shaped TiO ₂ particles 1 were mixed, the mass rod-shaped TiO ₂ particles 1: Paste 1 Mass = 30: 70 paste was prepared.

(Paste 5)
The paste 1, a rod-shaped TiO ₂ particles 1 were mixed, the mass rod-shaped TiO ₂ particles 1: Paste 1 Mass = 50: 50 paste was prepared.

(Paste 6)
The paste 1 is mixed with plate-like mica particles (diameter: 100 nm, aspect ratio: 6, hereinafter referred to as plate-like mica particles 1), and the mass of the plate-like mica particles 1: the mass of the paste 1 = 20: 80 paste. Was prepared.

(Paste 7)
The paste 1 is mixed with rod-like TiO ₂ particles (anatase, diameter: 30 nm, aspect ratio: 6.3, hereinafter referred to as rod-like TiO ₂ particles 2), the mass of the rod-like TiO ₂ particles 2: the mass of the paste 1 = 30: 70 pastes were prepared.

(Paste 8)
The paste 1 is mixed with rod-like TiO ₂ particles (anatase, diameter: 50 nm, aspect ratio: 6.1, hereinafter referred to as rod-like TiO ₂ particles 3), and the mass of the rod-like TiO ₂ particles 3: the mass of the paste 1 = 30. : 70 paste was prepared.

(Paste 9)
The paste 1 is mixed with rod-like TiO ₂ particles (anatase, diameter: 75 nm, aspect ratio: 5.8, hereinafter referred to as rod-like TiO ₂ particles 4), and the mass of the rod-like TiO ₂ particles 4: the mass of the paste 1 = 30. : 70 paste was prepared.

(Paste 10)
The paste 1 is mixed with rod-like TiO ₂ particles (anatase, diameter: 130 nm, aspect ratio: 5.2, hereinafter referred to as rod-like TiO ₂ particles 5), and the mass of the rod-like TiO ₂ particles 5: the mass of the paste 1 = 30. : 70 paste was prepared.

(Paste 11)
The paste 1 is mixed with rod-like TiO ₂ particles (anatase, diameter: 180 nm, aspect ratio: 5, hereinafter referred to as rod-like TiO ₂ particles 6), and the mass of the rod-like TiO ₂ particles 6: the mass of the paste 1 = 30: 70. A paste was prepared.

(Paste 12)
The paste 1 is mixed with rod-like TiO ₂ particles (anatase, diameter: 240 nm, aspect ratio: 5, hereinafter referred to as rod-like TiO ₂ particles 7), and the mass of the rod-like TiO ₂ particles 7: the mass of the paste 1 = 30: 70. A paste was prepared.

(Paste 13)
The paste 1 is mixed with rod-like TiO ₂ particles (anatase, diameter: 110 nm, aspect ratio: 4.1, hereinafter referred to as rod-like TiO ₂ particles 8), and the mass of the rod-like TiO ₂ particles 8: the mass of the paste 1 = 30. : 70 paste was prepared.

(Paste 14)
The paste 1 is mixed with rod-shaped TiO ₂ particles (anatase, diameter: 105 nm, aspect ratio: 3.4, hereinafter referred to as rod-shaped TiO ₂ particles 9), and the mass of the rod-shaped TiO ₂ particles 9: the mass of the paste 1 = 30. : 70 paste was prepared.

(Photoelectrochemical cell 1)
A photoelectrode having the same configuration as the photoelectrode 12 shown in FIG. 5 described in JP-A-2002-289274 is prepared by the following procedure, and further, using the photoelectrode, a dye-sensitized type other than the photoelectrode is used. A 10 × 10 mm scale photoelectrochemical cell 1 having the same configuration as that of the solar cell 20 was produced.

A transparent electrode in which a fluorine-doped SnO ₂ conductive film (film thickness: 500 nm) was formed on a glass substrate was prepared. Then, the paste 2 was screen-printed on the SnO ₂ conductive film and then dried. Then, it baked on the conditions of 450 degreeC in the air. Further, by repeating this screen printing and baking using the paste 4, a semiconductor electrode having the same configuration as the semiconductor electrode 2 shown in FIG. 5 on the SnO ₂ conductive film (area of light receiving surface; 10 mm × 10 mm, layer thickness) 10 μm, layer thickness of semiconductor layer; 6 μm, layer thickness of light scattering layer; 4 μm, content of rod-like TiO ₂ particles 1 contained in the light scattering layer; 30% by mass), containing sensitizing dye A photoelectrode was prepared.

Next, the pigment | dye was made to adsorb | suck to a semiconductor electrode as follows. First, anhydrous ethanol dehydrated with magnesium ethoxide was used as a solvent, and the dye of the present invention was dissolved therein so that the concentration thereof was 3 × 10 ⁻⁴ mol / L to prepare a dye solution. Next, the semiconductor electrode was immersed in this solution, thereby adsorbing about 1.5 mmol / m ² of the dye to the semiconductor electrode, and the photoelectrode 10 was completed.

  Next, a platinum electrode (thickness of Pt thin film; 100 nm) having the same shape and size as the above-described photoelectrode as a counter electrode, and an iodine redox solution containing iodine and lithium iodide as an electrolyte E were prepared. Furthermore, a spacer S (trade name: “Surlin”) manufactured by DuPont having a shape corresponding to the size of the semiconductor electrode is prepared. As shown in FIG. 3 of JP-A-2002-289274, the photoelectrode 10 and the counter electrode are prepared. The photoelectrochemical cell 1 was completed by facing the CE through the spacer S and filling the above electrolyte therein.

