KR101505790B1 - Photoelectric conversion element, photoelectrochemical cell, and dye for use therein - Google Patents

Abstract

(식 중, Q 는 방향 고리를 나타낸다. X¹, X² 는 황 원자, 셀렌 원자, 산소 원자, 또는 CR¹R² 를 나타낸다. R¹, R² 는 알킬기를 나타낸다. R, R'는 알킬기 또는 방향족기이다. P¹ 은 특정한 원자군을 나타낸다. P² 는 폴리메틴 색소를 형성하는 데에 필요한 원자군을 나타낸다. 단, P¹ 과 P² 는 상이한 것으로 한다. W¹ 은 전하를 중화시키는 데에 필요한 경우의 카운터 이온을 나타낸다.) (PROBLEMS TO BE SOLVED BY THE INVENTION) A photoelectric conversion element, a photoelectrochemical cell, and a dye used therefor, which exhibit a high IPCE in the long wavelength region to achieve photoelectric conversion efficiency and excellent durability, are provided.
A photovoltaic device comprising a photoconductor having a semiconductor fine particle layer on which a dye is adsorbed on a conductive support, a charge carrier, and a counter electrode, wherein at least one of the above dyes is represented by the following formula (1) Type photoelectric conversion element.

(In the formula, represents the Q is aromatic ring. X ^1, X ² represents a sulfur atom, a selenium atom, an oxygen atom, or ^{CR 1 R 2. R 1,} R 2 represents an alkyl group. R, R 'is an alkyl group or an aromatic group. P ¹ represents a specific group of atoms. P ² represents a group of atoms necessary for forming a polymethine dye. However, P ¹ and P ² will be different. W ¹ is to neutralize the charge Represents the counter ion in case of need.

Description

PHOTOELECTRIC CONVERSION ELEMENT, PHOTOELECTROCHEMICAL CELL, AND DYE FOR USE THEREIN}, a photoelectric conversion element, a photoelectrochemical cell,

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

Photoelectric conversion elements are used in various optical sensors, copying machines, solar cells, and the like. In this photoelectric conversion element, various methods such as a method using a metal, a method using a semiconductor, an method using an organic pigment or a dye, or a combination thereof have been put to practical use. Among them, a solar cell using solar energy of a non-heavily doped solar cell uses clean energy that is unnecessary for fuel and is expected to be put into practical use in earnest. Of these, silicon-based solar cells have been under development for a long time. There is policy consideration of each country and diffusion is proceeding. However, silicon is an inorganic material, and throughput and molecular modification are naturally limited.

Therefore, the research of the dye-sensitized solar cell is energetically performed. Particularly, it was the result of research by Graetzel et al. Of Lausanne University of Technology in Switzerland. They adopted a structure in which a dye comprising a ruthenium complex is fixed on the surface of a porous titanium oxide thin film to realize a conversion efficiency of amorphous silicon level. As a result, dye-sensitized solar cells have attracted attention from researchers in the world of hematology.

Patent Document 1 describes a dye-sensitized photoelectric conversion device using semiconductor fine particles increased or decreased by a ruthenium complex dye by applying this technique. However, the conventional ruthenium complex dye can be photoelectrically converted by using visible light, but since it can hardly absorb infrared light having a longer wavelength than 700 nm, the photoelectric conversion ability in the infrared region tends to be lowered. In addition, it is demanded that solar power generation is carried out not only by expensive rare metals such as ruthenium, but also by diffusion.

Therefore, research on photoelectric conversion elements using pigments other than metal complexes is also under way. The present applicant first developed a device using a specific polymethine dye (see Patent Document 2). As a result, a device exhibiting high photoelectric conversion characteristics in near-infrared to infrared regions has been completed. Patent Document 3 discloses that a high photoelectric conversion efficiency is achieved in a long wavelength region of 600 nm or more by using an asymmetric bis-squarylium dye.

U.S. Patent No. 5463057 Japanese Patent No. 4217320 Specification Japanese Patent Application Laid-Open No. 2009-242379

According to the technique described in Patent Document 2 and the like, a device capable of achieving high photoelectric conversion efficiency using a wide wavelength region without requiring a metal complex has been provided. However, the inventors of the present invention aimed at the development of a photoelectric conversion element which is not sufficient in its performance and exhibits higher characteristics, in view of its role as a full-scale supply source of green energy.

In view of the present situation of the art, the present invention provides a high IPCE (Incident Photon to Current Conversion Efficiency) in a wavelength range exceeding 800 nm, achieving high photoelectric conversion efficiency, A photoelectric conversion element having excellent durability, a photoelectrochemical cell, and a dye used therefor.

The above problem has been solved by the following means.

(1) A photoelectric conversion element having a laminate structure including a photoconductor having a semiconductor fine particle layer on which a dye is adsorbed, a charge carrier, and a counter electrode on a conductive support, wherein at least one of the above- 1). ≪ / RTI >

[Chemical Formula 1]

(In the formula, represents the Q is aromatic ring. X ^1, X ² represents a sulfur atom, a selenium atom, an oxygen atom, or ^{CR 1 R 2. R 1,} R 2 represents an alkyl group. R, R 'is an alkyl group Or an aromatic group, P ¹ represents an atomic group represented by the following formula P11 or P ¹² , P ² represents an atomic group necessary for forming a polymethine dye, provided that P ¹ and P ² are different from each other And W ¹ represents the counter ion when necessary to neutralize the charge.

