JP2013030320A - Photoelectric conversion element, photoelectrochemical cell, and dye for use therein - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a photoelectric conversion element and a photoelectrochemical cell that exhibit high IPCE in a long-wavelength region, achieve high photoelectric conversion efficiency, and moreover excel in durability; and a dye for use therein.SOLUTION: A photoelectric conversion element comprises a layer structure including, on a conductive substrate, a photoreceptor that has a layer of semiconductor fine particles on which dyes have been adsorbed, a charge-transfer body, and a counter electrode. At least one of the dyes has a structure represented by the following formula (1). (In the formula, Q represents an aromatic ring. Xand Xrepresent sulfur atoms, selenium atoms, oxygen atoms, or CRR. Rand Rrepresent alkyl groups. R and R' are alkyl groups or aromatic groups. Prepresents a specific group of atoms, and Prepresents a group of atoms necessary to form a polymethine dye, while Pand Pare different from one another. Wrepresents a counter ion, where necessary to neutralize charge.)

Description

  The present invention relates to a photoelectric conversion element, a photoelectrochemical cell, and a dye used for them, which have high conversion efficiency and excellent durability.

  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, a solar cell using non-depleting solar energy does not require fuel, and its full-scale practical use is expected as an inexhaustible clean energy. Among these, silicon solar cells have been researched and developed for a long time. It is spreading due to the policy considerations of each country. However, silicon is an inorganic material, and its throughput and molecular modification are naturally limited.

  Therefore, research on dye-sensitized solar cells has been vigorously conducted. In particular, it was the result of research by Graetzel of Lausanne University of Technology in Switzerland. They adopted a structure in which a dye composed of a ruthenium complex was fixed on the surface of a porous titanium oxide thin film, realizing conversion efficiency comparable to that of amorphous silicon. As a result, dye-sensitized solar cells have attracted a great deal of attention from researchers around the world.

  Patent Document 1 describes a dye-sensitized photoelectric conversion element using semiconductor fine particles sensitized with a ruthenium complex dye by applying this technique. However, although conventional ruthenium complex dyes can be photoelectrically converted using visible light, they can hardly absorb infrared light having a wavelength longer than 700 nm, and thus the photoelectric conversion ability in the infrared region tends to be low. In addition, it is desired for the spread that photovoltaic power generation is performed without using only an expensive rare metal such as ruthenium.

  Therefore, research on photoelectric conversion elements using dyes other than metal complexes is also underway. The present applicant has previously developed a device using a specific polymethine dye (see Patent Document 2). Thereby, the element which shows a high photoelectric conversion characteristic in a near infrared ray-infrared region was completed. Furthermore, Patent Document 3 discloses that high photoelectric conversion efficiency is achieved in a long wavelength region of 600 nm or longer by using an asymmetric bis-squarylium dye.

US Pat. No. 5,463,057 Japanese Patent No. 4217320 JP 2009-242379 A

By the technique of the said patent document 2 etc., the element which can achieve the high photoelectric conversion efficiency using a wide wavelength range, without making a metal complex essential. However, the present inventor has looked to play a role as a full-fledged supply source of green energy, and has aimed to develop a photoelectric conversion element that exhibits even higher performance without being sufficient in performance.
In view of the present state of the present technical field, the present invention exhibits high IPCE (Incident Photon to Current Conversion Efficiency) in a wavelength region exceeding 800 nm, achieves high photoelectric conversion efficiency, and is durable. An object is to provide an excellent photoelectric conversion element, a photoelectrochemical battery, and a dye used in them.

The above problem has been solved by the following means.
(1) A photoelectric conversion element having a laminate structure including a semiconductor fine particle layer adsorbed with a dye on a conductive support, a charge transfer body, and a counter electrode, wherein at least one of the dyes Is a photoelectric conversion element having a structure represented by the following formula (1).

（式中、Ｑは芳香環を表す。Ｘ^１、Ｘ^２は硫黄原子、セレン原子、酸素原子、またはＣＲ^１Ｒ^２を表す。Ｒ^１、Ｒ^２はアルキル基を表す。Ｒ、Ｒ’はアルキル基または芳香族基である。Ｐ^１は下記式Ｐ１１または下記式Ｐ１２で表される原子群を表す。Ｐ^２はポリメチン色素を形成するのに必要な原子群を表す。ただし、Ｐ^１とＰ^２とは異なるものとする。Ｗ^１は電荷を中和させるのに必要な場合の対イオンを表す。）

(In the formula, Q represents an aromatic ring. X ¹ and X ² represent a sulfur atom, a selenium atom, an oxygen atom, or CR ¹ R ^2. R ¹ and R ² represent an alkyl group. R and R ′ represent An alkyl group or an aromatic group, P ¹ represents an atomic group represented by the following formula P11 or P12, and P ² represents an atomic group necessary for forming a polymethine dye, provided that P ¹ and (It is different from P ^2. W ¹ represents a counter ion as necessary to neutralize the charge.)

（式中、Ｒ^５、Ｒ^６、Ｒ^１０、Ｒ^１１は、酸性基を有することがある脂肪族基、又は酸性基を有することがある芳香環基を表す。Ｒ^７、Ｒ^１２は硫黄原子または下記式Ｒ^Ａを表す。Ｒ^３、Ｒ^４、Ｒ^８は水素原子又は置換基を表す。Ｒ^９は酸素原子又は置換基を表す。ｎ２１は０以上の整数を表す。ｎ２２、ｎ３１は０又は１を示す。）

^{(Wherein, R 5, R 6, R} 10, R 11 are, ^{.R 7, R 12} is sulfur atom represents an aromatic ring group which may have an aliphatic group, or an acidic group which may have an acidic group or ^.R 3 representing the formula ^{R a, R 4, R 8} is .R ⁹ represents a hydrogen atom or a substituent represents .n21 is an integer of 0 or more representing an oxygen atom or a substituent .N22, is n31 0 Or 1)

（式Ｒ^ＡにおけるＲ^１３、Ｒ^１４はシアノ基又は酸性基を表す。）
（２）前記Ｐ^１が下記式Ｐ１１−１またはＰ１２−１である（１）記載の光電変換素子。

(R ¹³ and R ¹⁴ in the formula R ^A represent a cyano group or an acidic group.)
(2) The photoelectric conversion element according to (1), wherein the P ¹ is the following formula P11-1 or P12-1.

（式中、Ｒ^３、Ｒ^４、Ｒ^６、Ｒ^８、Ｒ^９、Ｒ^１１、ｎ^２１は、式Ｐ１１，Ｐ１２と同義である。）
（３）前記ｎ２２、ｎ３１が０である（１）又は（２）に記載の光電変換素子。
（４）前記Ｐ^１が下式Ｐ１１−２またはＰ１２−２で表される（１）又は（３）に記載の光電変換素子。

(In the formula, R ³ , R ⁴ , R ⁶ , R ⁸ , R ⁹ , R ¹¹ , and n ²¹ are synonymous with formulas P11 and P12.)
(3) The photoelectric conversion element according to (1) or (2), wherein n22 and n31 are 0.
(4) The photoelectric conversion element according to (1) or (3), wherein the P ¹ is represented by the following formula P11-2 or P12-2.

（式中、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^８、Ｒ^９、Ｒ^１０、ｎ^２１は、Ｐ１１、Ｐ１２と同義である。）
（５）前記ｎ２１が０または１である（１）〜（４）のいずれか１項に記載の光電変換素子。
（６）前記Ｒ^９が下記式Ｒ９１又はＲ９２で表される（１）〜（５）のいずれか１項に記載の光電変換素子。

(In the formula, R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ , R ¹⁰ , and n ²¹ have the same meanings as P11 and P12.)
(5) The photoelectric conversion element according to any one of (1) to (4), wherein the n21 is 0 or 1.
(6) The photoelectric conversion element according to any one of (1) to (5), wherein R ⁹ is represented by the following formula R91 or R92.

（式Ｒ９２中、Ｒ^１５は水素原子もしくはアルキル基を表す。）
（７）前記Ｒ^９が酸素原子ある（１）〜（５）のいずれか１項に記載の光電変換素子。
（８）前記Ｐ^２を形成する原子群が下記式Ｐ２１または下記式Ｐ２２で表される（１）〜（７）のいずれか１項に記載の光電変換素子。

(In the formula R92, R ¹⁵ represents a hydrogen atom or an alkyl group.)
(7) The photoelectric conversion element according to any one of (1) to (5), wherein R ⁹ is an oxygen atom.
(8) The photoelectric conversion element according to any one of (1) to (7), wherein an atomic group forming the P ² is represented by the following formula P21 or the following formula P22.

（式中、Ｒ^２１、Ｒ^２２、Ｒ^２３は水素原子又は置換基を表す。Ａｒ^１は、Ｈａｍｍｅｔｔ則におけるσｐ値が０以下の置換基又はπ過剰系複素環基を有する芳香環基を表す。ｎ４１は０以上の整数を表す。）
（９）前記Ａｒ^１が下記式Ｒ^Ｃ１、Ｒ^Ｃ２、又はＲ^Ｃ３で表される（１）〜（８）のいずれか１項に記載の光電変換素子。

(In the formula, R ²¹ , R ²² and R ²³ represent a hydrogen atom or a substituent. Ar ¹ represents a substituent having a σp value of 0 or less in Hammett's rule or an aromatic ring group having a π-excess heterocyclic group. N41 represents an integer of 0 or more.)
(9) The photoelectric conversion element according to any one of (1) to (8), wherein Ar ¹ is represented by the following formula R ^C1 , R ^C2 , or R ^C3 .

（式Ｒ^Ｃ１〜Ｒ^Ｃ４中、ＹはＳ、ＮＲ^２４、またはＣ（Ｒ^２５）_２を表す。Ｒ^２４はアルキル基を表す。Ｒ^２５は置換基を表す。Ａは芳香環を表す。Ｒ^２６〜Ｒ^２９は水素原子もしくは置換基を表す。ＥはＳ、ＮＲ^３０、Ｏを表す。Ｒ^３０はアルキル基を表す。ＤはＨａｍｍｅｔｔ則におけるσｐ値が０以下の置換基を表す。Ｂは芳香環を表す。Ｘは−ＳＲ^ｅ、−ＯＲ^ｅ、−ＮＲ^ｅ _２を表し、Ｒ^ｅはアルキル基、芳香族基、ヘテロ環基を表す。Ｒ^ｄは置換基を表す。ｎｄは０〜４の整数を表す。＊は結合手を表し、式Ｐ２１及び式Ｐ２２でみて、メチン鎖を介して連結しても、二重結合になって直接連結されてもよい。ｋは正の整数である。）
（１０）前記式（１）で表される色素において、前記Ｐ^１が電子のアクセプターをなし、Ｐ^２がドナーをなし、該色素がドナー・アクセプター型の分子を構成している（１）〜（９）のいずれか１項に記載の光電変換素子。
（１１）前記感光体が下記式（Ｉ）で表される色素をさらに有する（１）〜（１０）のいずれか１項に記載の光電変換素子。
Ｍｚ（ＬＬ^１）_ｍ１（ＬＬ^２）_ｍ２（Ｘ）_ｍ３・ＣＩ ： 式（Ｉ）
［式（Ｉ）において、Ｍｚは金属原子を表す。ＬＬ^１は下記式ＬＬ１で表される２座の配位子を表す。ＬＬ^２は下記式ＬＬ２で表される２座又は３座の配位子を表す。Ｘは１座又は２座の配位子を表す。ｍ１は０〜３の整数を表す。ｍ２は１〜３の整数を表す。ｍ３は０〜２の整数を表す。ＣＩは電荷を中和させるのに対イオンが必要な場合の対イオンを表す。］