(Photoelectrochemical cell 2)
The photoelectrode 10 shown in FIG. 1 described in JP-A No. 2002-289274 and the diagram described in JP-A No. 2002-289274 are the same as those of the photoelectrochemical cell 1 except that the semiconductor electrode is manufactured as follows. A photoelectrode and a photoelectrochemical cell 2 having the same configuration as the dye-sensitized solar cell 20 shown in FIG.

Paste 2 was used as a semiconductor layer forming paste. Then, paste 2 was screen-printed on the SnO ₂ conductive film and then dried. Then, it baked on the conditions of 450 degreeC in the air, and formed the semiconductor layer.

  Paste 3 was used as the innermost layer forming paste of the light scattering layer. The paste 5 was used as the outermost layer forming paste of the light scattering layer. Then, a light scattering layer was formed on the semiconductor layer in the same manner as in the dye-sensitized solar cell 1.

Then, on the SnO ₂ conductive film, a semiconductor electrode having the same configuration as the semiconductor electrode 2 shown in FIG. 1 described in JP-A-2002-289274 (light receiving surface area: 10 mm × 10 mm, layer thickness: 10 μm, layer thickness of the semiconductor layer) 3 μm, the thickness of the innermost layer; 4 μm, the content of rod-like TiO ₂ particles 1 contained in the innermost layer; 10% by mass, the thickness of the outermost layer; 3 μm, contained in the innermost layer The content ratio of the rod-like TiO ₂ particles 1 to be formed; 50% by mass) was formed, and a photoelectrode containing no sensitizing dye was produced. Similarly to the photoelectrochemical cell 1, the photoelectrochemical cell 2 was completed by making the photoelectrode, the counter electrode CE, and the spacer S face each other and filling the above electrolyte therein.

(Photoelectrochemical cell 3)
The light shown in FIG. 5 was prepared by the same procedure as that of the photoelectrochemical cell 1 except that the paste 1 was used as the semiconductor layer forming paste and the paste 4 was used as the light scattering layer forming paste when the semiconductor electrode was manufactured. A photoelectrode and photoelectrochemical cell 3 having the same configuration as the electrode 10 and the photoelectrochemical cell 20 shown in FIG. 3 described in JP-A-2002-289274 were produced. The semiconductor electrode has a light receiving surface area of 10 mm × 10 mm, a layer thickness of 10 μm, a semiconductor layer thickness of 5 μm, a light scattering layer thickness of 5 μm, and the rod-like TiO ₂ particles 1 contained in the light scattering layer. Content rate: 30% by mass.

(Photoelectrochemical cell 4)
In the production of the semiconductor electrode, the light shown in FIG. 5 was obtained by the same procedure as that of the photoelectrochemical cell 1 except that the paste 2 was used as the semiconductor layer forming paste and the paste 6 was used as the light scattering layer forming paste. A photoelectrode and photoelectrochemical cell 4 having the same configuration as the electrode 10 and the photoelectrochemical cell 20 shown in FIG. 3 described in JP-A-2002-289274 were produced. The semiconductor electrode has a light receiving surface area: 10 mm × 10 mm, layer thickness: 10 μm, semiconductor layer thickness: 6.5 μm, light scattering layer thickness: 3.5 μm, plate-like contained in the light scattering layer The content of mica particles 1 was 20% by mass.

(Photoelectrochemical cell 5)
In the production of the semiconductor electrode, the photoelectrode and the photoelectrochemistry were prepared in the same procedure as in the photoelectrochemical cell 1 except that the paste 2 was used as the semiconductor layer forming paste and the paste 8 was used as the light scattering layer forming paste. Battery 5 was produced. The content ratio of the rod-shaped TiO ₂ particles 3 contained in the light scattering layer of the semiconductor electrode; was 30 wt%.

(Photoelectrochemical cell 6)
In the production of the semiconductor electrode, the photoelectrode and the photoelectrochemical process were performed in the same manner as in the photoelectrochemical cell 1 except that the paste 2 was used as the semiconductor layer forming paste and the paste 9 was used as the light scattering layer forming paste. A battery 6 was produced. The content ratio of the rod-shaped TiO ₂ particles 4 contained in the light scattering layer of the semiconductor electrode; was 30 wt%.

(Photoelectrochemical cell 7)
In the production of the semiconductor electrode, the photoelectrode and the photoelectrochemistry were prepared in the same procedure as in the photoelectrochemical cell 1 except that the paste 2 was used as the semiconductor layer forming paste and the paste 10 was used as the light scattering layer forming paste. Battery 7 was produced. The content ratio of the rod-shaped TiO ₂ particles 5 contained in the light scattering layer of the semiconductor electrode; was 30 wt%.

(Photoelectrochemical cell 8)
In the production of the semiconductor electrode, the photoelectrode and the photoelectrochemistry were prepared in the same procedure as in the photoelectrochemical cell 1 except that the paste 2 was used as the semiconductor layer forming paste and the paste 11 was used as the light scattering layer forming paste. Battery 8 was produced. The content ratio of the rod-shaped TiO ₂ particles 6 contained in the light scattering layer of the semiconductor electrode; was 30 wt%.