(2)

(In the formula, R ^5, R ^6, R ^10, R ¹¹ is a case of having an acidic group represents an a aromatic ring which if having an aliphatic group, or an acid with a. R ^7, R ¹² is a sulfur atom or the formula R ^A represents ^{a. R 3, R 4, R} 8 represents a hydrogen atom or a substituent. R ⁹ is an oxygen atom or a substituent. n21 represents an integer of 0 or more. n22, n31 represents 0 or 1.)

(3)

(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 P ¹ is the following formula P11-1 or P12-1.

[Chemical Formula 4]

(Wherein R ³ , R ⁴ , R ⁶ , R ⁸ , R ⁹ , R ¹¹ and n ²¹ have the same meanings as in formulas P ¹¹ and P 12)

(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 P ¹ is represented by the following formula P11-2 or P12-2.

[Chemical Formula 5]

(Wherein R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ , R ¹⁰ and n ²¹ have the same meanings as P 11 and P 12)

(5) The photoelectric conversion element according to any one of (1) to (4), wherein 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.

[Chemical Formula 6]

(Wherein 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 the group of atoms forming P ² is represented by the following formula P21 or P22.

(7)

^{(Wherein, R 21, R 22, R} 23 represents a hydrogen atom or a substituent. Ar ¹ represents an aromatic ring having Hammett Chick (則) σp value is 0 or less substituent, or π over-based group heterocyclic ring in. 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 , R ^C3 , and R ^C4 .

[Chemical Formula 8]

(Wherein R ^C1 ~ R ^C4, Y represents a S, NR ^24, or _{^{C (R 25) 2. R}} 24 represents an alkyl group. R ²⁵ represents a substituent. A represents an aromatic ring. R ²⁶ ~ R ²⁹ represents a hydrogen atom or a substituent. E represents an ^{S, NR 30, O. R} 30 represents an alkyl group. D represents the σp value of the substituent less than or equal to zero in the Hammett law. B 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 represents an integer of 0 to 4, Represents a hand (binding hand), and may be connected via a methine chain, as shown in the formulas P21 and P22, or may be a double bond, and may be directly connected, where k is a positive integer.

(10) In the dye represented by the above formula (1), it is preferable that P ¹ is an electron acceptor, P ² is a donor, and the dye is a donor / acceptor type molecule. (9). ≪ / RTI >

(11) The photoelectric conversion element according to any one of (1) to (10), wherein the photoconductor further has a dye represented by the following formula (I).

_{^{Mz (LL 1) m1 (LL}} 2) m2 (X) m3 · CI: formula (I)

[In the formula (I), Mz represents a metal atom. LL ¹ represents a 2-position ligand represented by the following formula LL ¹ . LL ² represents a 2-left or 3-position ligand represented by the following formula LL2. X represents a 1-left or 2-position ligand. m1 represents an integer of 0 to 3; m2 represents an integer of 1 to 3; and m3 represents an integer of 0 to 2. CI represents the counter ion when counter ions are required to neutralize charge.]

[Chemical Formula 9]

(In the formula LL1, R ⁵¹ and R ^{52 each} represent an acidic group, R ⁵³ and R ^{54 each} represent a substituent, R ⁵⁵ and R ^{56 each} represent an alkyl group or an aromatic ring group, and d1 and d2 represent an integer of 0 to 5 . L ¹ and L ² represents a conjugated chain. a1 and a2 represents an integer of 0 to 3. d3 represents 0 or 1. b1 and b2 represents an integer of 0 to 3.)

[Chemical formula 10]

(In formula (LL2), Za, Zb and Zc represent a group of atoms capable of forming a 5 or 6-membered ring, and c represents 0 or 1. provided that at least one of the rings formed by Za, Zb and Zc 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).

(11)

(In the formula, represents the Q is aromatic ring. X ^1, X ² represents a sulfur atom, a selenium atom, an oxygen atom, or ^{CR 1 R 2. R 1,} R 2 represents an alkyl group. R, R 'is an alkyl group Or an aromatic group, P ¹ represents an atomic group represented by the following formula P11 or P ¹² , P ² represents an atomic group necessary for forming a polymethine dye, provided that P ¹ and P ² are different from each other And W ¹ represents the counter ion when necessary to neutralize the charge.

[Chemical Formula 12]

(In the ^{formula, R 5, R 6, R} 10, R 11 represents an aliphatic group or an aromatic ring. R ^7, R ¹² denotes a sulfur atom or the formula ^{R A. R 3, R 4} , R 8 is hydrogen N21 represents an integer of 0 or more, and n22 and n31 represent 0 or 1.) In the formula, R < ⁹ > represents an oxygen atom or a substituent.

[Chemical Formula 13]

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

In the present specification, an aromatic ring is used to mean an aromatic ring and heterocyclic rings (aliphatic heterocyclic rings and aromatic heterocyclic rings). The carbon-carbon double bond may be either E-type or Z-type. When plural substituents or ligands are simultaneously defined at the same time, the respective substituents or ligands may be the same or different. When a plurality of substituents or ligands are adjacent to each other, they may be connected to each other or may be ringed to form a ring.