(In the formulas R ^{C1 to} R ^C4 , Y represents S, NR ²⁴ , or C (R ²⁵ ) _2. R ²⁴ represents an alkyl group, R ²⁵ represents a substituent, and A represents an aromatic ring. ^{26 to} R ²⁹ each represents a hydrogen atom or a substituent, E represents S, NR ³⁰ , or O. R ³⁰ represents an alkyl group, D represents a substituent having a σp value of 0 or less in Hammett's rule, and B represents Represents an aromatic ring, X represents —SR ^e , —OR ^e , —NR ^e ₂ , R ^e represents an alkyl group, an aromatic group, or a heterocyclic group, R ^d represents a substituent, and nd represents 0 to 0. Represents an integer of 4. * represents a bond, and may be linked via a methine chain or directly linked as a double bond as seen in Formulas P21 and P22, k is a positive integer is there.)
(10) In the dye represented by the formula (1), the P ¹ serves as an electron acceptor, the P ² serves as a donor, and the dye constitutes a donor-acceptor type molecule. The photoelectric conversion element according to any one of (9).
(11) The photoelectric conversion element according to any one of (1) to (10), wherein the photoreceptor further has a dye represented by the following formula (I).
Mz (LL ¹ ) _m1 (LL ² ) _m2 (X) _m3 · CI: Formula (I)
[In Formula (I), Mz represents a metal atom. LL ¹ represents a bidentate ligand represented by the following formula LL1. LL ² represents a bidentate or tridentate ligand represented by the following formula LL2. X represents a monodentate or bidentate ligand. m1 represents an integer of 0 to 3. m2 represents an integer of 1 to 3. m3 represents an integer of 0-2. CI represents a counter ion when a counter ion is required to neutralize the charge. ]

（式ＬＬ１において、Ｒ^５１及びＲ^５２は酸性基を表す。Ｒ^５３及びＲ^５４は置換基を表す。Ｒ^５５及びＲ^５６はアルキル基又は芳香環基を表す。ｄ１及びｄ２は０〜５の整数を表す。Ｌ^１及びＬ^２は共役鎖を表す。ａ１及びａ２は０〜３の整数を表す。ｄ３は０又は１を表す。ｂ１およびｂ２は０〜３の整数を表す。）

(In Formula LL1, R ⁵¹ and R ⁵² represent an acidic group. R ⁵³ and R ⁵⁴ represent a substituent. R ⁵⁵ and R ⁵⁶ represent an alkyl group or an aromatic ring group. D1 and d2 are 0-5. L ¹ and L ² represent a conjugated chain, a ¹ and a ² represent an integer of 0 to 3, d 3 represents 0 or 1, b 1 and b 2 represent an integer of 0 to 3)

（式ＬＬ２において、Ｚａ、Ｚｂ及びＺｃは５又は６員環を形成しうる原子群を表す。ｃは０又は１を表す。ただし、Ｚａ、Ｚｂ及びＺｃが形成する環のうち少なくとも１つは酸性基を有する。）
（１２）（１）〜（１１）のいずれか１項に記載の光電変換素子を備える光電気化学電池。
（１３）下記式（１）で表される構造を有する色素化合物。

(In formula LL2, Za, Zb and Zc represent an atomic group capable of forming a 5- or 6-membered ring. C represents 0 or 1. However, at least one of the rings formed by Za, Zb and Zc is Has an acidic group.)
(12) A photoelectrochemical cell comprising the photoelectric conversion element according to any one of (1) to (11).
(13) A dye compound having a structure represented by the following formula (1).

（式中、Ｑは芳香環を表す。Ｘ^１、Ｘ^２は硫黄原子、セレン原子、酸素原子、またはＣＲ^１Ｒ^２を表す。Ｒ^１、Ｒ^２はアルキル基を表す。Ｒ、Ｒ’はアルキル基または芳香族基である。Ｐ^１は下記式Ｐ１１または下記式Ｐ１２で表される原子群を表す。Ｐ^２はポリメチン色素を形成するのに必要な原子群を表す。ただし、Ｐ^１とＰ^２は異なるものとする。Ｗ^１は電荷を中和させるのに必要な場合の対イオンを表す。）

(In the formula, Q represents an aromatic ring. X ¹ and X ² represent a sulfur atom, a selenium atom, an oxygen atom, or CR ¹ R ^2. R ¹ and R ² represent an alkyl group. R and R ′ represent An alkyl group or an aromatic group, P ¹ represents an atomic group represented by the following formula P11 or P12, and P ² represents an atomic group necessary for forming a polymethine dye, provided that P ¹ and P ² is different, W ¹ represents the counter ion as needed to neutralize the charge.)

（式中、Ｒ^５、Ｒ^６、Ｒ^１０、Ｒ^１１は脂肪族基又は芳香環基を表す。Ｒ^７、Ｒ^１２は硫黄原子または下記式Ｒ^Ａを表す。Ｒ^３、Ｒ^４、Ｒ^８は水素原子又は置換基を表す。Ｒ^９は酸素原子又は置換基を表す。ｎ２１は０以上の整数を表す。ｎ２２、ｎ３１は０又は１を示す。）

^{(Wherein, R 5, R 6, R} 10, R 11 is ^.R 7 which represents an aliphatic group or an aromatic ring ^{group, R 12} is ^.R 3 representing a sulfur atom or the following formula ^{R A, R 4, R 8} Represents a hydrogen atom or a substituent, R ⁹ represents an oxygen atom or a substituent, n21 represents an integer of 0 or more, and n22 and n31 represent 0 or 1.)

（式Ｒ^ＡにおけるＲ^１３、Ｒ^１４はシアノ基又は酸性基を表す。）

(R ¹³ and R ¹⁴ in the formula R ^A represent a cyano group or an acidic group.)

  In this specification, an aromatic ring is used to mean an aromatic ring and a heterocyclic ring (aliphatic heterocyclic ring and aromatic heterocyclic ring). The carbon-carbon double bond may be either E-type or Z-type. When a plurality of substituents or ligands are alternatively defined, the respective substituents or ligands may be the same or different from each other. Further, when a plurality of substituents or ligands are close to each other, they may be connected to each other or condensed to form a ring.

  The photoelectric conversion element and the photoelectrochemical cell of the present invention exhibit high IPCE in a wavelength region exceeding 800 nm, achieve high photoelectric conversion efficiency, and are excellent in durability. The dye compound of the present invention is a novel compound and is useful as a sensitizing dye for use in the photoelectric conversion element and the photoelectrochemical cell exhibiting the above-described high performance.

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

The photoelectric conversion element of the present invention comprises a photoreceptor having a layer of semiconductor fine particles adsorbing a sensitizing dye having a specific structure. The dye compound has atomic groups (P ¹ , P ² ) having different functionalities on the left and right of the mother nucleus (a cyclic atomic group sandwiched between P ¹ and P ² in formula (1)). . This structure promotes localization of HOMO (highest occupied orbital) / LUMO (lowest empty orbit) while delocalizing π electrons in the molecule. What is important here is not simply an asymmetric structure, but a mother nucleus peculiar to the central polycyclic structure is adopted, and an electron-withdrawing rhodanine residue is present in one atomic group (P ¹ ). It has been introduced. Thereby, in the photoelectric conversion element, high IPCE was exhibited even in a long wavelength region exceeding 800 nm, high photoelectric conversion efficiency was realized, and higher durability was achieved.
This reason includes unclear points, but can be explained as follows, including estimation. In other words, when the specific dye is adsorbed on semiconductor fine particles such as titania, it is expected that the HOMO localized side functions as a donor in the molecule, and the LUMO localized side functions as an acceptor. . Thus, it is considered that high photoelectric conversion efficiency was achieved by sending electrons to the semiconductor fine particles more efficiently than LUMO arranged on the semiconductor fine particle side and suppressing the reverse movement of the electrons. It is presumed that the molecular structure including the high electron withdrawing property of rhodanine residue and the mother nucleus of the polycyclic structure contributed to the improvement of the characteristics and the improvement of durability in the ultralong wavelength region. Hereinafter, the present invention will be described in detail based on preferred embodiments thereof.

[Element structure]
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, a charge transfer layer 3, and a counter electrode 4 arranged in that order on the conductive support 1. The conductive support 1 and the photoreceptor 2 constitute a light receiving electrode 5. The photoreceptor 2 has conductive fine particles 22 and a sensitizing dye 21, and the dye 21 is adsorbed on the conductive fine particles 22 at least in part (the dye is in an adsorption equilibrium state, It may be present in the partial charge transfer layer.) The conductive support 1 on which the photoreceptor 2 is formed functions as a working electrode in the photoelectric conversion element 10. The photoelectric conversion element 10 can be operated as the photoelectrochemical cell 100 by causing the external circuit 6 to work.

The light-receiving electrode 5 is an electrode composed of a conductive support 1 and a photosensitive layer (semiconductor film) 2 including semiconductor fine particles 22 adsorbed with a dye 21 coated on the conductive support. Light incident on the photoreceptor layer (semiconductor film) 2 excites the dye. The excited dye has high energy electrons. Therefore, the electrons are transferred from the dye 21 to the conduction band of the semiconductor fine particles 22 and further reach the conductive support 1 by diffusion. At this time, the molecule of the dye 21 is an oxidant. While the electrons on the electrode work in the external circuit, the excited and oxidized dye receives electrons from the reducing agent (eg, I ⁻ ) in the electrolyte and returns to the ground state dye, thereby allowing the photoelectrochemical cell to Acts as At this time, the light receiving electrode 5 functions as a negative electrode of the battery.

As can be seen from the operation principle of the above element, it is generally preferable to reduce the HOMO / LUMO gap of the dye in order to realize a longer wavelength in the sensitizing region of the sensitizing dye. Therefore, it is conceivable to increase the energy level of the HOMO of the dye and lower the LUMO as necessary. By increasing the energy level of the HOMO, the difference between the energy level of the HOMO of the dye and the energy level of the reducing agent (for example, I ⁻ ) in the electrolyte is reduced. Reduction rate is slow. In addition, when the LUMO energy level of the dye is lowered, the difference from the energy level of the conductive band of the semiconductor fine particles (for example, titanium oxide) is reduced, so that the electron injection efficiency is lowered, and the short-circuit current and the fill factor are reduced. Therefore, it is difficult to increase the photoelectric conversion efficiency.
On the other hand, it is conceivable to increase the electron injection efficiency by lowering the energy level of the conduction band of the semiconductor particles. In this method, the short circuit current can be increased, but the open circuit voltage is decreased.
On the other hand, according to a preferred embodiment of the present invention, along with the reduction of the band gap, the above-mentioned localization of both orbits is greatly promoted, and the photoelectric conversion efficiency and the durability are improved at an ultra-long wavelength. It is preferable that the molecular design can be achieved more effectively.

  The photoelectric conversion element of this embodiment has a photoreceptor having a layer of porous semiconductor fine particles on which an after-mentioned dye is adsorbed on a conductive support. At this time, a part of the dye dissociated in the electrolyte may be present. The photoreceptor is designed according to the purpose, and may have a single layer structure or a multilayer structure. The photoconductor of the photoelectric conversion element of the present embodiment includes semiconductor fine particles adsorbed with a specific sensitizing dye, has high sensitivity, and can be used as a photoelectrochemical cell, and high conversion efficiency can be obtained. The upper and lower sides of the photoelectric conversion element do not need to be defined in particular, but in this specification, based on what is illustrated, the side of the counter electrode 4 serving as the light receiving side is the upper (top) direction, and the support The side of 1 is the lower (bottom) direction.