(Photoelectrochemical cell 9)
In the production of the semiconductor electrode, the photoelectrode and the photoelectrochemistry were prepared in the same procedure as in the photoelectrochemical cell 1 except that the paste 2 was used as the semiconductor layer forming paste and the paste 13 was used as the light scattering layer forming paste. A battery 9 was produced. The content ratio of the rod-shaped TiO ₂ particles 8 contained in the light scattering layer of the semiconductor electrode; was 30 wt%.

(Photoelectrochemical cell 10)
In the production of the semiconductor electrode, the photoelectrode and the photoelectrochemical process were performed in the same manner as in the photoelectrochemical cell 1 except that the paste 2 was used as the semiconductor layer forming paste and the paste 14 was used as the light scattering layer forming paste. Battery 10 was produced. The content of the rod-like TiO ₂ particles 9 contained in the light scattering layer of the semiconductor electrode was 30% by mass.

(Photoelectrochemical cell 11)
Similar to the photoelectrochemical cell 1 except that a semiconductor electrode (light-receiving surface area: 10 mm × 10 mm, layer thickness: 10 μm) made of only the semiconductor layer using only the paste 2 was manufactured in the manufacture of the semiconductor electrode. A photoelectrode and a comparative photoelectrochemical cell 1 were prepared according to the procedure.

(Electrochemical battery 12)
In the production of the semiconductor electrode, the photoelectrode and the comparative photoelectricity were prepared in the same procedure as in the photoelectrochemical cell 1 except that the paste 2 was used as the semiconductor layer forming paste and the paste 7 was used as the light scattering layer forming paste. A chemical battery 2 was produced. The content ratio of the rod-shaped TiO ₂ particles 2 contained in the light scattering layer of the semiconductor electrode; was 30 wt%.

[Battery characteristics test]
A battery characteristic test was performed, and conversion efficiency η was measured for photoelectrochemical cells 1 to 10 and comparative photoelectrochemical cells 1 and 2. The battery characteristic test was performed by irradiating 1000 W / m 2 of pseudo sunlight from a xenon lamp that passed through an AM1.5 filter using a solar simulator (manufactured by WACOM, WXS-85H). Current-voltage characteristics were measured using an IV tester, and energy conversion efficiency (η /%) was determined. The results are shown in Table 6. As a result, conversion efficiency of 5% or more is indicated as ◎, 2% or more and less than 5% as ◯, 0.5% or more and less than 2% as △, and less than 0.5% as x. .

  As shown in Table 6, it was found that the dye of the present invention has high conversion efficiency.

(Example 7)
A slurry obtained by adding metal alkoxide to metal oxide fine particles was applied to a conductive substrate, and then UV ozone irradiation, UV irradiation or drying was performed to produce an electrode. Then, the photoelectrochemical cell was produced and the conversion efficiency was measured.

(Metal oxide fine particles)
Titanium oxide was used as the metal oxide fine particles. As the titanium oxide, P25 powder (trade name, manufactured by Degussa) having a mass ratio of 30% rutile type and 70% anatase type and an average particle size of 25 nm was used.

(Pretreatment of metal oxide fine particle powder)
The metal oxide fine particles were previously heat-treated to remove surface organic substances and moisture. In the case of titanium oxide fine particles, the fine particles were heated in an oven at 450 ° C. in the atmosphere for 30 minutes.

(Measurement of water content in metal oxide fine particles)
When the moisture content contained in titanium oxide and P25 powder (trade name, manufactured by Degussa) stored in an environment of temperature 26 ° C. and humidity 72% is reduced by thermogravimetry and heated to 300 ° C. The amount of moisture desorbed was determined by Karl Fischer titration.

  When the amount of water desorbed when titanium oxide, P25 powder (trade name, manufactured by Degussa) was heated at 300 ° C. was quantified by Karl Fischer titration, 0.253 mg of water was found in 0.1033 g of titanium oxide fine powder. It was included. That is, since the titanium oxide fine powder contained about 2.5 wt% of water, the metal oxide fine particle powder was heat-treated in an oven at 450 ° C. for 30 minutes before mixing with the metal alkoxide, and stored in a desiccator after cooling. Used.

(Preparation of metal alkoxide paste)
The metal alkoxide that plays a role in bonding metal oxide fine particles includes titanium (IV) tetraisopropoxide (TTIP) as a titanium raw material, zirconium (IV) tetra n-propoxide as a zirconium raw material, and niobium as a niobium raw material. (V) Pentaethoxide (all manufactured by Aldrich) was used.

The molar concentration ratio between the metal oxide fine particles and the metal alkoxide is appropriately adjusted according to the metal oxide fine particle diameter so that the amorphous layer generated by hydrolysis of the metal alkoxide is not excessively thick and the particles can be sufficiently bonded to each other. did. All metal alkoxides were 0.1M ethanol solutions. When mixing titanium oxide fine particles and titanium (IV) tetraisopropoxide (TTIP), 3.55 g of 0.1M TTIP solution was mixed with 1 g of titanium oxide fine particles. At this time, the titanium oxide concentration in the obtained paste was about 22% by mass, and the viscosity was appropriate for coating. Moreover, the titanium oxide, TTIP, and ethanol at this time were 1: 0.127: 3.42 by mass ratio, and 1: 0.036: 5.92 by molar ratio.
Similarly, a mixed paste of titanium oxide fine particles and an alkoxide other than TTIP was prepared so that the fine particle concentration was 22% by mass. In the paste using zinc oxide and tin oxide fine particles, the content was 16% by mass. In the case of zinc oxide and tin oxide, the metal alkoxide solution was mixed at a ratio of 5.25 g to 1 g of the metal oxide fine particles.