The photoelectric conversion element and the photoelectrochemical cell of the present invention exhibit high IPCE in the wavelength range 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 used in the photoelectric conversion element and photoelectrochemical cell exhibiting high performance.

These and other features and advantages of the present invention will become more apparent from the following description with reference to the accompanying drawings, as appropriate.

1 is a cross-sectional view schematically showing one embodiment of the photoelectric conversion element of the present invention.

The photoelectric conversion element of the present invention comprises a photoconductor having a semiconductor fine particle layer on which a sensitizing dye having a specific structure is adsorbed. The dye compound has functional group (P ¹ , P ² ) having different functionalities on the right and left of the parent of the recurring structure (group of cyclic atoms sandwiched between P ¹ and P ^{2 in} the formula (1)). This structure promotes the localization of HOMO (highest point orbital) / LUMO (lowest borehole) on the one hand as π electrons become non-localized in the molecule. What is important here is not merely an asymmetric structure but adopts a nucleus unique to the central ring structure and introduces an electron attractive rhodanine residue to the atom group (P ¹ ) on one side. As a result, 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 high durability was achieved.

This reason includes the point of unexplained explanation, but it can be explained as follows including the estimation. That is, when the specific dye is adsorbed to the semiconductor fine particles such as titania, the localized side of the HOMO functions as a donor in the molecule, and conversely, the localized side of the LUMO functions as an acceptor. Thus, it is considered that electrons are efficiently sent from the LUMO disposed on the semiconductor fine particle side to the semiconductor fine particles, and conversely, reverse movement of electrons is suppressed, thereby achieving high photoelectric conversion efficiency. It is presumed that the high electron withdrawing property of the rhodanine residue and the molecular structure containing the nuclei of the recursive structure contributed to the quantification of properties and the durability in the ultrahigh wavelength region. Hereinafter, the present invention will be described in detail on the basis of preferred embodiments thereof.

[Device Structure]

Preferred embodiments of the photoelectric conversion element of the present invention will be described with reference to the drawings. 1, the photoelectric conversion element 10 includes an electroconductive substrate 1, a photoconductor layer 2, a charge carrier layer 3, and a counter electrode 4 disposed on the electroconductive substrate 1 in this order ). The light receiving electrode 5 is constituted by the conductive support 1 and the photosensitive layer 2. The photoconductor layer 2 has conductive fine particles 22 and a sensitizing dye 21. The dye 21 is adsorbed on the conductive fine particles 22 at least in part thereof (the dye is in an adsorption equilibrium state , Or may be present in some charge transport layer). The electroconductive support 1 on which the photoconductor layer 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 consisting of a conductive support 1 and a photoconductor layer (semiconductor film) 2 containing semiconductor fine particles 22 on which a dye 21 to be coated and formed on the conductive support is adsorbed. Light incident on the photoconductor layer (semiconductor film) 2 excites the dye. Here, the dye has high energy electrons. Thus, the electrons are transmitted from the dye 21 to the conduction band of the semiconductor fine particles 22 and reach the conductive support 1 by diffusion. At this time, the molecules of the dye 21 are oxidized. Electrolytes on the electrode are excited while being excited while working in an external circuit, and the oxidized dye receives electrons from a reducing agent (for example, I < ^- >) in the electrolyte and returns to the pigment in the ground state, thereby acting as a photoelectrochemical cell. At this time, the light-receiving electrode 5 acts as a negative electrode of the battery.

As can be seen from the working principle of the device, it is generally desirable to reduce the HOMO / LUMO gap of the dye in order to achieve a longer wavelength of increase / decrease of the sensitizing dye. Therefore, it is conceivable to increase the energy level of the HOMO of the dye and to lower the LUMO as needed. By raising 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 (e.g., I < ^- >) in the electrolytic solution becomes smaller, so that the reduction rate of the oxidized dye by the reducing agent becomes slower. In addition, when the energy level of the LUMO 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. As a result, the electron injection efficiency is lowered and the short circuit current and the fill factor are reduced. It is difficult to increase the conversion efficiency.

On the other hand, it can be considered that the energy level of the conductive band of the semiconductor fine particles is lowered and the electron injection efficiency is increased. In this method, although the short-circuit current can be increased, the open-circuit voltage is reduced.

On the other hand, according to the preferred embodiment of the present invention, along with the reduction of the band gap, the localization of the above-described two orbits is greatly promoted and the improvement of the photoelectric conversion efficiency and the improvement of the durability at the ultra- The molecular design can be performed.

The photoelectric conversion element of this embodiment has a photoconductor having a porous semiconductor fine particle layer on which a dye described later is adsorbed on a conductive support. At this time, there may be dissociated in some electrolytes in the dye. The photoreceptor is designed according to purposes, and may be a single layer structure or a multilayer structure. The photoreceptor of the photoelectric conversion element of the present embodiment contains semiconductor fine particles adsorbed with specific sensitizing dyes and has high sensitivity and can obtain high conversion efficiency when used as a photoelectrochemical cell. In the present specification, based on what is shown in the present specification, the side of the counter electrode 4, which is the light receiving side, is set to the direction of the upper part (top part) ) Side is set to the lower (bottom) direction.