[Dye]
(Dye made of compound of general formula (1))
In the photoelectric conversion element of the present invention, a dye comprising at least a compound represented by the following general formula (1) is used. The dye of the general formula (1) includes those represented by a resonance structural formula different from that formula. This is the general formula (1) in the similar for all chemical formulas of the introduced group of atoms (P11, P12, Ar ^1, etc.) should be construed as the conjugated structure to align the whole molecule.

・ Q
In formula (1), Q represents an aromatic ring. The aromatic ring includes an aromatic ring and a heterocyclic ring as described above. As the aromatic ring, a benzene ring or a naphthalene ring is preferable, and a benzene ring is preferable. Examples of the heterocyclic ring include the ring structure of the exemplified substituent HARex described later.

· ^X 1, ^{X 2}
X ¹ and X ² represent a sulfur atom, a selenium atom, an oxygen atom, or CR ¹ R ² . Here, R ¹ and R ² represent an alkyl group. Examples of the alkyl group include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, hexyl, heptyl, decyl, 1-ethylpentyl, 2-ethylhexyl, benzyl, 2-ethoxy. Ethyl, 1-carboxymethyl and the like are preferable, methyl, ethyl, isopropyl, decyl, 1-ethylpentyl, 2-ethoxyethyl and benzyl are more preferable, and methyl, ethyl, decyl and 2-ethoxyethyl are particularly preferable. Hereinafter, examples and preferable examples of the alkyl group are referred to as an alkyl group “Rex”. X ¹ and X ² are preferably an oxygen atom or CR ¹ R ² , and more preferably CR ¹ R ² . In the general formula (1), the vertical relationship between X ¹ , X ² and N—R, N—R ′ may be reversed (that is, N—R is lower, N—R). 'May be the relationship above.)

・ R, R '
R and R ′ are an alkyl group or an aromatic group. Examples of the alkyl group include the alkyl group Rex. Examples of the aromatic group include aryl groups having 6 to 26 carbon atoms, and phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, and 3-methylphenyl are preferable, and phenyl, 4-methoxyphenyl, 3- Methylphenyl is more preferred. Hereinafter, examples and preferred examples of the aromatic group (aryl group) are referred to as an aromatic group “Alex”.

・ P ¹
P ¹ represents an atomic group represented by the following formula P11 or formula P12.

・ P ²
P ² represents an atomic group necessary for forming a polymethine dye.

However, ^{P 1} and ^{P 2} will be different. Here, it is sufficient that the two atomic groups are different from each other as long as the effects of the present invention are achieved, and the specific structure is not limited. Typically, in the dye represented by the formula (1), it is preferable that the P ¹ forms an electron acceptor and the P ² forms a donor, and the dye forms a donor-acceptor type molecule. Here, the donor-acceptor type dye means a dye that causes intramolecular photoinduced electron transfer in which electrons are transferred from the donor site in the dye to the acceptor site via conjugation in the molecule when irradiated with light.

・ W ¹
W ¹ represents a counter ion when a counter ion is required to neutralize the charge. Generally, whether a dye is a cation, an anion, or has a net ionic charge depends on the auxiliary color groups and substituents in the dye. When the dye having the structure of the general formula (1) has a dissociable substituent, it may be dissociated and have a negative charge. In this case, the charge of the whole molecule is neutralized by W ^1.
When W ¹ is a cation, for example, it is a proton, an inorganic or organic ammonium ion (for example, a tetraalkylammonium ion, a pyridinium ion) or an alkali metal ion. When W ¹ is an anion, either an inorganic anion or an organic anion may be used. For example, halogen anion (for example, fluoride ion, chloride ion, bromide ion, iodide ion), substituted aryl sulfonate ion (for example, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion), aryl disulfone Acid ion (for example, 1,3-benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion Perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion and the like. Furthermore, an ionic polymer or another dye having a charge opposite to that of the dye may be used as the charge balance counter ion, or a metal complex ion (for example, bisbenzene-1,2-dithiolatonickel (III)) may be used.

・ R ⁵ , R ⁶ , R ¹⁰ , R ^{11
Wherein, R 5, R 6, R} 10, R 11 represents that there aromatic ring group having the certain aliphatic group, or an acidic group having an acidic group. Examples of the aliphatic group include the following cycloalkyl group CRex in addition to the alkyl group Rex. CRex is preferably a cycloalkyl group having 3 to 20 carbon atoms, and more preferably cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl and the like. Examples of the aromatic ring group include the following heterocyclic group HARex in addition to the aromatic group Arex. HARex is preferably a heterocyclic group having 2 to 20 carbon atoms, and more preferably 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl and the like.

  The acidic group is a substituent having a dissociative proton, and examples thereof include a carboxy group, a phosphonyl group, a phosphoryl group, a sulfo group, a boric acid group, and the like, or a group having any one of these. A group or a group having this. Further, the acidic group may take a form of releasing a proton and dissociating, or may be a salt. The acidic group is preferably a carboxy group, a sulfonic acid group, a phosphonyl group, a phosphoryl group, or a salt thereof. The acidic group may be a group bonded through a linking group. For example, a carboxyvinylene group, a dicarboxyvinylene group, a cyanocarboxyvinylene group, a carboxyphenyl group, and the like can be mentioned as preferable examples. In addition, the acidic group mentioned here and its preferable range may be called acidic group Ac.

· ^{R 7, R 12}
R ⁷ and R ¹² represent a sulfur atom or the following formula ^RA .

式Ｒ^ＡにおけるＲ^１３、Ｒ^１４はシアノ基又は酸性基を表す。Ｒ^１３、Ｒ^１４はは両者がシアノ基もしくは酸性基であってもよいが、シアノ基と酸性基との組合せであることが好ましい。好ましい酸性基としては、前記酸性基Ａｃが挙げられる。

R ¹³ and R ¹⁴ in the formula R ^A represent a cyano group or an acidic group. R ¹³ and R ¹⁴ may both be a cyano group or an acidic group, but are preferably a combination of a cyano group and an acidic group. A preferable acidic group includes the acidic group Ac.

・ R ³ , R ⁴ , R ⁸
R ³ , R ⁴ and R ⁸ represent a hydrogen atom or a substituent. Examples of the substituent include the substituent T. R ³ , R ⁴ , and R ⁸ are preferably an alkyl group Rex or a hydrogen atom, and more preferably a hydrogen atom.
・ R ⁹
R ⁹ represents an oxygen atom or a substituent. When R ⁹ is a divalent substituent, it is preferably represented by the following formula R91 or R92.

式Ｒ９２中、Ｒ１５は水素原子もしくはアルキル基を表す。アルキル基としては、上記アルキル基Ｒｅｘが挙げられる。

In formula R92, R15 represents a hydrogen atom or an alkyl group. Examples of the alkyl group include the alkyl group Rex.

  n21 represents an integer of 0 or more, preferably 0 to 3, and more preferably 0 or 1. n22 and n31 each represents 0 or 1, and is preferably 0.

In the present invention, the P ¹ is preferably the following formula P11-1 or P12-1.

式中、Ｒ^３、Ｒ^４、Ｒ^６、Ｒ^８、Ｒ^９、Ｒ^１１、ｎ^２１は、式Ｐ１１，Ｐ１２と同義である。

In the formula, R ³ , R ⁴ , R ⁶ , R ⁸ , R ⁹ , R ¹¹ , and n ²¹ are synonymous with formulas P11 and P12.

式中、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^８、Ｒ^９、Ｒ^１０、ｎ^２１は、Ｐ１１、Ｐ１２と同義である。 In the present invention, it is also preferable that the P ¹ is represented by the following formula P11-2 or P12-2.

In the formula, R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ , R ¹⁰ and n ²¹ have the same meanings as P11 and P12.

In the present invention, the P ² is preferably the following formula P21 or P22.

^{· R 21, R 22, R} 23
^{Wherein, R 21, R 22, R} 23 represents a substituent. Examples of the substituent include the substituent T described later. R ²¹ , R ²² , and R ²³ are preferably an alkyl group Rex or a hydrogen atom, and more preferably a hydrogen atom.

・ N41
n41 represents an integer of 0 or more, preferably 0 to 3, and more preferably 0 to 2.

・ Ar ¹
Ar ¹ represents an aromatic ring group having a substituent with a σp value of 0 or less in the Hammett rule or a π-excess heterocyclic group having a substituent with a σp value of 0 or less. The π-excess heterocyclic group means a residue of a π-excess heterocyclic compound. The π-excess system typically means a state in which the number of π electron systems including a loan pair such as a nitrogen atom exceeds the number of atoms constituting the ring. For details, for example, “New edition heterocyclic compound basic edition” (Kodansha Scientific) p15 can be referred to.

  Here, the substituent constant σp value in Hammett's rule will be described. Hammett's rule is described in 1935 by L.L. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. This is a rule of thumb advocated by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include σp value and σm value, and these values can be found in many general books. For example, J. et al. A. Dean, "Lange's Handbook of Chemistry", 12th edition, 1979 (McGraw-Hill) and "Area of Chemistry" extra edition, 122, 96-103, 1979 (Nankodo), Chem. Rev. 1991, 91, 165-195.

Examples of the substituent having a substituent constant σ _p of 0 or less include an electron-donating substituent, and specifically include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, an alkylamino group, and an aryl group. An amino group is mentioned, Preferably, an alkyl group, an alkoxy group, and an alkylamino group are mentioned. Preferably it is a C1-C20 alkyl group as an alkyl group, More preferably, the said Rex is mentioned. The alkoxy group is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably methoxy, ethoxy, isopropyloxy, benzyloxy or the like. In a substituent having a σp value of 0 or less, the σp value is preferably −0.13 or less, and more preferably −0.2 or less. Although there is no lower limit in particular, it is practical that it is -1.2 or more.

  On the other hand, those having a positive substituent constant σp value include halogen atoms, nitro groups, cyano groups, sulfo groups, carboxy groups, formyl groups, acyl groups, carbamoyl groups, sulfamoyl groups, mercapto groups, alkyl or arylsulfonyl groups. An alkyl or arylsulfinyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a perfluoroalkyl group, a heterocyclic group (for example, a heterocyclic ring is a pyridine ring or a pyrimidine ring, a 2-pyrimidinyl group, a 4-pyrimidinyl group, a 5- Pyrimidinyl group, 2-thienyl group, 2-pyridyl group, 3-pyridinyl group, 4-pyridinyl group), a phenyl group substituted with an electron withdrawing group (the electron withdrawing group has a positive substituent constant σp as described above) Among the groups mentioned as groups, a carboxy group is particularly preferred, and a 3-carboxyphenyl group or Is 4-carboxyphenyl group). In a substituent having a positive σp value, the σp value is preferably 0.01 or more, and more preferably 0.05 or more. Although there is no upper limit in particular, it is practical that it is 1.4 or less.

Ar ¹ may be linked directly or via a methine chain, and when directly linked, it means that the conjugated structure is different from the above formula.

The Ar ¹ is preferably represented by the following formulas R ^C1 , R ^C2 , R ^C3 , R ^C4 .

・ Y
In the formula, Y represents S, NR ²⁴ , or C (R ²⁵ ) ₂ . R ²⁴ represents an alkyl group. Preferred examples of the alkyl group include the above Rex. R ²⁵ represents a substituent. Examples of the substituent include the substituent T described later.

・ A
A represents an aromatic ring. Preferable examples of the aromatic ring include the aromatic group Arex and the heterocyclic group HARex.

・ R ^{26 to} R ²⁹
R ^{26 to} R ²⁹ represent a hydrogen atom or a substituent. Preferable examples of the substituent include the substituent T described later. Preferred are an alkyl group, an aryl group, a heterocyclic group and the like.

・ E
E represents S, NR ²⁹ , or O. R ²⁹ represents an alkyl group. Preferred examples of the alkyl group include the above Rex.