The metal oxide fine particles and the metal alkoxide solution were stirred for 2 hours with a magnetic stirrer in a sealed container to obtain a uniform paste.
As a method for applying the paste to the conductive substrate, a doctor blade method, a screen printing method, a spray coating method, or the like can be used, and an appropriate paste viscosity is appropriately selected depending on the application method. Here, a method of applying simply with a glass rod (similar to the doctor blade method) was used. In this case, the concentration of the metal oxide fine particles giving an appropriate paste viscosity was approximately in the range of 5 to 30% by mass.

  In this embodiment, the layer thickness of the amorphous metal oxide produced by the decomposition of the metal alkoxide is in the range of about 0.1 to 0.6 nm. A range of about 0.05 to 1.3 nm was suitable for room temperature film formation by this method.

(Applying paste on conductive substrate and air-drying treatment)
Two adhesive tapes as spacers on a polyethylene terephthalate (PET) film substrate (20Ω / cm ² ) with tin-doped indium oxide (ITO) conductive film or a glass substrate (10Ω / cm ² ) with fluorine-doped tin oxide (FTO) conductive film The pastes were applied in parallel at regular intervals, and each paste prepared according to the above method was uniformly applied using a glass rod.

After applying the paste and before dye adsorption, a porous film was prepared by changing the conditions for the presence or absence of UV ozone treatment, UV irradiation treatment, or drying treatment.
(Drying process)
The film after application to the conductive substrate was air-dried at room temperature in the atmosphere for about 2 minutes. During this process, the metal alkoxide in the paste was hydrolyzed by moisture in the atmosphere, and amorphous titanium oxide, zirconium oxide, and niobium oxide were formed from Ti alkoxide, Zr alkoxide, and Nb alkoxide, respectively.
Since the produced amorphous metal oxide plays a role of adhering metal oxide fine particles and the film to the conductive substrate, a porous film excellent in mechanical strength and adhesion was obtained only by air drying.

(UV ozone treatment)
NL-UV253 UV ozone cleaner manufactured by Nippon Laser Electronics Co., Ltd. was used for the UV ozone treatment. The UV light source was equipped with three 4.5 W mercury lamps having emission lines at 185 nm and 254 nm, and the sample was placed horizontally at a distance of about 6.5 cm from the light source. Ozone is generated by introducing an oxygen stream into the chamber. In this example, this UV ozone treatment was performed for 2 hours. Note that no decrease in the conductivity of the ITO film and the FTO film due to this UV ozone treatment was observed.

(UV treatment)
Similarly to the UV ozone treatment, the treatment was performed for 2 hours, except that the inside of the chamber was replaced with nitrogen. No decrease in the conductivity of the ITO film and FTO film due to the UV treatment was observed.

(Dye adsorption)
The dye of the present invention was used as a sensitizing dye, and a 0.5 mM ethanol solution was prepared. In this example, the porous film produced by the above process was dried in an oven at 100 ° C. for 1 hour, then immersed in a sensitizing dye solution, and allowed to stand at room temperature for 50 minutes to adsorb the sensitizing dye on the titanium oxide surface. did. The sample after adsorption of the sensitizing dye was washed with ethanol and air-dried.

(Production of photoelectrochemical cell and evaluation of battery characteristics)
A photoelectrochemical cell was fabricated by using a conductive substrate on which a porous film after dye adsorption was formed as a photoelectrode, and an ITO / PET film or FTO / glass counter electrode in which platinum fine particles were modified by sputtering. The effective area of the photoelectrode was about 0.2 cm ² . As the electrolyte solution, 3-methoxypropionitrile containing 0.5 M LiI, 0.05 M I ₂ and 0.5 M t-butylpyridine was introduced into the gap between the two electrodes by capillary action.

The battery performance was evaluated by photocurrent action spectrum measurement under irradiation with a constant number of photons (1016 cm ⁻² ) and IV measurement under irradiation with AM1.5 simulated sunlight (100 mW / cm ² ). A CEP-2000 type spectral sensitivity measuring device manufactured by Spectrometer Co., Ltd. was used for these measurements.
The obtained output characteristic values are summarized in Table 7. As a result, conversion efficiency of 3% or more was indicated as ◎, 2% or more and less than 5% as ◯, 0.5% or more and less than 2% as △, and less than 0.5% as x. .

In Table 7, the columns of “UV ozone”, “UV”, and “dry” indicate the presence / absence of UV ozone treatment, UV irradiation treatment, and drying treatment after formation of the porous film and before sensitizing dye adsorption, respectively. The processed one is “◯”, and the unprocessed one is “×”.
The column of _“ Pretreatment of TiO ₂ ” in Table 7 indicates the presence or absence of pretreatment of titanium oxide fine particles (heat treatment in an oven at 450 ° C. for 30 minutes). Samples 6, 14, and 22 represent samples using a paste having a high TTIP concentration (titanium oxide: TTIP molar ratio of 1: 0.356). The other samples (samples 1 to 5, 7 to 13, 23, 24) all use a paste of titanium oxide: TTIP = 1: 0.0356.