[Coloring matter]

(A coloring matter comprising the compound of (1)

In the photoelectric conversion element of the present invention, a dye comprising at least the following compound (1) is used. (1) may also be represented by a resonance structure different from the formula. This is the same and for any group of atoms of formula (P11, P12, Ar ^1, and so on) to be introduced to (1), will be interpreted as a conjugated structure of the matching as a whole molecule.

[Chemical Formula 14]

· Q

In the 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. As the heterocyclic ring, the ring structure of the exemplified substituent HArex of the latter-mentioned example may be mentioned.

X ¹ , X ²

X ¹ and X ² represent a sulfur atom, a selenium atom, an oxygen atom, or CR ¹ R ² . Wherein R ¹ and R ² represent an alkyl group. Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms and include methyl, ethyl, isopropyl, t-butyl, pentyl, hexyl, heptyl, decyl, 1- ethylhexyl, Methyl, ethyl, isopropyl, decyl, 1-ethylpentyl, 2-ethoxyethyl and benzyl are more preferable, and methyl, ethyl, decyl, 2-ethoxyethyl Is particularly preferable. Hereinafter, examples and preferred 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 relationship between X ¹ and X ² and the relationship between NR and NR 'may be inverted (in other words, NR may be lower and NR' may be higher).

R, R '

R and R 'are an alkyl group or an aromatic group. As the alkyl group, the alkyl group Rex may be mentioned. Examples of the aromatic group include an aryl group having 6 to 26 carbon atoms and phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl and 3-methylphenyl are preferable, and phenyl, 4-methoxyphenyl, More preferred is 3-methylphenyl. Hereinafter, examples and preferred examples of the aromatic group (aryl group) are referred to as an aromatic group " Arex ".

· P ¹

P ¹ represents an atom 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 are assumed to be different. Here, the two different atom groups are different from each other in the range of exhibiting the effect of the present invention, and the specific structure thereof is not limited. Typically, in the dye represented by the above formula (1), it is preferable that P ¹ constitutes an electron acceptor, P ² constitutes a donor, and the dye constitutes a donor · acceptor type molecule. Here, the donor acceptor type dye refers to a dye that causes a donor moiety in a dye to cause photoluminescent electron transfer in a molecule that transfers electrons to an acceptor moiety through a conjugate in a molecule when light is irradiated.

· W ¹

And W ¹ represents a counter ion in the case where a counter ion is required to neutralize the charge. In general, whether a dye has a cation, an anion, or a net ionic charge depends on the chromophore and the substituent in the dye. When the dye having the structure of the general formula (1) has a dissociative substituent, it may dissociate 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, it is, for example, 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. (E.g., fluoride ion, chloride ion, bromide ion, iodide ion), substituted arylsulfonate ion (e.g., p-toluenesulfonate ion, p-chlorobenzenesulfonate ion), aryl Naphthalene disulfonic acid ion, 2,6-naphthalene disulfonic acid ion), alkylsulfuric acid ion (for example, methylsulfate ion), sulfuric acid (for example, Ion, thiocyanic acid ion, perchloric acid ion, tetrafluoroboric acid ion, picric acid ion, acetic acid ion, trifluoromethanesulfonic acid ion and the like. As the charge balance counter ion, an ionic polymer or another dye having a reverse charge to the dye may be used, or a metal complex ion (for example, bisbenzene-1,2-dithiolato nickel (III)) may be used .

[Chemical Formula 15]

R ⁵ , R ⁶ , R ¹⁰ , R ¹¹

In the formulas, R ⁵ , R ⁶ , R ¹⁰ and R ¹¹ represent an aliphatic group which may have an acidic group or a aromatic cyclic group which may have an acidic group. Examples of the aliphatic group include the following cycloalkyl group CRex in addition to the alkyl group Rex. As the CRex, a cycloalkyl group preferably having 3 to 20 carbon atoms is preferable, and cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl and the like are more preferable. As the aromatic ring group, the following heterocyclic group HArex may be mentioned in addition to the aromatic group Arex. HArex is preferably a heterocyclic group having 2 to 20 carbon atoms, more preferably 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-oxazolyl, and the like.

The acidic group is a substituent having a proton of dissociation, and examples thereof include a carboxyl group, a phosphonyl group, a phosphoryl group, a sulfo group, a boric acid group and the like, or a group having any one of them, preferably a carboxyl group or a group to be. In addition, the acid group may adopt a dissociated form by emitting protons, or may be a salt. The acidic group is preferably a carboxyl group, a sulfonic acid group, a phosphonyl group, a phosphoryl group, or a salt thereof. The acidic group may be a bond which is bonded through a linking group, and examples thereof include a carboxyvinylene group, a dicarboxyvinylene group, a cyanocarboxyvinylene group, and a carboxyphenyl group. The acid group and the preferred range thereof may be referred to as acid group Ac.

R ⁷ , R ¹²

R ⁷ and R ¹² represent a sulfur atom or the following formula: R ^A.

[Chemical Formula 16]

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 a combination of a cyano group and an acid group is preferable. The preferable acid group is the acid group Ac.

R ³ , R ⁴ , R ⁸

R ³ , R ⁴ and R ⁸ represent a hydrogen atom or a substituent. As the substituent, a substituent T can be mentioned. 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: R 91 or R 92.