・ D
D represents a substituent having a σp value of 0 or less according to Hammett's rule.

・ B
B represents an aromatic ring. Preferable examples of the aromatic ring include the aromatic group Arex and the heterocyclic group HARex.

・ R ^d , nd
X represents SR ^e , OR ^e , NR ^e ₂ , and R ^e represents an alkyl group, an aromatic group, or a heterocyclic group. R ^d represents a substituent. nd represents an integer of 0 to 4. Preferable substituents for R ^d include the substituent T described below. Preferred are an alkyl group, an aryl group, a heterocyclic group and the like.

* Represents a bond and may be linked via a methine chain.
k is a positive integer. 1-4 are preferable and 1-2 are more preferable.

  The structure formed by the formula P21 or P22 together with the mother nucleus of the formula (1) is the following formula (1-1-1), formula (1-1-2), formula (1-2-1), formula (1-2) -2) is preferable.

式中、Ｑ、Ｐ^１、Ｘ^１、Ｘ^２、Ｒ、Ｒ’、Ｗ^１、Ａｒ^１、ｎ４１は前記式（１）と同じ意味を表す。Ｒ^２１０、Ｒ^２１１、Ｒ^２１２、Ｒ^２２０、Ｒ^２２１は水素原子又は置換基を表し、好ましいものはＲ^２１、Ｒ^２２、Ｒ^２３と同じである。

In the formula, Q, P ¹ , X ¹ , X ² , R, R ′, W ^1, Ar ¹ , and n41 represent the same meaning as in the formula (1). R ²¹⁰ , R ²¹¹ , R ²¹² , R ²²⁰ and R ²²¹ each represent a hydrogen atom or a substituent, and preferred ones are the same as R ²¹ , R ²² and R ²³ .

  In the present specification, when the term “compound” is added to the end or indicated by a specific name or chemical formula, it is used in the meaning including its salt, complex, and ion in addition to the compound itself. Moreover, it is the meaning including the derivative modified with the predetermined form in the range with the desired effect. In the present specification, when a substituent or a ligand is referred to by its name, or when the term “group” is added at the end, an arbitrary substituent is added to the group within a range where a desired effect is achieved. It means that you may have. This is also synonymous for compounds that do not specify substitution / non-substitution. Preferred substituents include the following substituent T.

As a preferable substituent that can be introduced (hereinafter referred to as substituent T),
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl A group (preferably an alkenyl group having 2 to 20 carbon atoms, such as vinyl, allyl, oleyl, etc.), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms, such as ethynyl, butadiynyl, phenylethynyl, etc.), A cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), an aryl group (preferably an aryl group having 6 to 26 carbon atoms, for example, Phenyl, 1-naphthyl, 4-methoxyphenyl, -Chlorophenyl, 3-methylphenyl, etc.), heterocyclic groups (preferably heterocyclic groups having 2 to 20 carbon atoms, such as 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2 -Oxazolyl etc.), an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, such as methoxy, ethoxy, isopropyloxy, benzyloxy etc.), an aryloxy group (preferably an aryloxy group having 6 to 26 carbon atoms) , For example, phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), alkoxycarbonyl groups (preferably C2-C20 alkoxycarbonyl groups such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.) ), Amino group (preferably carbon Amino group having 0 to 20 children, such as amino, N, N-dimethylamino, N, N-diethylamino, N-ethylamino, anilino, etc.), sulfonamide group (preferably sulfonamide having 0 to 20 carbon atoms) A group such as N, N-dimethylsulfonamide, N-phenylsulfonamide, etc., an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms such as acetyloxy, benzoyloxy, etc.), a carbamoyl group (preferably A carbamoyl group having 1 to 20 carbon atoms, such as N, N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.), an acylamino group (preferably an acylamino group having 1 to 20 carbon atoms, such as acetylamino, benzoylamino, etc.) , A cyano group, or a halogen atom (eg, fluorine atom, chlorine atom, bromine atom) More preferably an alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkoxycarbonyl group, amino group, acylamino group, cyano group or halogen atom, Particularly preferred are an alkyl group, an alkenyl group, a heterocyclic group, an alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group, and a cyano group.

The maximum absorption wavelength in the ethanol solution of the dye of the present invention represented by the general formula (1) is preferably in the range of 500 to 1300 nm, more preferably in the range of 600 to 1100 nm.
Although the preferable specific example of the pigment | dye represented by General formula (1) of this invention below is shown, this invention is not limited to this. * Represents the position of the carbon atom bonded to the mother nucleus in the following general scheme. Bu represents a butyl group.

Synthesis of a dye comprising the compound represented by the general formula (1) is described in Ukrainski Kimicheskii Zhurnal, Vol. 40 (No. 3), pages 253 to 258, Dies and Pigments, Vol. 21, pages 227 to 234 and these documents. This can be done with reference to the description of the documents cited in the document.
For example, the exemplified dye 14 can be obtained by the following scheme. Other dyes can be obtained in the same manner.

ＮＭＰ：１−メチル−２−ピロリドン、Ｃｌ−Ｐｈ：クロロベンゼン、ＡｃＯＨ：酢酸、ＤＭＦ：Ｎ，Ｎ−ジメチルホルムアミド、Ｐｙ：ピリジン、Ａｌｌｙｌ：アリル基

NMP: 1-methyl-2-pyrrolidone, Cl-Ph: chlorobenzene, AcOH: acetic acid, DMF: N, N-dimethylformamide, Py: pyridine, Allyl: allyl group

(Dye made of compound of general formula (I))
In the photoelectric conversion element and the photoelectrochemical cell of the present invention, it is preferable to use in combination with a metal complex dye. By using together with a metal complex dye, the mutual adsorption state can be controlled, and higher efficiency and durability than each can be achieved.

The metal complex dye preferably includes a dye composed of a compound represented by the following general formula (I).
Mz (LL ¹ ) _m1 (LL ² ) _m2 (X) _m3 · CI: Formula (I)
(In the formula (I), Mz is .ll ¹ is .ll ² is coordination of bidentate or tridentate represented by the following formula LL2 representing a bidentate ligand represented by the following formula LL1 representing a metal atom X represents a monodentate or bidentate ligand other than LL ¹ and LL ^2. m1 represents an integer of 0 to 3. m2 represents an integer of 1 to 3. m3 represents 0. Represents an integer of ˜2. CI represents a counter ion when a counter ion is required to neutralize the charge.)

（式ＬＬ１において、Ｒ^５１及びＲ^５２は酸性基を表す。Ｒ^５３及びＲ^５４は置換基を表す。Ｒ^５５及びＲ^５６はアルキル基又は芳香基を表す。ｄ１及びｄ２は０〜５の整数を表す。Ｌ^１及びＬ^２は共役鎖を表す。ａ１及びａ２は０〜３の整数を表す。ｂ１及びｂ２は０〜３の整数を表す。ｄ３は０又は１を表す。）

(In Formula LL1, R ⁵¹ and R ⁵² represent an acidic group. R ⁵³ and R ⁵⁴ represent a substituent. R ⁵⁵ and R ⁵⁶ represent an alkyl group or an aromatic group. D1 and d2 are integers of 0 to 5. L ¹ and L ² represent a conjugated chain, a ¹ and a ² represent an integer of 0 to 3, b 1 and b 2 represent an integer of 0 to 3. d 3 represents 0 or 1.)

（式ＬＬ２において、Ｚａ、Ｚｂ及びＺｃは５又は６員環を形成しうる原子群を表す。ｃは０又は１を表す。ただし、Ｚａ、Ｚｂ及びＺｃが形成する環のうち少なくとも１つは酸性基を有する。）

(In formula LL2, Za, Zb and Zc represent an atomic group capable of forming a 5- or 6-membered ring. C represents 0 or 1. However, at least one of the rings formed by Za, Zb and Zc is Has an acidic group.)

・ Metal atom Mz
Mz represents a metal atom. Mz is preferably a metal capable of tetracoordinate or hexacoordinate, and more preferably Ru, Fe, Os, Cu, W, Cr, Mo, Ni, Pd, Pt, Co, Ir, Rh, Re, Mn Or it is Zn. Particularly preferred is Ru, Os, Zn or Cu, and most preferred is Ru.

* LL ¹ (Formula LL1)
・ M1
m1 is an integer of 0 to 3, preferably 1 to 3, and more preferably 1. When m1 is 2 or more, LL ¹ may be the same or different.

R ⁵¹ and R ⁵²
R ⁵¹ and R ⁵² each independently represent an acidic group. Such as carboxy group, sulfonic acid group, hydroxy group, hydroxamic acid group (preferably a hydroxamic acid group having 1 to 20 carbon atoms, for example, -CONHOH, -CON _(CH 3) OH and the like), a phosphoryl group (e.g., -OP ( O) (OH) ₂ etc.) and phosphonyl groups (for example -P (O) (OH) ₂ etc.) and salts thereof, preferably carboxy group, phosphonyl group and salts thereof, more preferably carboxy A group or a salt thereof. R ⁵¹ and R ⁵² may be substituted on any carbon atom on the pyridine ring.

R ⁵³ and R ⁵⁴
R ⁵³ and R ⁵⁴ each independently represent a substituent, and preferably the substituent T.

When the ligand LL ¹ contains an alkyl group, an alkenyl group or the like, these may be linear or branched, and may be substituted or unsubstituted. Further, when the ligand LL ¹ contains an aryl group, a heterocyclic group or the like, they may be monocyclic or condensed and may be substituted or unsubstituted.

R ⁵⁵ and R ⁵⁶
In the formula, R ⁵⁵ and R ⁵⁶ each independently represents an alkyl group or an aromatic ring group. The aromatic group is preferably an aromatic group having 6 to 30 carbon atoms, such as phenyl, substituted phenyl, naphthyl, and substituted naphthyl. The heterocyclic (heterocyclic) group is preferably a heterocyclic group having 1 to 30 carbon atoms, such as 2-thienyl, 2-pyrrolyl, 2-imidazolyl, 1-imidazolyl, 4-pyridyl, and 3-indolyl. . Preferably it is a heterocyclic group having 1 to 3 electron donating groups, more preferably thienyl. The electron donating group is an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an amino group, an acylamino group (preferred examples are the same as those for R ⁵³ and R ⁵⁴ ) or a hydroxy group. Of these, an alkyl group, an alkoxy group, an amino group or a hydroxy group is more preferred, and an alkyl group is particularly preferred. R ⁵⁵ and R ⁵⁶ may be the same or different, but are preferably the same.
R ⁵⁵ and R ⁵⁶ may be directly bonded to the benzene ring. R ⁵⁵ and R ⁵⁶ may be bonded to the benzene ring via L ¹ and / or L ² .

・ D1, d2
d1 and d2 are integers of 0 to 5, preferably 0 to 3, and more preferably 0 to 2.

L ¹ and L ²
L ¹ and L ² each independently represents a conjugated chain, and represents a conjugated chain composed of an arylene group, a heteroarylene group, an ethenylene group, and / or an ethynylene group. The ethenylene group, ethynylene group, and the like may be unsubstituted or substituted. When the ethenylene group has a substituent, the substituent is preferably an alkyl group, and more preferably methyl. L ¹ and L ² are each independently preferably a conjugated chain having 2 to 6 carbon atoms, more preferably thiophenediyl, ethenylene, butadienylene, ethynylene, butadienylene, methylethenylene or dimethylethenylene, Butadienylene is particularly preferred and ethenylene is most preferred. L ¹ and L ² may be the same or different, but are preferably the same. When the conjugated chain includes a carbon-carbon double bond, each double bond may be E-type or Z-type, or a mixture thereof.