  From the results shown in Table 7, when the dye of the present invention is used, the photoelectricity is measured regardless of the presence or absence of UV ozone treatment, UV irradiation treatment, and drying treatment after the formation of the porous film and before adsorption of the sensitizing dye. It was found that the conversion efficiency of the chemical battery was high.

(Example 8)
Using acetonitrile as a solvent, an electrolyte solution was prepared in which lithium iodide 0.1 mol / l, iodine 0.05 mol / l, and dimethylpropylimidazolium iodide 0.62 mol / l were dissolved. No. shown below. 1-No. 8 benzimidazole compounds were separately added and dissolved to a concentration of 0.5 mol / l.

A conductive film was formed on a glass substrate by sputtering tin oxide doped with fluorine as a transparent conductive film. Dispersion liquid containing anatase-type titanium oxide particles on this conductive film (
Mixing 32g of anatase-type titanium oxide (P-25 (trade name) manufactured by Nippon Aerosil Co., Ltd.) with 100ml of a mixed solvent consisting of water and acetonitrile in a volume ratio of 4: 1 and using a rotating / revolving mixing conditioner A semiconductor fine particle dispersion obtained by uniformly dispersing and mixing was applied, and then sintered at 500 ° C. to form a photosensitive layer having a thickness of 15 μm. In this photosensitive layer, no. 1-No. 8 benzimidazole compound electrolyte was added dropwise.
A frame type spacer (thickness: 25 μm) made of a polyethylene film was placed thereon, and this was covered with a platinum counter electrode to produce a photoelectric conversion element.
The obtained photoelectric conversion element was irradiated with light having an intensity of 100 mW / cm ^{2 using} a Xe lamp as a light source. Table 8 shows the open circuit voltage and photoelectric conversion efficiency obtained. The open-circuit voltage is indicated as ◎ for those with 7.0 V or higher, ◯ for those with 6.5 V or more but less than 7.0 V, Δ for those with 6.0 V or more and less than 6.5 V, and “X” with less than 6.0 V. . A conversion efficiency of 3% or more was indicated as ◎, 2% or more and less than 5% as 未 満, 0.5% or more and less than 2% as Δ, and less than 0.5% as ×.
Table 8 also shows the results of photoelectric conversion elements using an electrolytic solution to which no benzimidazole compound was added.

  From the results in Table 8, it can be seen that the dye of the present invention has high conversion efficiency.

Example 9
(Photoelectrochemical cell 1)
According to the following procedure, a photoelectrode having the same configuration as the photoelectrode 10 shown in FIG. 1 described in JP-A No. 2004-152613 (however, the semiconductor electrode 2 has a two-layer structure) is manufactured. A photoelectrochemical cell having the same configuration as the dye-sensitized solar cell 20 shown in FIG. 1 described in JP-A-2004-152613 except that a photoelectrode is used (the area of the light receiving surface F2 of the semiconductor electrode 2 is 1 cm ² ). Was made. For each layer of the semiconductor electrode 2 having a two-layer structure, the layer disposed on the side close to the transparent electrode 1 is referred to as “first layer”, and the layer disposed on the side close to the porous body layer PS is referred to as “second layer”. It is called “layer”.

  First, P25 powder having an average particle diameter of 25 nm (trade name, manufactured by Degussa), titanium oxide particles having a different particle diameter, and P200 powder (average particle diameter: 200 nm, product name, manufactured by Degussa) were used. And P200 are 15% by mass, and the mass ratio of P25 and P200 is P25: P200 = 30: 70, so that acetylacetone, ion-exchanged water, surfactant (manufactured by Tokyo Chemical Industry Co., Ltd.) , Trade name: “Triton-X”) and kneaded to prepare a slurry for forming a second layer (hereinafter referred to as “slurry 1”).

  Next, a slurry for forming a first layer (P1 content; 15 mass%; hereinafter, “slurry 2” is prepared by the same preparation procedure as that of the slurry 1 except that only P25 is used without using P200. Was prepared).

On the other hand, a transparent electrode (thickness: 1.1 mm) in which a fluorine-doped SnO ₂ conductive film (film thickness: 700 nm) was formed on a glass substrate (transparent conductive glass) was prepared. Then, the SnO ₂ conductive film, the slurry 2 described above was coated with Bakoda, then dried. Then, it baked for 30 minutes at 450 degreeC in air | atmosphere. In this way, the first layer of the semiconductor electrode 2 was formed on the transparent electrode.

Furthermore, the second layer was formed on the first layer by repeating the same application and firing as described above using the slurry 1. In this way, the semiconductor electrode 2 (light-receiving surface area; 1.0 cm ² , the total thickness of the first layer and the second layer: 10 μm (the thickness of the first layer: 3 μm, the first layer) on the SnO ₂ conductive film No. 2 layer thickness: 7 μm)), and a photoelectrode 10 containing no sensitizing dye was prepared.