[Chemical Formula 17]

Wherein R92, R ¹⁵ represents a hydrogen atom or an alkyl group; As the alkyl group, the alkyl group Rex may be mentioned.

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

In the present invention, it is preferable that P ¹ is the following formula P11-1 or P12-1.

[Chemical Formula 18]

R ³ , R ⁴ , R ⁶ , R ⁸ , R ⁹ , R ¹¹ and n ²¹ have the same meanings as in formulas P ¹¹ and P 12.

In the present invention, it is also preferable that P ¹ is represented by the following formula P 11-2 or P 12-2.

[Chemical Formula 19]

R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ , R ¹⁰ and n ²¹ have the same meanings as P 11 and P 12.

In the present invention, it is preferable that P ² is the following formula P 21 or P ²² .

[Chemical Formula 20]

R ²¹ , R ²² , R ²³

In the formula, R ²¹ , R ²² and R ²³ represent a substituent. Examples of the substituent include a later substituent T. 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, more preferably 0 to 2.

Ar ¹

Ar ¹ represents an aromatic ring group having a substituent having a σp value of 0 or less in Hammett's rule or a π-heterocyclic ring group having a substituent having a σp value of 0 or less. The π excess system heterocyclic ring means a residue of a π-excess system heterocyclic compound. means a state in which the number of pi electron systems exceeds the number of atoms constituting the ring, including a pair of electrons such as a pi-excess egg, typically a nitrogen atom. For details, reference can be made to, for example, " New Heterocyclic Compound Foundation " (Kodansha Scientific) p15.

Here, the substituent constant p value in the Hammett rule will be described. Hammett's law is an empirical rule proposed by L. P. Hammet in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives, but this is now widely accepted. Substituent constants obtained by Hammett's rule have σp and σm values, which can be found in many general Bibles. See, for example, J. A. Dean, Lange ' s Handbook of Chemistry, 12th Edition, 1979 (McGraw-Hill) or in Chemistry, 122, 96-103, 1979 (Nankodo), Chem. Rev., 1991, vol. 91, pp. 165-195.

Examples of the substituent having a substituent constant σ _p of 0 or less include an electron-donating substituent, and specific examples thereof include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, an alkylamino group and an arylamino group, Include an alkyl group, an alkoxy group, and an alkylamino group. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably Rex. The alkoxy group is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably methoxy, ethoxy, isopropyloxy, benzyloxy and the like. In a substituent having a? p value of 0 or less, the? p value is preferably -0.13 or less, more preferably -0.2 or less. Although there is no particular lower limit, it is practically at least -1.2.

Conversely, examples of the substituent constant p value being positive include a halogen atom, a nitro group, a cyano group, a sulfo group, a carboxyl group, a formyl group, an acyl group, a carbamoyl group, a sulfamoyl group, An aryloxycarbonyl group, an aryloxycarbonyl group, a perfluoroalkyl group, a heterocyclic group (e.g., a heterocyclic group is a pyridine ring, a pyrimidine ring, a 2-pyrimidinyl group, a 4-pyrimidyl group, 2-thienyl, 2-pyridyl, 3-pyridinyl and 4-pyridinyl), a phenyl group substituted with an electron-withdrawing group (the electron-withdrawing group is defined as the substituent constant σp A carboxyl group is preferable, and a 3-carboxyphenyl group or a 4-carboxyphenyl group). In the substituent in which the [sigma] p value is constant, the [sigma] p value is preferably 0.01 or more, more preferably 0.05 or more. There is no upper limit, but it is practically 1.4 or less.

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

It is preferable that Ar ¹ is represented by the following formulas R ^C1 , R ^C2 , R ^C3 , and R ^C4 .

[Chemical Formula 21]

· Y

Wherein Y represents S, NR ²⁴ , or C (R ²⁵ ) ₂ . R ²⁴ represents an alkyl group. Preferable examples of the alkyl group include Rex described above. R ²⁵ represents a substituent. As the substituent, a later substituent T can be mentioned.

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 a later substituent T. Preferably an alkyl group, an aryl group, a heterocyclic group and the like.

· E

E represents S, NR < ²⁹ > R ²⁹ represents an alkyl group. Preferable examples of the alkyl group include Rex described above.

· D

D represents a substituent having a? P value of 0 or less in the Hammett rule. For example, an alkoxy group, an amino group, an alkylamino group, an arylamino group, and a phenyl group substituted thereon.

· B

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

· X, R ^d , and nd

X represents SR ^e , OR ^e or NR ^e ₂ , and R ^e represents an alkyl group, an aromatic group or a heterocyclic group. R ^d represents a substituent. and nd represents an integer of 0 to 4. The substituent of R ^d is preferably the latter substituent T. Preferably an alkyl group, an aryl group, a heterocyclic group and the like.

* Indicates a binding hand and may be connected via a methine chain.

k is a positive integer. Is preferably 1 to 4, more preferably 1 to 2.

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

[Chemical Formula 22]

In the formula, Q, P ¹ , X ¹ , X ² , R, R ', W ¹ , Ar ¹ and n ⁴¹ have the same meanings as in the formula (1) or P 21. R ²¹⁰ , R ²¹¹ , R ²¹² , R ²²⁰ , and R ²²¹ represent a hydrogen atom or a substituent, and preferred examples thereof are the same as those of R ²¹ , R ²² and R ²³ .