・ D3
d3 is 0 or 1. In particular, when d3 is 0, a2 is preferably 1 or 2, and when d3 is 1, a2 is preferably 0 or 1. The sum of a1 and a2 is preferably an integer of 0-2.

B1 and b2
b1 and b2 each independently represent an integer of 0 to 3, preferably an integer of 0 to 2. When b1 is 2 or more, R ⁵³ may be the same or different and may be connected to each other to form a ring. When b2 is 2 or more, R ⁵⁴ may be the same or different, and may be connected to each other to form a ring. When both b1 and b2 are 1 or more, R ⁵³ and R ⁵⁴ may be connected to form a ring. Preferable examples of the ring to be formed include a benzene ring, a pyridine ring, a thiophene ring, a pyrrole ring, a cyclohexane ring, a cyclopentane ring and the like.

・ A1 and a2
a1 and a2 each independently represent an integer of 0 to 3. When the sum of a1 and a2 is 1 or more and the ligand LL ¹ has at least one acidic group, m1 in the general formula (I) is preferably 2 or 3, and is preferably 2. Is more preferable. a1 is may be the R ⁵¹ when two or more be the same or different, R ⁵² when a2 is 2 or more may be the same or different. a1 is preferably 0 or 1, and a2 is preferably an integer of 0 to 2.

* LL ² (Formula LL2)
・ M ₂
m2 is an integer of 1 to 3, and preferably 1 or 2. When m ₂ is 2, LL ² may be the same or different.

・ Za, Zb, Zc
Za, Zb and Zc each independently represent a nonmetallic atom group capable of forming a 5-membered ring or a 6-membered ring. The formed 5-membered or 6-membered ring may be substituted or unsubstituted, and may be monocyclic or condensed. Za, Zb and Zc are preferably composed of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom and / or a halogen atom, and preferably form an aromatic ring. In the case of a 5-membered ring, an imidazole ring, an oxazole ring, a thiazole ring or a triazole ring is preferably formed. In the case of a 6-membered ring, a pyridine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring is preferably formed. Of these, an imidazole ring or a pyridine ring is more preferable.

・ C
c represents 0 or 1; c is preferably 0, and LL ² is preferably a bidentate ligand.
Ligand LL ² is preferably represented by any of the following general formula (LL2-1) ~ (LL2-8), the general formula (LL2-1), (LL2-2), (LL2-4 ) Or (LL2-6), more preferably represented by formula (LL2-1) or (LL2-2), and represented by formula (LL2-1). Is particularly preferred.

In formula, R < ¹⁰¹ > -R < ¹⁰⁸ > represents an acidic group or its salt each independently. R ^{101 to} R ¹⁰⁸ are, for example, a carboxy group, a sulfonic acid group, a hydroxy group, a hydroxamic acid group (preferably a hydroxamic acid group having 1 to 20 carbon atoms, such as —CONHOH, —CON (CH ₃ ) OH, etc.), A phosphoryl group (for example, —OP (O) (OH) ₂ or the like) or a phosphonyl group (for example, —P (O) (OH) ₂ or the like) or a salt thereof is represented. R ^{101 to} R ¹⁰⁸ are preferably a carboxy group, a phosphoryl group, a phosphonyl group, or a salt thereof, more preferably a carboxy group, a phosphonyl group, or a salt thereof, and more preferably a carboxy group or a salt thereof.

In the formula, R ^{109 to} R ¹¹⁶ each independently represent a substituent, preferably an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an amino group, An acyl group, a sulfonamide group, an acyloxy group, a carbamoyl group, an acylamino group, a cyano group, or a halogen atom (preferred examples are the same as those for R ⁵³ and R ⁵⁴ ), more preferably an alkyl group, an alkenyl group, An aryl group, heterocyclic group, alkoxy group, alkoxycarbonyl group, amino group, acylamino group or halogen atom, particularly preferably an alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, amino group or acylamino group.

In the formula, R ^{117 to} R ¹²¹ are each independently bonded with a hydrogen atom, an aliphatic group (preferably having 1 to 20 carbon atoms), an aromatic group (preferably having 6 to 26 carbon atoms), or a carbon atom. It represents a heterocyclic group (preferably a 5- or 6-membered ring), preferably an aliphatic group or an aromatic group, and more preferably an aliphatic group having a carboxy group. When the ligand LL ² contains an alkyl group, an alkenyl group or the like, they may be linear or branched and may be unsubstituted substituted. Further, LL ² is an aryl group, when containing heterocyclic group, they may be a condensed ring may be monocyclic or unsubstituted substituted.

In the formula, R ^{101 to} R ¹¹⁶ may be bonded to any position on the ring. E1 to e6 each independently represents an integer of 0 to 4, preferably an integer of 1 to 2. e7 and e8 each independently represents an integer of 0 to 4, preferably an integer of 1 to 3. e9 to e12 and e15 each independently represents an integer of 0 to 6, and e13, e14 and e16 each independently represents an integer of 0 to 4. e9 to e16 are each independently preferably an integer of 0 to 3.

When e1 to e8 is 2 or more, R ^{101 to} R ¹⁰⁸ may be the same or different, and when e9 to e16 is 2 or more, R ^{109 to} R ¹¹⁶ may be the same or different. R ^{101 to} R ¹¹⁶ may be connected to each other or condensed to form a ring.
In the above formulas LL2-1 to LL2-8, the substituents R ^{101 to} R ¹¹⁶ are shown with a bond extended to a predetermined aromatic ring, but are not limited to those substituted with the aromatic ring. That is, for example, in Formula LL2-1, the left pyridine ring is substituted with R ¹⁰¹ and R ¹⁰⁹ , but the right pyridine ring may be substituted.

* Ligand X
In general formula (4), X represents a monodentate or bidentate ligand. M3 representing the number of ligands X represents an integer of 0 to 2, and m3 is preferably 1 or 2. When X is a monodentate ligand, m3 is preferably 2. When X is a bidentate ligand, m3 is preferably 1. When m3 is 2 or more, Xs may be the same or different, and Xs may be linked together.

The ligand X is preferably a ligand other than LL ¹ and LL ² . Specifically, an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms, for example, acetyloxy, benzoyloxy, salicylic acid, glycyloxy, N, N-dimethylglycyloxy, oxalylene (—OC (O) C (O ) O-) etc.), an acylthio group (preferably an acylthio group having 1 to 20 carbon atoms, such as acetylthio, benzoylthio, etc.), a thioacyloxy group (preferably a thioacyloxy group having 1 to 20 carbon atoms, for example, Thioacetyloxy group (CH ₃ C (S) O—) and the like)), thioacylthio group (preferably a thioacylthio group having 1 to 20 carbon atoms, such as thioacetylthio (CH ₃ C (S) S—), thio Benzoylthio (PhC (S) S-) etc.)), acylaminooxy group (preferably acyl having 1 to 20 carbon atoms) Ruaminooxy groups such as N-methylbenzoylaminooxy (PhC (O) N (CH ₃ ) O—), acetylaminooxy (CH ₃ C (O) NHO—) etc.)), thiocarbamate groups (preferably carbon atoms) A thiocarbamate group having 1 to 20 carbon atoms such as N, N-diethylthiocarbamate, a dithiocarbamate group (preferably a dithiocarbamate group having 1 to 20 carbon atoms such as N-phenyldithiocarbamate, N, N- Dimethyldithiocarbamate, N, N-diethyldithiocarbamate, N, N-dibenzyldithiocarbamate, etc.), thiocarbonate group (preferably a thiocarbonate group having 1 to 20 carbon atoms, such as ethylthiocarbonate) , Dithiocarbonates (preferably dithiocarbonates having 1 to 20 carbon atoms , For example, ethyl dithiocarbonate _{(C 2 H 5 OC (S} ) S-) and the like), trithiocarbonate groups (preferably trithiocarbonate group having 1 to 20 carbon atoms, e.g., ethyl trithiocarbonate (C ₂ H ₅ SC (S) S—) and the like), acyl groups (preferably acyl groups having 1 to 20 carbon atoms, such as acetyl and benzoyl), thiocyanate groups, isothiocyanate groups, cyanate groups, isocyanate groups , A cyano group, an alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms such as methanethio and ethylenedithio), an arylthio group (preferably an arylthio group having 6 to 20 carbon atoms such as benzenethio, 1,2- Phenylenedithio, etc.), alkoxy groups (preferably alkoxy groups having 1 to 20 carbon atoms, such as methoxy Etc.) and an aryloxy group (preferably an aryloxy group having 6 to 20 carbon atoms such as phenoxy, quinoline-8-hydroxy, etc.) coordinated with a monodentate or bidentate Ligand or halogen atom (preferably chlorine atom, bromine atom, iodine atom etc.), carbonyl (... CO), dialkyl ketone (preferably dialkyl ketone having 3 to 20 carbon atoms, for example acetone ((CH ₃ ) ₂ CO Etc.), 1,3-diketone (preferably 1,3-diketone having 3 to 20 carbon atoms, for example, acetylacetone (CH ₃ C (O ...) CH═C (O—) CH ₃ ), trifluoro acetylacetone _{(CF 3 C (O ...)} CH = C (O-) CH 3), dipivaloylmethane _{(t-C 4 H 9 C} (O ...) CH = C (O-) t-C 4 H 9 Dibenzoylmethane (PhC (O ...) CH = C (O-) Ph), 3- chloro-acetylacetone _{(CH 3 C (O ...)} CCl = C (O-) CH 3) , etc.), carbonamido (preferably Carbonamide having 1 to 20 carbon atoms, for example, CH ₃ N═C (CH ₃ ) O—, —OC (═NH) —C (═NH) O—, etc.), thiocarbonamide (preferably having 1 carbon atom) ˜20 thiocarbonamide, such as CH ₃ N═C (CH ₃ ) S—, or thiourea (preferably thiourea having 1 to 20 carbon atoms, eg NH (...) = C (S—) NH ₂ , CH ₃ N (...) = C (S—) NHCH ₃ , (CH ₃ ) ₂ N—C (S...) N (CH ₃ ) _2, etc.). "..." indicates a coordination bond coordinated to Mz.

  The ligand X is preferably an acyloxy group, a thioacylthio group, an acylaminooxy group, a dithiocarbamate group, a dithiocarbonate group, a trithiocarbonate group, a thiocyanate group, an isothiocyanate group, a cyanate group, an isocyanate group, a cyano group, A ligand coordinated by a group selected from the group consisting of an alkylthio group, an arylthio group, an alkoxy group and an aryloxy group, or a ligand consisting of a halogen atom, carbonyl, 1,3-diketone or thiourea, More preferably, a ligand coordinated by a group selected from the group consisting of acyloxy group, acylaminooxy group, dithiocarbamate group, thiocyanate group, isothiocyanate group, cyanate group, isocyanate group, cyano group or arylthio group, or Halogen atom 1,3 A ligand comprising a diketone or thiourea, particularly preferably a ligand coordinated by a group selected from the group consisting of a dithiocarbamate group, a thiocyanate group, an isothiocyanate group, a cyanate group and an isocyanate group, or a halogen atom Or a ligand consisting of a 1,3-diketone, most preferably a ligand coordinated with a group selected from the group consisting of a dithiocarbamate group, a thiocyanate group and an isothiocyanate group, or a 1,3-diketone A ligand consisting of In addition, when the ligand X contains an alkyl group, an alkenyl group, an alkynyl group, an alkylene group or the like, these may be linear or branched, and may be substituted or unsubstituted. Moreover, when an aryl group, a heterocyclic group, a cycloalkyl group, etc. are included, they may be substituted or unsubstituted, and may be monocyclic or condensed.