Next, an ethanol solution of the dye of the present invention (sensitizing dye concentration; 3 × 10 ⁻⁴ mol / L) was prepared as a sensitizing dye. The photoelectrode 10 was immersed in this solution and allowed to stand for 20 hours under a temperature condition of 80 ° C. to adsorb the sensitizing dye. Thereafter, in order to improve the open circuit voltage Voc, the semiconductor electrode after dye adsorption was immersed in an acetonitrile solution of 4-tert-butylpyridine for 15 minutes, and then dried in a nitrogen stream kept at 25 ° C., and the photoelectrode 10 Was completed.

  Next, a counter electrode CE having the same shape and size as the above photoelectrode was produced. First, an isopropanol solution of chloroplatinic acid hexahydrate was dropped on a transparent conductive glass, dried in air, and then baked at 450 ° C. for 30 minutes to obtain a platinum sintered counter electrode CE. The counter electrode CE was previously provided with a hole for injection of the electrolyte E (diameter 1 mm).

  Next, zinc iodide, 1,2-dimethyl-3-propylimidazolium iodide, iodine, and 4-tert-butylpyridine are dissolved in methoxyacetonitrile as a solvent to form a liquid electrolyte (iodide). Zinc concentration: 10 mmol / L, dimethylpropylimidazolium iodide concentration: 0.6 mol / L, iodine concentration: 0.05 mol / L, 4-tert-butylpyridine concentration: 1 mol / L).

  Next, a spacer S (trade name: “HIMILAN”, ethylene / methacrylic acid random copolymer ionomer film) manufactured by Mitsui Dupont Polychemical Co., Ltd. having a shape matched to the size of the semiconductor electrode was prepared. As shown in FIG. 1 described in 15613, the photoelectrode and the counter electrode were opposed to each other through a spacer, and each was bonded by thermal welding to obtain a battery casing (no electrolyte filled).

  Next, after injecting the liquid electrolyte into the housing from the hole of the counter electrode, the hole is closed with a member made of the same material as the spacer, and this member is thermally welded to the hole of the counter electrode to seal the hole. 1 was completed.

(Photoelectrochemical cell 2)
The photoelectrochemical cell 2 was produced in the same procedure and conditions as the photoelectrochemical cell 1 except that the concentration of zinc iodide in the liquid electrolyte was 50 mmol / L.

(Photoelectrochemical cell 3)
Comparative photoelectrochemistry was performed in the same procedure and conditions as in the photoelectrochemical cell 1 except that lithium iodide was added instead of zinc iodide in the liquid electrolyte, and the concentration of lithium iodide in the liquid electrolyte was 20 mmol / L. A battery 1 was produced.

(Electrochemical battery 4)
Comparative photoelectrochemistry in the same procedure and conditions as in the photoelectrochemical cell 1 except that lithium iodide was added instead of zinc iodide in the liquid electrolyte, and the concentration of lithium iodide in the liquid electrolyte was 100 mmol / L. Battery 2 was produced.

(Battery characteristics evaluation test)
The photoelectric conversion efficiency (η (%)) of the photoelectrochemical cells 1 and 2 and the comparative electrochemical cells 1 and 2 was measured by the following procedure.

The battery characteristic evaluation test uses a solar simulator (trade name; “WXS-85-H type”, manufactured by Wacom), and the irradiation conditions of pseudo-sunlight from a xenon lamp light source through an AM filter (AM1.5), The measurement was performed under measurement conditions of 100 mW / cm ² (so-called “1Sun” irradiation conditions).

  About each photoelectrochemical cell, the current-voltage characteristic was measured at room temperature using the IV tester, and photoelectric conversion efficiency (eta) [%] was calculated | required from these. The obtained results are shown as “fresh” in Table 9 (1 Sun irradiation conditions). In addition, the photoelectric conversion efficiency η [%] of the dye-sensitized solar cells 1 and 2 and the comparative dye-sensitized solar cells 1 and 2 was examined after 300 hours with the operation condition of 60 ° C., 1 Sun irradiation and 10Ω load. The results of the durability evaluation test are also shown in Table 9.

  As is apparent from the results shown in Table 9, the dye of the present invention was found to be excellent even when zinc iodide was added to the electrolyte.

(Example 10)
1. Preparation of Titanium Dioxide Dispersion 15 g of titanium dioxide fine particles (Nippon Aerosil Co., Ltd., Degussa P-25), 45 g of water, dispersant (Triron X, manufactured by Aldrich Co., Ltd.) −100) 1 g and 30 g of zirconia beads having a diameter of 0.5 mm (manufactured by Nikkato Co., Ltd.) were added, and dispersion treatment was performed at 1500 rpm for 2 hours using a sand grinder mill (manufactured by Imex). Zirconia beads were filtered off from the resulting dispersion. The average particle diameter of the titanium dioxide fine particles in the obtained dispersion was 2.5 μm. The particle size was measured with a master sizer manufactured by MALVERN.