In the present specification, when the word "compound" is appended to the end or when it is represented by a specific name or chemical formula, the term "compound" is used in addition to the compound itself to mean salts, complexes and ions thereof. It is meant to include a derivative modified in a predetermined form within a range that exhibits a desired effect. In the present specification, when the substituent or ligand is referred to by its name, or when the word " group " is appended to the end thereof, it means that the group may have an arbitrary substituent in the range of exhibiting a desired effect. This also applies to compounds which do not specify substituted or unsubstituted rings. As the preferable substituent, the following substituent T can be mentioned.

As a preferable substituent which can be introduced (hereinafter referred to as substituent T)

(Preferably an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, (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, for example, (Preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.) (Preferably an aryl group having 6 to 26 carbon atoms such as phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl and 3-methylphenyl), a heterocyclic group Is a heterocyclic group having 2 to 20 carbon atoms, for example, 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2- An alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms such as methoxy, ethoxy, isopropyloxy, benzyloxy, etc.), aryl (Preferably an aryloxy group having 6 to 26 carbon atoms such as phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy and the like), an alkoxycarbonyl group Is an alkoxycarbonyl group having 2 to 20 carbon atoms, such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), an amino group (preferably an amino group having 0 to 20 carbon atoms, such as amino N, N-diethylamino, N-ethylamino, anilino), a sulfonamide group (preferably a sulfonamide group having 0 to 20 carbon atoms such as N, N-dimethylamino, N-dimethylsulfonamide, N-phenylsulfonamide and the like), an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms, 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 or benzoylamino), a cyano group or a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, An alkoxy group, an aryloxy group, an alkoxycarbonyl group, an amino group, an acylamino group, a cyano group or a halogen atom, more preferably an alkyl group, an alkenyl group, an alkenyl group, , A heterocyclic group, an alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group or a cyano group.

 The dye of the present invention represented by the general formula (1) has a maximum absorption wavelength in the ethanol solution, preferably in the range of 500 to 1300 nm, and more preferably in the range of 600 to 1100 nm.

Specific preferred examples of the dye represented by the general formula (1) of the present invention are shown below, but the present invention is not limited thereto. * Represents the position of the carbon atom bonded to the parent of the following general scheme. Bu represents a butyl group.

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≪ EMI ID =

(25)

(26)

(27)

(28)

[Chemical Formula 29]

(30)

(31)

(32)

[Table A]

The synthesis of a dye comprising a compound represented by the general formula (1) is described in Ukrainskii Khimicheskii Zhurnal, Vol. 40 (3), pp. 253-258, Dyes and Pigments, vol. 21, pp. 227-243, The description of the document, and the like.

For example, the exemplary dye 14 can be obtained by the following scheme. Other pigments can be obtained in the same way.

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

(A coloring matter comprising the compound of formula (I)

In the photoelectric conversion element and the photoelectrochemical cell of the present invention, it is preferable to use it in combination with the metal complex coloring matter. By using the metal complex dye together with the metal complex dye, it is possible to control the adsorption state of each other to achieve higher efficiency and durability.

As the metal complex dye, it is preferable to contain a dye comprising 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 represents a metal atom, LL ¹ represents a 2-position ligand represented by the following formula LL1, LL ² represents a 2-position or 3-position ligand represented by the following formula . X represents a ligand of 1 L or 2 L other than the LL ¹ and LL ^2. m1 represents an integer of 0 to 3. m2 represents an integer of 1 ~ 3. m3 represents an integer of 0 to 2 CI represents the counter ion when a counter ion is needed to neutralize the charge.)

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(Wherein R ⁵¹ and R ^{52 each} represent an acidic group, R ⁵³ and R ^{54 each} represent a substituent, R ⁵⁵ and R ^{56 each} represent an alkyl group or an aromatic group, and d 1 and d 2 represent an integer of 0 to 5. L ¹ and L ² represents a conjugated chain. a1 and a2 represents an integer of 0 ~ 3. b1 and b2 represents an integer of 0 ~ 3. d3 represents 0 or 1.)

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

Metal atom Mz

Mz represents a metal atom. Mz is preferably a metal that is capable of coordinating four or more times in coordination and more preferably Ru, Fe, Os, Cu, W, Cr, Mo, Ni, Pd, Pt, Co, Ir, Rh, to be. Particularly preferably Ru, Os, Zn or Cu, and most preferably Ru.

* LL ¹ (expression LL1)

· M1

m1 is an integer of 0 to 3, preferably 1 to 3, more preferably 1. When m1 is 2 or more, and may LL ¹ are be the same or different.

R ⁵¹ and R ⁵²

R ⁵¹ and R ⁵² each independently represent an acidic group. For example, a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxyl group trioxide (preferably a hydroxyl group trioxide carbon atoms of 1 to 20, for example, -CONHOH, -CON (CH ₃₎ OH and the like), phosphonium (For example, -OP (O) (OH) _2, etc.) and a phosphonyl group (for example, -P (O) (OH) ₂ and the like) and salts thereof, and preferably a carboxyl group, A sulfonyl group and a sulfonyl group, and more preferably a carboxyl group or a salt thereof. R ⁵¹ and R ⁵² may be substituted with any carbon atom on the pyridine ring.