  When X is a bidentate ligand, X is acyloxy group, acylthio group, thioacyloxy group, thioacylthio group, acylaminooxy group, thiocarbamate group, dithiocarbamate group, thiocarbonate group, dithiocarbonate group, trithio A ligand coordinated by a group selected from the group consisting of a carbonate group, an acyl group, an alkylthio group, an arylthio group, an alkoxy group and an aryloxy group, or a 1,3-diketone, carbonamide, thiocarbonamide, or thio A ligand composed of urea is preferable. When X is a monodentate ligand, X is a ligand coordinated by a group selected from the group consisting of a thiocyanate group, an isothiocyanate group, a cyanate group, an isocyanate group, a cyano group, an alkylthio group, and an arylthio group, or A ligand composed of a halogen atom, carbonyl, dialkyl ketone, or thiourea is preferred.

* Counter ion CI
CI in the general formula (I) represents a counter ion when a counter ion is required to neutralize the charge. In general, whether a dye is a cation or an anion or has a net ionic charge depends on the metal, ligand and substituent in the dye.
The dye of general formula (I) may be dissociated and have a negative charge, for example, because the substituent has a dissociable group. In this case, the overall charge of the dye of the general formula (I) is neutralized by CI.

When the counter ion CI is a positive counter ion, for example, the counter ion CI is an inorganic or organic ammonium ion (for example, tetraalkylammonium ion, pyridinium ion, etc.), an alkali metal ion, or a proton.
When the counter ion CI is a negative counter ion, for example, the counter ion CI may be an inorganic anion or an organic anion. For example, halogen anions (eg, fluoride ions, chloride ions, bromide ions, iodide ions, etc.), substituted aryl sulfonate ions (eg, p-toluene sulfonate ions, p-chlorobenzene sulfonate ions, etc.), aryl disulfones Acid ion (for example, 1,3-benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion, etc.), alkyl sulfate ion (for example, methyl sulfate ion, etc.), sulfate ion, thiocyanate ion Perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion and the like. Further, as the charge balance counter ion, an ionic polymer or another dye having a charge opposite to that of the dye may be used, and a metal complex ion (for example, bisbenzene-1,2-dithiolatonickel (III)) can also be used. is there.

* Bonding Group The dye having the structure represented by the general formula (I) preferably has at least one suitable interlinking group for the surface of the semiconductor fine particles. It is more preferable to have 1 to 6 bonding groups in the dye, and it is particularly preferable to have 1 to 4 bonding groups. Carboxy group, sulfonic acid group, hydroxy group, hydroxamic acid group (for example, —CONHOH), phosphoryl group (for example, —OP (O) (OH) _2, etc.), phosphonyl group (for example, —P (O) (OH) _2, etc.) It is preferable that the dye has an acidic group (substituent having a dissociable proton).

  Specific examples of the dye having the structure represented by the general formula (I) are shown below, but the present invention is not limited thereto. In addition, when the pigment | dye in the following specific example contains the ligand which has a proton dissociable group, this ligand may dissociate as needed and may discharge | release a proton.

The dye represented by the general formula (I) of the present invention can be synthesized with reference to JP-A No. 2001-291534 and the methods cited in the publication.
The dye comprising the compound represented by formula (I) has a maximum absorption wavelength in the solution of preferably 300 to 1000 nm, more preferably 350 to 950 nm, and particularly preferably 370 to 900 nm. It is a range.
In the photoelectric conversion element and the photoelectrochemical cell of the present invention, at least a wide range of dyes comprising a compound represented by the general formula (1) and a compound represented by the general formula (I) are used. By using light of a wavelength, high conversion efficiency can be ensured.

  The blending ratio of the dye composed of the compound represented by the general formula (I) and the dye composed of the compound represented by the general formula (1) is as follows. S = 95 / 5-10 / 90, preferably R / S = 95 / 5-50 / 50, more preferably R / S = 95 / 5-60 / 40, even more preferably R / S = 95/5 ~ 65/35, most preferably R / S = 95/5 to 70/30.

［一般式（１）’において、Ｑ’は４価の芳香族基を示し、Ｘ^１’、Ｘ^２’はそれぞれ独立に硫黄原子、酸素原子、又はＣＲ^１Ｒ^２を表す。ここでＲ^１、Ｒ^２はそれぞれ独立に、水素原子、脂肪族基、芳香族基、炭素原子で結合するヘテロ環基を表し、これらは置換されていてもよい。Ｒ^ａ、Ｒ^ａ’はそれぞれ独立に脂肪族基、芳香族基、炭素原子で結合するヘテロ環基を表し、これらは置換されていてもよい。Ｐ^１’、Ｐ^２’はそれぞれ独立に色素残基を表す。Ｗ^１’は電荷を中和させるのに必要な場合の対イオンを表す。］
一般式（１）’の例として下記が挙げられる。

You may use the pigment | dye of this invention simultaneously with what is represented by following General formula (1) '.

[In General Formula (1) ′, Q ′ represents a tetravalent aromatic group, and X ^{1 ′} and X ^{2 ′} each independently represent a sulfur atom, an oxygen atom, or CR ¹ R ² . Here, R ¹ and R ² each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group bonded with a carbon atom, and these may be substituted. R ^a and R ^a ′ each independently represents an aliphatic group, an aromatic group, or a heterocyclic group bonded with a carbon atom, and these may be substituted. P ^{1 ′} and P ^{2 ′} each independently represent a dye residue. W ^{1 ′} represents a counter ion as necessary to neutralize the charge. ]
Examples of the general formula (1) ′ include the following.

[Photoelectric conversion element]
(Photoreceptor layer)
The embodiment of the photoelectric conversion element has already been described with reference to FIG. In the present embodiment, the photoreceptor layer 2 is composed of a porous semiconductor layer composed of a layer of semiconductor fine particles 22 on which a dye described later is adsorbed. This dye may be partially dissociated in the electrolyte. The photoreceptor layer 2 may be designed according to the purpose and may have a multilayer structure.
As described above, since the photosensitive layer 2 includes the semiconductor fine particles 22 on which a specific dye is adsorbed, the light receiving sensitivity is high, and when used as the photoelectrochemical cell 100, high photoelectric conversion efficiency can be obtained. Furthermore, it has high durability.

(Charge transfer body)
The electrolyte composition used for the photoelectric conversion element 10 of the present invention includes, for example, a combination of iodine and iodide (for example, lithium iodide, tetrabutylammonium iodide, tetrapropylammonium iodide, etc.) as an oxidation-reduction pair, alkyl Combinations of viologens (for example, methyl viologen chloride, hexyl viologen bromide, benzyl viologen tetrafluoroborate) and reduced forms thereof, combinations of polyhydroxybenzenes (for example, hydroquinone, naphthohydroquinone, etc.) and oxidized forms thereof, bivalent and trivalent And a combination of iron complexes (for example, red blood salt and yellow blood salt). Of these, a combination of iodine and iodide is preferred.

  The cation of the iodine salt is preferably a 5-membered or 6-membered nitrogen-containing aromatic cation. In particular, when the compound represented by the general formula (1) is not an iodine salt, republished WO95 / 18456, JP-A-8-259543, Electrochemistry, Vol.65, No.11, p.923 (1997) It is preferable to use iodine salts such as pyridinium salts, imidazolium salts, and triazolium salts described in the above.

  The electrolyte composition used for the photoelectric conversion element 10 of the present invention preferably contains iodine together with the heterocyclic quaternary salt compound. The iodine content is preferably 0.1 to 20% by mass, and more preferably 0.5 to 5% by mass with respect to the entire electrolyte composition.

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

  As the solvent, those having a low viscosity and high ion mobility, a high dielectric constant and capable of increasing the effective carrier concentration, or both are preferable because they can exhibit excellent ion conductivity. As such a solvent, carbonate compounds (ethylene carbonate, propylene carbonate, etc.), heterocyclic compounds (3-methyl-2-oxazolidinone, etc.), ether compounds (dioxane, diethyl ether, etc.), chain ethers (ethylene glycol dialkyl ether, Propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, etc.), alcohols (methanol, ethanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, etc.), Polyhydric alcohols (ethylene glycol, propylene glycol, polyethylene glycol Nitrile compounds (acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, benzonitrile, biscyanoethyl ether, etc.), esters (carboxylic esters, phosphate esters, phosphonates, etc.) ), Aprotic polar solvent (dimethyl sulfoxide (DMSO), sulfolane, etc.), water, hydrous electrolyte described in JP-A No. 2002-110262, JP-A No. 2000-36332, JP-A No. 2000-243134, and republication Examples include electrolyte solvents described in WO / 00-54361. These solvents may be used as a mixture of two or more.

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

  In addition, an electrode layer, a photoreceptor layer (photoelectric conversion layer), a charge transfer layer (hole transport layer), a conductive layer, and a counter electrode layer can be sequentially stacked. A hole transport material that functions as a p-type semiconductor can be used as the hole transport layer. As a preferred hole transport layer, for example, an inorganic or organic hole transport material can be used. Examples of the inorganic hole transport material include CuI, CuO, and NiO. Examples of the organic hole transport material include high molecular weight materials and low molecular weight materials, and examples of the high molecular weight materials include polyvinyl carbazole, polyamine, and organic polysilane. Moreover, as a low molecular weight thing, a triphenylamine derivative, a stilbene derivative, a hydrazone derivative, a phenamine derivative etc. are mentioned, for example. Among these, organic polysilanes are preferable because, unlike conventional carbon-based polymers, σ electrons delocalized along the main chain Si contribute to photoconductivity and have high hole mobility (Phys. Rev.). B, 35, 2818 (1987)).

(Conductive support)
As shown in FIG. 1, in the photoelectric conversion element of the present invention, a photosensitive layer 2 in which a sensitizing dye 21 is adsorbed on porous semiconductor fine particles 22 is formed on a conductive support 1. As will be described later, for example, the photoreceptor layer 2 can be produced by immersing the dispersion of semiconductor fine particles in the dye solution of the present invention after coating and drying on a conductive support.

As the conductive support 1, glass or a polymer material having a conductive film on the surface can be used as the support itself, such as metal. The conductive support 1 is preferably 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 1, 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 1, 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 JP-A-2002-260746 is improved.

  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.

(Semiconductor fine particles)
As shown in FIG. 1, in the photoelectric conversion element 10 of the present invention, a photosensitive layer 2 in which a sensitizing dye 21 is adsorbed on porous semiconductor fine particles 22 is formed on a conductive support 1. As will be described later, for example, the photoreceptor layer 2 can be produced by immersing the dispersion of the semiconductor fine particles 22 on the conductive support 1 and then immersing it in the above dye solution. In the present invention, the semiconductor fine particles prepared using the specific surfactant are applied.

(Semiconductor fine particle dispersion)
In the present invention, the semiconductor fine particle dispersion having a solid content other than the semiconductor fine particles of 10% by mass or less of the whole of the semiconductor fine particle dispersion is applied to the conductive support 1 and heated appropriately. Quality semiconductor fine particle coating layer can be obtained.

  In addition to the sol-gel method, semiconductor fine particle dispersions can be prepared by depositing fine particles in a solvent and using them as they are when synthesizing semiconductors. Or a method of pulverizing and grinding mechanically using a mill or a mortar. As the dispersion solvent, one or more of water and 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, the application system method and the metering system method can be made the same part. The wire bar method disclosed in Japanese Patent Publication No. 58-4589, the slide hopper method described in US Pat. No. 2,681,294, etc., the extrusion The method and the curtain method 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 1 is increased, and it becomes easy to apply the semiconductor fine particle dispersion. .

The preferred thickness of the entire semiconductor fine particle layer is 0.1 μm to 100 μm. The thickness of the semiconductor fine particle layer is further preferably 1 μm to 30 μm, and more preferably 2 μm 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 g to 100 g. The method for forming the film by applying the fine particle dispersion is not particularly limited, and a known method may be applied as appropriate.