2. Production of Titanium Oxide Fine Particle Layer (Electrode A) Adsorbed with Dye 20 mm × 20 mm conductive glass plate coated with fluorine-doped tin oxide (Asahi Glass Co., Ltd., TCO glass-U, surface resistance: about 30Ω / m ² ) was prepared, and an adhesive tape for spacers was applied to both ends (a portion having a width of 3 mm from the end) on the conductive layer side, and then the dispersion was applied onto the conductive layer using a glass rod. After application of the dispersion, the adhesive tape was peeled off and air-dried at room temperature for 1 day. Next, this semiconductor-coated glass plate was placed in an electric furnace (muffle furnace FP-32 type manufactured by Yamato Scientific Co., Ltd.) and baked at 450 ° C. for 30 minutes. The semiconductor-coated glass plate was taken out and cooled, and then immersed in an ethanol solution of the dyes shown in Table 10 (concentration: 3 × 10 ⁻⁴ mol / L) for 3 hours. The semiconductor-coated glass plate on which the dye was adsorbed was immersed in 4-tert-butylpyridine for 15 minutes, washed with ethanol, and air dried. The thickness of the dye-sensitized titanium oxide fine particle layer thus obtained was 10 μm, and the coating amount of the titanium oxide fine particles was 20 g / m ² . Moreover, the adsorption amount of the pigment | dye was in the range of 0.1-10 mmol / m < ² > according to the kind.

3. Production of Photoelectrochemical Battery Using the solvent shown in Table 1, a solution containing 0.5 mol / L electrolyte salt and 0.05 mol / L iodine was prepared. Nitrogen-containing polymer compound (1-1) was added to this solution at a mass composition ratio described in Table 10 (mass composition ratio when solvent + nitrogen-containing polymer compound + salt was 100 wt%). The electrophile (2-6) was mixed at the described molar ratio (molar ratio of the electrophilic site to the reactive nitrogen atom of the nitrogen-containing polymer compound) to obtain a uniform reaction solution.

On the other hand, on the dye-sensitized titanium oxide fine particle layer formed on the conductive glass plate, the platinum thin film side of the counter electrode made of a glass plate on which platinum is vapor-deposited through a spacer is placed. A glass plate was fixed. The open end of the obtained assembly was immersed in the electrolyte solution, and the reaction solution was infiltrated into the dye-sensitized titanium oxide fine particle layer by capillary action.
Subsequently, it heated at 80 degreeC for 30 minute (s), and the crosslinking reaction was performed. In this way, as shown in FIG. 2 of JP 2000-323190 A, the dye-sensitized titanium oxide fine particle layer 20, the electrolyte layer 30, the platinum thin film 42, and the glass are formed on the conductive layer 12 of the conductive glass plate 10. The photoelectrochemical cell 1-1 (sample No. 1) of the present invention in which the counter electrode 40 composed of the plate 41 was sequentially laminated was obtained.
Further, by repeating the above process except that the combination of the composition of the dye and the electrolyte composition is changed as shown in Table 10, photoelectrochemical cells 1-2, 1- having different photosensitive layers 20 and / or charge transfer layers 30 are obtained. 3 was obtained.

4). Production of photoelectrochemical cells A and B (1) Photoelectrochemical cell A
An electrode A (20 mm × 20 mm) composed of a titanium oxide fine particle layer dye-sensitized with the dye of the present invention as described above was superimposed on a platinum-deposited glass plate of the same size via a spacer. Next, using a capillary phenomenon in the gap between the two glass plates, an electrolyte (0.05 mol / L of iodine using a mixture of acetonitrile and 3-methyl-2-oxazolidinone in a volume ratio of 90/10 as a solvent, lithium iodide 0) .5 mol / L solution) was infiltrated to produce photoelectrochemical cell A-1. Photoelectrochemical cells A-2 and A-3 were obtained by repeating the above steps except that the dye was changed as shown in Table 10.

(2) Photoelectrochemical cell B (electrolyte described in JP-A-9-27352)
The electrolytic solution was applied and impregnated on the electrode A (20 mm × 20 mm) composed of the titanium oxide fine particle layer dye-sensitized with the dye of the present invention as described above. The electrolyte was 1 g of hexaethylene glycol methacrylate (manufactured by Nippon Oil & Fats Chemical Co., Ltd., Bremer PE-350), 1 g of ethylene glycol, and 2-hydroxy-2-methyl-1-phenyl-propane as a polymerization initiator. It was obtained by dissolving 500 mg of lithium iodide in a mixed solution containing 20 mg of -1-one (manufactured by Ciba Geigy Japan, Darocur 1173) and vacuum degassing for 10 minutes. Next, the porous titanium oxide layer impregnated with the mixed solution is placed under a reduced pressure to remove bubbles in the porous titanium oxide layer, promote penetration of the monomer, and then polymerize by irradiation with ultraviolet light. A uniform gel of the compound was filled into the fine pores of the porous titanium oxide layer. The product thus obtained was exposed to an iodine atmosphere for 30 minutes to diffuse iodine in the polymer compound, and then a platinum-deposited glass plate was overlaid to obtain a photoelectrochemical cell B-1. Photoelectrochemical cells B-2 and B-3 were obtained by repeating the above steps except that the dye was changed as shown in Table 10.

5. Measurement of photoelectric conversion efficiency Simulated sun which does not contain ultraviolet rays by passing light of 500W xenon lamp (made by USHIO INC.) Through AM1.5 filter (made by Oriel) and sharp cut filter (Kenko L-42) It was light. The light intensity was 89 mW / cm ² .