R ⁵³ and R ⁵⁴

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

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

R ⁵⁵ and R ⁵⁶

In the formulas, R ⁵⁵ and R ⁵⁶ each independently represent an alkyl group or an aromatic ring group. The aromatic group is preferably an aromatic group having 6 to 30 carbon atoms, for example, phenyl, substituted phenyl, naphthyl, substituted naphthyl, and the like. The 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, 3-indolyl. Preferably a heterocyclic group having 1 to 3 electron hole groups, more preferably a thienyl group. The electron-donating group is preferably an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an amino group, an acylamino group (more preferable examples are the same as R ⁵³ and R ⁵⁴ ) More preferably an alkyl group, an alkoxy group, an amino group or a hydroxyl group, particularly preferably an alkyl group. R ⁵⁵ and R ⁵⁶ may be the same or different and are preferably the same.

R ⁵⁵ and R ⁵⁶ may be bonded directly 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 represent 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 may be substituted. When the ethenylene group has a substituent, the substituent is preferably an alkyl group, more preferably methyl. L ¹ and L ² are each independently preferably a conjugated chain having 2 to 6 carbon atoms, and it is preferable that thiophene, ethylene, butadienylene, ethynylene, butadienylene, methylethenylene or dimethylethenylene More preferred are ethenylene or butadienylene, with ethenylene being most preferred. L ¹ and L ² may be the same or different and are preferably the same. When the conjugated chain contains 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 to 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 b1 and b2 are both 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 and a cyclopentane ring.

A1 and a2

a1 and a2 each independently represent an integer of 0 to 3; It is at least the sum of a1 and a2 1, LL when the ligand is ¹ to have at least one acidic group, m1 in the general formula (I) should preferably be 2 or 3, more preferably 2. when a1 is 2 or more, R ⁵¹ may be the same or different and are, when a2 is 2 or greater, R ⁵² is may be the same or different. a1 is preferably 0 or 1, and a2 is preferably an integer of 0 to 2.

* LL ² (expression LL2)

· M ₂

m ₂ is an integer of 1 to 3, preferably 1 to 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 group of a nonmetal atom capable of forming a five-membered ring or a six-membered ring. The formed 5-membered ring or 6-membered ring may be substituted or unsubstituted, and may be monocyclic or bicyclic. 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, it is preferable to form an imidazole ring, an oxazole ring, a thiazole ring or a triazole ring, and in the case of a 6-membered ring, a pyridine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring . Among them, an imidazole ring or a pyridine ring is more preferable.

· C

and c represents 0 or 1. c is preferably 0, and LL ² is preferably a bidentate ligand.

The ligand LL ² is preferably represented by any one of the following general formulas (LL2-1) to (LL2-8), and is preferably represented by any of the general formulas (LL2-1), (LL2-2), (LL2-4) More preferably represented by the formula (LL2-2), particularly preferably by the formula (LL2-1) or (LL2-2), particularly preferably by the formula (LL2-1).

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In the formulas, R ¹⁰¹ to R ¹⁰⁸ independently represent an acidic group or a salt thereof. R ¹⁰¹ ~ R ¹⁰⁸ are, for example, a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxyl group trioxide (preferably a hydroxyl group trioxide carbon atoms of 1 to 20, for example, -CONHOH, -CON (CH ₃ (For example, -OP (O) (OH) ₂ ) or a phosphonyl group (for example, -P (O) (OH) ₂ or the like) or a salt thereof. R ¹⁰¹ to R ¹⁰⁸ are preferably a carboxyl group, a phosphoryl group or a phosphonyl group or a salt thereof, more preferably a carboxyl group or a phosphonyl group or a salt thereof, more preferably a carboxyl group or a salt thereof.

In the formulas, R ¹⁰⁹ to R ¹¹⁶ each independently represents a substituent and is 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 acyl group, an acyl group, an acyl group, an acyl group, an acyl group, an amide group, an acyloxy group, a carbamoyl group, an acylamino group, a cyano group or a halogen atom (preferable examples are the same as those of R ⁵³ and R ⁵⁴ ) An alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group or a halogen atom, and particularly preferably an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an amino group or an acylamino group.

In the formula, R ¹¹⁷ to R ¹²¹ each independently represent a hydrogen atom, an aliphatic group (preferably having 1 to 20 carbon atoms), an aromatic group (preferably having 6 to 26 carbon atoms), a heterocyclic group (Preferably a 5 or 6-membered ring), preferably an aliphatic group or an aromatic group, more preferably an aliphatic group having a carboxyl group. When the ligand LL ² contains an alkyl group, an alkenyl group or the like, they may be linear, branched, substituted or unsubstituted. When LL ² contains an aryl group, a heterocyclic group or the like, they may be monocyclic or bicyclic, substituted or unsubstituted.

In the formula, R ¹⁰¹ to R ¹¹⁶ may be bonded at any positions on the ring. Each of e1 to e6 independently represents an integer of 0 to 4, preferably an integer of 1 to 2. e7 and e8 each independently represent an integer of 0 to 4, preferably an integer of 1 to 3; e9 to e12 and e15 each independently represent an integer of 0 to 6; e13, e14 and e16 each independently represent an integer of 0 to 4; and each of e9 to e16 is independently an integer of 0 to 3.