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

  In order to adsorb the sensitizing dye 21 to the semiconductor fine particles 22, it is preferable to immerse the well-dried semiconductor fine particles 22 in a dye adsorbing dye solution comprising the solution and the dye according to the present invention for a long time. The solution used for the dye solution for dye adsorption can be used without particular limitation as long as it can dissolve the sensitizing dye 21 according to 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 total amount of the sensitizing dye 21 used is preferably from 0.01 mmol to 100 mmol, more preferably from 0.1 mmol to 50 mmol, and particularly preferably from 0.1 mmol to 10 mmol, per 1 m ² of the support. . In this case, the amount of the sensitizing dye 21 according to the present invention is preferably 5 mol% or more.

  Further, the adsorption amount of the sensitizing dye 21 to the semiconductor fine particles 22 is preferably 0.001 mmol 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 is 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.

(Counter electrode)
The counter electrode 4 functions as a positive electrode of the photoelectrochemical cell. The counter electrode 4 is usually synonymous with the conductive support 1 described above, but a support for the counter electrode 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 4 include platinum, carbon, and conductive polymer. Preferable examples include platinum, carbon, and conductive polymer.

  The structure of the counter electrode 4 is preferably a structure having a high current collecting effect. Preferable examples include JP-A-10-505192.

(Reception electrode)
The light receiving electrode 5 may be a tandem type in order to increase the utilization rate of incident light. Preferred examples of the tandem type configuration include those described in JP-A Nos. 2000-90989 and 2002-90989.

  A light management function for efficiently performing light scattering and reflection inside the layer of the light receiving electrode 5 may be provided. Preferably, the thing of Unexamined-Japanese-Patent No. 2002-93476 is mentioned.

  It is preferable to form a short-circuit prevention layer between the conductive support 1 and the porous semiconductor fine particle layer in order to prevent a reverse current due to direct contact between the electrolyte and the electrode. Preferable examples include Japanese Patent Application Laid-Open No. 06-507999.

  In order to prevent contact between the light receiving electrode 5 and the counter electrode 4, it is preferable to use a spacer or a separator. A preferable example is JP-A No. 2001-283941.

  Cell and module sealing methods include polyisobutylene thermosetting resin, novolak resin, photo-curing (meth) acrylate resin, epoxy resin, ionomer resin, glass frit, method using aluminum alkoxide for alumina, low melting point glass paste It is preferable to use a laser melting method. When glass frit is used, powder glass mixed with acrylic resin as a binder may be used.

Example 1
1. Preparation of Dye Hereinafter, the method for preparing the dye of the present invention will be described in detail with reference to Examples, but the starting material, dye intermediate and preparation route are not limited thereto.

(1) Preparation Example 1
(Preparation of Exemplified Compound 14)
Dye 14 was prepared according to the scheme shown below.

(1-1) Synthesis of Compound 1-3 0.58 g of Compound 1-1 and 0.82 g of Compound 1-2 were mixed in a mixed solvent of 1-butanol 7 mL and toluene 10 mL, and heated at 90 ° C. for 5 hours. Stir. Thereafter, the reaction solution was concentrated, and the resulting residue was purified by column chromatography to obtain 0.40 g of compound 1-3.

(1-2) Synthesis of Compound 1-5 0.38 g of Compound 1-3 and 0.2 g of Compound 1-4 were mixed in a mixed solvent of 5 mL of 1-butanol and 8 mL of toluene, and 90 ml of triethylamine was added thereto. The mixture was heated and stirred at 4 ° C. for 4 hours. Thereafter, the reaction solution was concentrated, and the resulting residue was purified by column chromatography to obtain 0.40 g of Compound 1-5.

(1-3) Synthesis of Compound 14 0.4 g of Compound 1-5 and 0.4 g of morpholine were mixed in 10 ml of acetonitrile and cooled on ice. 0.04 g of tetrakis (triphenylphosphine) palladium (0) was added thereto, and the reaction was performed for 3 hours. Thereafter, the reaction solution was concentrated, and the resulting residue was purified by column chromatography to obtain 0.2 g of Compound 14. When identification was performed by Millimas, the following results were obtained.
Mass measured value (m / z); (M + H) ⁺ : 1180.7051
Mass calculated value (m / z); (M + H) ⁺ : 1180.7058 (C ₇₁ H ₉₈ N ₅ O ₈ S)

(2) Preparation Example 2
(Preparation of dye 19)
Dye 19 was prepared according to the scheme shown below.

(2-1) Synthesis of Compound 2-2 0.41 g of Compound 1-3 and 0.25 g of Compound 2-1 were mixed in a mixed solvent of 5 mL of 1-butanol and 8 mL of toluene. The mixture was heated and stirred at 4 ° C. for 4 hours. Thereafter, the reaction solution was concentrated, and the resulting residue was purified by column chromatography to obtain 0.48 g of compound 2-2.

(2-2) Synthesis of Compound 19 0.45 g of Compound 2-2 and 0.41 g of morpholine were mixed in 10 ml of acetonitrile and cooled on ice. Thereto was added 0.06 g of tetrakis (triphenylphosphine) palladium (0) and reacted for 4 hours. Thereafter, the reaction solution was concentrated, and the resulting residue was purified by column chromatography to obtain 0.25 g of Compound 19. When identification was performed by Millimas, the following results were obtained.
Mass measured value (m / z); (M + H) ⁺ : 1210.6797
Mass calculated value (m / z); (M + H) ⁺ : 1210.6800 (C ₇₁ H ₉₆ N ₅ O ₁₀ S)

(3) Preparation Example 3
(Preparation of dye 67)
Compound 67 was prepared according to the scheme shown below.

(3-1) Synthesis of Compound 3-3 1.08 g of Compound 3-1, 1.04 g of Compound 3-2 and 1 mL of triethylamine were mixed in a mixed solvent of 5 mL of 1-butanol and 15 mL of toluene, and 100 ° C. And stirred for 6 hours. Thereafter, the reaction solution was concentrated, and the resulting residue was purified by column chromatography to obtain 0.32 g of Compound 3-3.

(3-2) Synthesis of Compound 67 0.25 g of Compound 3-3 and 0.10 g of Compound 3-4 were mixed in a mixed solvent of 5 mL of 1-butanol and 5 mL of toluene, and heated at 90 ° C. for 3 hours. Stir. Thereafter, water and ethyl acetate were added to the reaction solution to perform extraction / separation, and the ethyl acetate layer was concentrated. The obtained residue was purified by column chromatography to obtain 0.13 g of 67. When identification was performed by Millimas, the following results were obtained.
Mass measured value (m / z); (M + H) ⁺ : 1773.9112
Mass calculated value (m / z); (M + H) ⁺ : 1773.9116 (C ₁₀₇ H ₁₃₃ N ₆ O ₁₁ S ₃ )

  By the same method, the dye of general formula (1) of the present invention used in the experiment was prepared. Moreover, the pigment | dye represented by general formula (I) of this invention was prepared referring to the patent 4576494 and the method quoted in the said gazette.

(Measurement of maximum absorption wavelength of dye)
The maximum absorption wavelength of the dye used was measured. The results are shown in the table. The measurement was performed with a spectrophotometer (U-4100 (trade name), manufactured by Hitachi High-Tech), and the solution was adjusted to a concentration of 2 μM using ethanol.

Example 2
1. Preparation of Titanium Dioxide Dispersion 15 g of titanium dioxide fine particles (Nippon Aerosil Co., Ltd., Degussa P-25), water 45 g, dispersant (Aldrich, Triron X −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. Preparation of electrode 1A A 20 mm × 20 mm conductive glass plate coated with fluorine-doped tin oxide (Asahi Glass Co., Ltd., trade name: TCO glass-U, surface resistance: about 30 Ω / m ² ) was prepared. After applying an adhesive tape for spacers to both ends of the conductive layer side (a portion having a width of 3 mm from the end), 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 the table (concentration: 2 × 10 ⁻⁴ mol / L) for 1 hour. The semiconductor-coated glass plate on which the dye was adsorbed was immersed in 4-tert-butylpyridine for 15 minutes, then washed with ethanol and naturally dried to obtain a titanium oxide fine particle layer (electrode A) on which the dye was adsorbed. The thickness of the dye-sensitized titanium oxide fine particle layer of the electrode A 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 acetonitrile as a solvent, a solution containing 0.5 mol / L of 1-methyl-3-hexylimidazolium iodine salt electrolyte and 0.05 mol / L of iodine was prepared. Nitrogen-containing polymer compound (1-1) is added to this solution so that the weight composition ratio when solvent + nitrogen-containing polymer compound + salt is 100 wt% is 10 wt%, and this nitrogen-containing polymer compound is further added. An electrophile (1-2) in an amount such that the molar ratio of the electrophilic site to the reactive nitrogen atom is 0.5 was mixed to obtain a uniform reaction solution.

On the other hand, on the dye-sensitized TiO ₂ 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 via 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 TiO ₂ fine particle layer by capillary action. Subsequently, it heated at 80 degreeC for 30 minutes, and the crosslinking reaction was performed.

  As a result, as shown in FIG. 1, from a conductive support 1 made of conductive glass (with a conductive layer formed on a transparent glass substrate), a photoreceptor layer 2, a charge transfer layer 3, and platinum. Thus, a photoelectrochemical cell of the present invention in which a counter electrode 4 and a glass transparent substrate (not shown) were sequentially laminated was obtained.

3-1. Measurement of IPCE (Quantum Yield) IPCE at 400 to 900 nm of the produced photoelectrochemical cell was measured with an IPCE measuring device manufactured by Pexel. The IPCE at 850 nm of each photoelectrochemical cell is shown in the following table.
3-2. Measurement of photoelectric conversion efficiency Simulated without UV light by passing light of 500W xenon lamp (USHIO ELECTRIC CO., LTD.) Through AM1.5 filter (Oriel) and sharp cut filter (KenkoL-37, trade name) Sunlight was generated. The intensity of this light was 70 mW / cm ² . This simulated sunlight was irradiated to the photoelectrochemical cell produced as described above at 50 ° C., and the generated electricity was measured with a current-voltage measuring device (Keutley SMU238 type). This initial battery performance result shows that conversion efficiency (3.5% or more: AA, 2.5% or more and less than 3.5%: A, 2.0% or more and less than 2.5%: B, less than 2.0% : Evaluation by C), open circuit voltage and fill factor (open circuit voltage (V), fill factor: 0.6 or more: AA, 0.45-0.6: A, 0.3-0.45: B, Less than 0.3: evaluated by C).
Moreover, the reduction rate of the conversion efficiency after 1000-hour dark storage at 85 degreeC and the reduction rate of the conversion efficiency after 500-hour continuous light irradiation were also measured. The results of this durability test are as follows: AA when the rate of decrease after the test is 10% or less, A when the rate is 10 to 25%, B when 25% to 40%, and C when the rate of decrease is 40% or more. It was evaluated. These results are shown in the table below.
In sample numbers c11, c12, and c13, S-1, S-2, and S-3 were used as dyes, respectively. S-2 corresponds to the dye disclosed in JP2009-242379A, and S-1 and S-3 are dyes S-14 and S-18 disclosed in JP2000-195570A.

  From the above table, it can be seen that all the samples using the dye of the present invention are excellent in conversion efficiency, and that the conversion efficiency reduction rate after storage in the dark and the conversion efficiency reduction rate after continuous light irradiation are both low. .