  Alligator clips were connected to the conductive glass plate 10 and the platinum-deposited glass plate 40 of the above-described photoelectrochemical cell, and each alligator clip was connected to a current-voltage measuring device (Keutley SMU238 type). This was irradiated with simulated sunlight from the conductive glass plate 10 side, and the generated electricity was measured with a current-voltage measuring device. Table 10 summarizes the initial value (fresh) of the conversion efficiency (η) of the photoelectrochemical cell determined in this way and the rate of decrease in conversion efficiency after 300 hours of continuous irradiation.

(Remarks)
(1) Symbols of pigments are as described in the text.
(2) Nitrogen-containing polymer 1-1 represents the following compound.

(3) Electrolyte salt MHIm: 1-methyl-3-hexylimidazolium iodine salt MBIm: 1-butyl-3-methylimidazolium iodine salt (4) Solvent AN: acetonitrile.
PC: Propylene carbonate.
NMO: 3-methyl-2-oxazolidinone.
(5) Electrophile

  As is clear from the results shown in Table 10, it was found that the dye of the present invention was excellent in conversion efficiency and durability even in this case.

DESCRIPTION OF SYMBOLS 1 Conductive support body 2 Photosensitive layer 21 Dye compound 22 Semiconductor fine particle 23 Electrolyte 3 Hole transport layer 4 Counter electrode 5 Photosensitive electrode 6 Circuit 10 Photoelectric conversion element

Claims (12)

A dye having a structure represented by the following general formula (1) in a molecule.

[In the general formula (1), X represents a nonmetallic atom group necessary for forming a seven-membered nitrogen-containing heterocycle by linking with a benzene ring. Y represents a dye residue, and n represents an integer of 1 or more. Z represents a substituent, and m represents 0 or a positive integer. When m is 2 or more, Z may be the same or different. R ¹ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group bonded with a carbon atom. ] 2. The dye according to claim 1, wherein the dye represented by the general formula (1) has a structure represented by the following general formula (2).

[In General Formula (2), X represents a nonmetallic atom group required in order to connect with a benzene ring and to form a seven-membered nitrogen-containing heterocyclic ring. R ¹ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group bonded with a carbon atom. R ^{2 to} R ⁹ represent a hydrogen atom or a substituent, and at least one of the substituents represents a dye residue represented by the general formula (3).
In General Formula (3), R ¹⁰ , R ¹¹ , and R ¹³ each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. r represents an integer of 0 or more. The carbon-carbon double bond in general formula (3) may be either E-type or Z-type. R ¹² represents a group having at least one acidic group or an acidic nucleus. ] The dye according to claim 1 or 2, wherein the dye having a structure represented by the general formula (1) or the general formula (2) is represented by the following general formula (4).

[In the general formula ^{(4), R 1 ~R 3} , R 5 ~R 13 are each synonymous with ^{R 1 ~R 3, R 5 ~R} 13 in the general formula (2) and the general formula (3). ] The dye according to claim 1 or 2, wherein the dye having the structure represented by the general formula (1) or the general formula (2) is represented by the following general formula (5).

[In the general formula ^(5), R 1 ^{to R 13} are the same meanings as ^R 1 ^{to R 13} in the general formula (2) and the general formula (3).
In the general formula (5), R ¹⁴ represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, or a heterocyclic group. ] The dye according to claim 1 or 2, wherein the dye having the structure represented by the general formula (1) or (2) is represented by the following general formula (6).

[In the general formula ^{(6), R 1 ~R 3} , R 5, R 6, R 8 ~R 13 is, ^R 1 ^{to R} 3, respectively, in the general formula (2) and the general formula ^{(3), R 5, R 6} , which is synonymous with R ^{8 to} R ¹³ . ] The dye according to any one of claims 2 to 5, wherein R ¹² is represented by the following general formula (7) or general formula (8).

[In the general formula (7), R ¹⁵ and R ¹⁶ are each independently an aliphatic group, an aromatic group or a heterocyclic group (at least one functional group may have an acidic group). l represents 0 or 1; The carbon-carbon double bond in the general formula (7) may be either E-type or Z-type. R ¹⁷ in general formula (7) represents a sulfur atom or general formula (9), and the carbon-carbon double bond in general formula (9) may be either E-type or Z-type.
R ¹⁸ and R ¹⁹ in the general formula (8) each independently represent a cyano group or an acidic group, and may be the same as or different from each other. The carbon-carbon double bond in the general formula (8) may be either E type or Z type.
R ²⁰ and R ²¹ in the general formula (9) each independently represent a cyano group or an acidic group, and may be the same or different from each other. The carbon-carbon double bond in the general formula (9) may be any of E type and Z type. ] The dye according to claim 6, wherein the general formula (7) is represented by the following general formula (10).

[In the general formula (10), R ¹⁶ is an aliphatic group, an aromatic group or a heterocyclic group (may have an acidic group)]. The dye according to any one of claims 2 to 5, wherein R ¹² is represented by the following general formula (11).

[In the general formula (11), R ¹⁵ is an aliphatic group, an aromatic group or a heterocyclic group (may have an acidic group)]. The dye according to any one of claims 2 to 5, wherein R ¹² is represented by the following general formula (12).

  A photoelectric conversion element, wherein the light-receiving electrode contains semiconductor fine particles sensitized by the dye according to claim 1.   The photoelectric conversion element according to claim 10, further comprising an insulating porous body between the light receiving electrode and the counter electrode.   A photoelectrochemical cell comprising the photoelectric conversion device according to claim 10.

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