Example 3
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. A dispersion containing anatase-type titanium oxide particles on this conductive film (anatase-type titanium oxide (P-25 (trade name) manufactured by Nippon Aerosil Co., Ltd.)) was added to 100 ml of a mixed solvent having a volume ratio of water and acetonitrile of 4: 1. 32 g of the mixture, and using a rotating / revolving mixing conditioner, uniformly dispersed and mixed to obtain a semiconductor fine particle dispersion), and then sintered at 500 ° C. to form a photosensitive layer having a thickness of 15 μm. Formed. In this photosensitive layer, the above-mentioned 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. The open circuit voltage and photoelectric conversion efficiency obtained in the table are shown. The open circuit voltage is indicated as AA when the voltage is 6.3 V or higher, A as 6.0 V or higher and lower than 6.3 V, B as 5.7 V or higher and lower than 6.0 V, and C as lower than 5.7 V. . Conversion efficiency is AA for 3.5% or more, A for 2.5% or more and less than 3.5%, B for 2.0% or more and less than 2.5%, and less than 2.0%. The thing was displayed as C.
In addition, in the following Table 7, the result of the photoelectric conversion element using the electrolyte solution which has not added the benzimidazole-type compound was also shown.

  From the results in the above table, it can be seen that all the dyes of the present invention have high conversion efficiency.

Example 4
(1) Formation of first photoelectric conversion layer 4.0 g of commercially available titanium oxide particles (manufactured by Teika Co., Ltd., average particle size 30 nm) and 20 ml of diethylene glycol monomethyl ether were dispersed by a paint shaker for 6 hours using hard glass beads and oxidized. A titanium suspension was made. Next, this titanium oxide suspension was applied to a glass plate to which a tin oxide conductive layer had been previously adhered using a doctor blade, pre-dried at 100 ° C. for 30 minutes, and then in an electric furnace at 500 ° C. for 40 minutes. Firing was performed to obtain a titanium oxide film.

  Separately, Ru-1 was dissolved in ethanol.

The concentration of this dye was 3 × 10 ⁻⁴ mol. Next, the glass plate on which film-like titanium oxide is formed is put in this solution, and after dye adsorption at 720 minutes at 60 ° C., drying is performed to obtain the first photoelectric conversion layer (sample A) of the present invention. It was.

(2) Formation of the second photoelectric conversion layer 4.0 g of commercially available nickel oxide particles (Kishida Chemical, average particle size 100 nm) and 20 ml of diethylene glycol monomethyl ether were dispersed with a paint shaker using glass beads for 8 hours to suspend nickel oxide. Liquid. Next, this titanium oxide suspension was applied to a glass plate to which a tin oxide conductive layer was adhered using a doctor blade, pre-dried at 100 ° C. for 30 minutes, and then baked at 300 ° C. for 30 minutes. A membrane was obtained.

Separately from this, the dye of the present invention and the comparative dye S-1 were dissolved in dimethyl sulfoxide, respectively.
The concentration of this dye was 0.5 × 10 ⁻⁴ mol. Next, the glass plate on which the film-like titanium oxide is formed is put in this solution, and dye adsorption is performed at 40 ° C. for 70 minutes, followed by drying to obtain the second photoelectric conversion layer (sample B) of the present invention. It was.

(3) The sample B is positioned on the sample A. A liquid electrolyte was put between these two electrodes, and this side surface was sealed with resin, and then a lead wire was attached to produce a photoelectric conversion element (element configuration C) of the present invention. In addition, the liquid electrolyte is a mixed solvent of acetonitrile / ethylene carbonate (volume ratio is 1: 4), tetrapropylammonium iodide and iodine, with respective concentrations of 0.46 mol / l and 0.06 mol / l. What was melt | dissolved so that it might become was used.

  Moreover, the transparent conductive glass plate which equipped the said sample A as one electrode and carry | supported platinum as a counter electrode was used. A liquid electrolyte was placed between the two electrodes, and this side surface was sealed with resin, and then a lead wire was attached to produce a photoelectric conversion element (element configuration D) of the present invention.

The obtained photoelectric conversion elements (element configurations C and D) were irradiated with light having an intensity of 1000 W / m ^{2 using} a solar simulator. Conversion efficiency is 6.5% or more for AA, 6.0% to less than 6.5% A, 5.0% to less than 6.0% B, less than 5.0%. This is shown in the table below as C.

  From the above table, it can be seen that all of the dyes of the present invention are excellent in photoelectric conversion efficiency and are effective even in this system.

Example 5
(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 material was formed was immersed in an ethanol solution of a sensitizing dye (mixed or single) described in the following table for 1 hour. 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 naturally 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 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 determined are shown in the following table. As a result, conversion efficiency of 7.5% or more is AA, 7.2% or more and less than 7.5% is A, 6.9% or more and less than 7.2% is B, 6.9% Less than C was evaluated as C.

吸着溶液濃度 色素１：１×１０^−４ｍｏ１／Ｌ
色素２：０．２×１０^−４ｍｏｌ／Ｌ

Adsorbed solution concentration Dye 1: 1 × 10 ⁻⁴ mo1 / L
Dye 2: 0.2 × 10 ⁻⁴ mol / L

  As apparent from Table 5 above, all the samples (electrochemical cells) prepared using the dye of the present invention showed a high conversion efficiency of 7.5% or more. On the other hand, all of the samples of the comparative examples had an insufficient conversion efficiency of less than 7.2%.

DESCRIPTION OF SYMBOLS 1 Conductive support body 2 Photoconductor layer 21 Dye 22 Semiconductor fine particle 3 Charge transfer body layer 4 Counter electrode 5 Photosensitive electrode 6 Circuit 10 Photoelectric conversion element 100 Photoelectrochemical cell

Claims (13)

A photoelectric conversion element having a laminated structure comprising a semiconductor fine particle layer adsorbed with a dye on a conductive support, a charge transfer body, and a counter electrode, wherein at least one of the dyes is represented by the following formula: A photoelectric conversion element having a structure represented by (1).

(In the formula, Q represents an aromatic ring. X ¹ and X ² represent a sulfur atom, a selenium atom, an oxygen atom, or CR ¹ R ^2. R ¹ and R ² represent an alkyl group. R and R ′ represent An alkyl group or an aromatic group, P ¹ represents an atomic group represented by the following formula P11 or P12, and P ² represents an atomic group necessary for forming a polymethine dye, provided that P ¹ and (It is different from P ^2. W ¹ represents a counter ion as necessary to neutralize the charge.)

^{(Wherein, R 5, R 6, R} 10, R 11 are, ^{.R 7, R 12} is sulfur atom represents an aromatic ring group which may have an aliphatic group, or an acidic group which may have an acidic group or ^.R 3 representing the formula ^{R a, R 4, R 8} is .R ⁹ represents a hydrogen atom or a substituent represents .n21 is an integer of 0 or more representing an oxygen atom or a substituent .N22, is n31 0 Or 1)

(R ¹³ and R ¹⁴ in the formula R ^A represent a cyano group or an acidic group.) The photoelectric conversion element according to claim ^1, wherein the P ¹ is the following formula P11-1 or P12-1.

(In the formula, R ³ , R ⁴ , R ⁶ , R ⁸ , R ⁹ , R ¹¹ , and n ²¹ are synonymous with formulas P11 and P12.)   The photoelectric conversion element according to claim 1, wherein the n22 and n31 are 0. The photoelectric conversion element according to claim ^1, wherein the P ¹ is represented by the following formula P11-2 or P12-2.

(In the formula, R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ , R ¹⁰ , and n ²¹ have the same meanings as P11 and P12.)   The photoelectric conversion element according to any one of claims 1 to 4, wherein the n21 is 0 or 1. The photoelectric conversion element according to claim 1, wherein R ⁹ is represented by the following formula R91 or R92.

(In the formula R92, R ¹⁵ represents a hydrogen atom or an alkyl group.) The photoelectric conversion element according to claim 1, wherein R ⁹ is an oxygen atom. The photoelectric conversion device according to any one of claims 1 to 7 atoms forming the P ² are represented by the following formula P21 or the following formula P22.

(In the formula, R ²¹ , R ²² and R ²³ represent a hydrogen atom or a substituent. Ar ¹ represents a substituent having a σp value of 0 or less in Hammett's rule or an aromatic ring group having a π-excess heterocyclic group. N41 represents an integer of 0 or more.) The photoelectric conversion device according to claim 1, wherein Ar ¹ is represented by the following formula R ^C1 , R ^C2 , or R ^C3 .

(In the formulas R ^{C1 to} R ^C4 , Y represents S, NR ²⁴ , or C (R ²⁵ ) _2. R ²⁴ represents an alkyl group, R ²⁵ represents a substituent, and A represents an aromatic ring. ^{26 to} R ²⁹ each represents a hydrogen atom or a substituent, E represents S, NR ³⁰ , or O. R ³⁰ represents an alkyl group, D represents a substituent having a σp value of 0 or less in Hammett's rule, and B represents Represents an aromatic ring, X represents SR ^e , OR ^e , NR ^e ₂ , R ^e represents an alkyl group, an aromatic group, or a heterocyclic group, R ^d represents a substituent, nd is an integer of 0 to 4 * Represents a bond, and may be linked through a methine chain or directly in a double bond as seen in Formulas P21 and P22. K is a positive integer.) The dye represented by the formula (1), wherein P ¹ is an electron acceptor, P ² is a donor, and the dye constitutes a donor-acceptor type molecule. The photoelectric conversion element of Claim 1. The photoelectric conversion element of any one of Claims 1-10 in which the said photoreceptor further has the pigment | dye represented by following formula (I).
Mz (LL ¹ ) _m1 (LL ² ) _m2 (X) _m3 · CI: Formula (I)
[In Formula (I), Mz represents a metal atom. LL ¹ represents a bidentate ligand represented by the following formula LL1. LL ² represents a bidentate or tridentate ligand represented by the following formula LL2. X represents a monodentate or bidentate ligand. m1 represents an integer of 0 to 3. m2 represents an integer of 1 to 3. m3 represents an integer of 0-2. CI represents a counter ion when a counter ion is required to neutralize the charge. ]

(In Formula LL1, R ⁵¹ and R ⁵² represent an acidic group. R ⁵³ and R ⁵⁴ represent a substituent. R ⁵⁵ and R ⁵⁶ represent an alkyl group or an aromatic ring group. D1 and d2 are 0-5. L ¹ and L ² represent a conjugated chain, a ¹ and a ² represent an integer of 0 to 3, d 3 represents 0 or 1, b 1 and b 2 represent an integer of 0 to 3)

(In formula LL2, Za, Zb and Zc represent an atomic group capable of forming a 5- or 6-membered ring. C represents 0 or 1. However, at least one of the rings formed by Za, Zb and Zc is Has an acidic group.)   A photoelectrochemical cell provided with the photoelectric conversion element of any one of Claims 1-11. A dye compound having a structure represented by the following formula (1).

(In the formula, Q represents an aromatic ring. X ¹ and X ² represent a sulfur atom, a selenium atom, an oxygen atom, or CR ¹ R ^2. R ¹ and R ² represent an alkyl group. R and R ′ represent An alkyl group or an aromatic group, P ¹ represents an atomic group represented by the following formula P11 or P12, and P ² represents an atomic group necessary for forming a polymethine dye, provided that P ¹ and P ² is different, W ¹ represents the counter ion as needed to neutralize the charge.)

^{(Wherein, R 5, R 6, R} 10, R 11 is ^.R 7 which represents an aliphatic group or an aromatic ring ^{group, R 12} is ^.R 3 representing a sulfur atom or the following formula ^{R A, R 4, R 8} Represents a hydrogen atom or a substituent, R ⁹ represents an oxygen atom or a substituent, n21 represents an integer of 0 or more, and n22 and n31 represent 0 or 1.)

(R ¹³ and R ¹⁴ in the formula R ^A represent a cyano group or an acidic group.)

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