When e1 ~ e8 is 2 or more, R ¹⁰¹ ~ R ¹⁰⁸ are may be the same or different, respectively, when e9 ~ e16 is 2 or more, R ¹⁰⁹ ~ R ¹¹⁶ are may be the same or different, respectively. R ¹⁰¹ to R ¹¹⁶ may be connected to each other or may be ring-opened to form a ring.

In addition, although the expression LL2-1 LL2-8 the substituent ~ R ¹⁰¹ ~ R ¹¹⁶ represents increasing the bonding hand to a predetermined aromatic ring, but is not limited to those substituted in the aromatic ring. In short, for example, in the formula LL2-1, R ¹⁰¹ and R ¹⁰⁹ are substituted in the pyridine ring on the left, but they may be substituted with the pyridine ring on the right.

* Ligand X

In the formula, X represents a 1-left or 2-position ligand. M3 representing the number of the ligands X represents an integer of 0 to 2, and m3 is preferably 1 or 2. When X is a one-coordinate ligand, m3 is preferably 2, and when X is a two-coordinate ligand, m3 is preferably 1. When m3 is 2 or more, X may be the same or different and X may be connected to each other.

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 such as acetyloxy, benzoyloxy, salicylic acid, glycyloxy, N, N-dimethylglycyloxy, oxalylene (- OC (O) C (O) O-), an acylthio group (preferably an acylthio group having 1 to 20 carbon atoms such as acetylthio and benzoylthio), a thioacyloxy group A thioacyloxy group having 1 to 20 carbon atoms such as thioacetyloxy group (CH ₃ C (S) O-)), a thioacylthio group (preferably having 1 to 20 carbon atoms For example, thioacetylthio (CH ₃ C (S) S-), thiobenzoylthio (PhC (S) S-)), an acylaminooxy group For example, N-methylbenzoylaminooxy (PhC (O) N (CH ₃ ) O-), acetylaminooxy (CH ₃ C (O) NHO-) Thiocarbamate group (preferably a carbon atom A thiocarbamate group having a number of 1 to 20, for example, N, N-diethylthiocarbamate), a dithiocarbamate group (preferably a dithiocarbamate group having 1 to 20 carbon atoms Group such as N-phenyldithiocarbamate, N, N-dimethyldithiocarbamate, N, N-diethyldithiocarbamate, N, N-dibenzyldithiocarbamate, etc. ), A thiocarbonate group (preferably a thiocarbonate group having 1 to 20 carbon atoms, such as ethyl thiocarbonate), dithiocarbonate (preferably having 1 to 20 carbon atoms (C ₂ H ₅ OC (S) S-)), a trithiocarbonate group (preferably a trithiocarbocyanine group having 1 to 20 carbon atoms, such as dithiocarbonate, for example, ethyldithiocarbonate (C ₂ H ₅ SC (S) S-)), an acyl group (preferably an acyl group having 1 to 20 carbon atoms, for example, An isothiocyanate group, a cyanate group, an isocyanate group, a cyano group, an alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms, such as acetyl or benzoyl), a thiocyanate group, , An arylthio group (preferably an arylthio group having 6 to 20 carbon atoms such as benzenethio, 1,2-phenylene dithio, etc.), an alkoxy group such as a methoxy group, (Preferably an alkoxy group having 1 to 20 carbon atoms, such as methoxy and the like) and an aryloxy group (preferably an aryloxy group having 6 to 20 carbon atoms, such as phenoxy, quinoline-8 (E.g., a chlorine atom, a bromine atom, an iodine atom and the like), a carbonyl group (e.g., a chlorine atom, a bromine atom, or an iodine atom) coordinated to a group selected from the group consisting of CO), dialkyl ketones (preferably dialkyl ketones having 3 to 20 carbon atoms such as acetone ((CH ₃ ) ₂ CO), etc.), 1,3-diketones (preferably, CH ₃ C (O) CH ₃ ), trifluoroacetylacetone (CF ₃ C (O) CH (CH ₃ ) _{= C (O-) CH 3)} , one methane Diffie feet _{(tC 4 H 9 C (O} ...) CH = C (O-) tC 4 H 9), dibenzoylmethane (PhC (O ...) CH = C ( O-) Ph), 3-chloroacetylacetone (CH ₃ C (O) CCl═C (O-) CH ₃ ), and the like), a carboxylic amide (preferably a carboxylic amide having 1 to 20 carbon atoms, For example, CH ₃ N═C (CH ₃ ) O-, -OC (═NH) -C (═NH) O- and the like), thiocarbamides (preferably thiocarnams having 1 to 20 carbon atoms the amide, for example, CH ₃ N = C (CH ₃₎ S-, etc.), or thiourea (preferably such thiourea, for example, carbon atoms, 1 ~ 20, NH (...) = C (S be done _{by) NH 2, CH 3 N (} ...) = C (S-) NHCH 3, (CH 3) 2 NC (S ...) N (CH 3) 2 , etc.) It represents a ligand. Also, "… Represents a coordination bond 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 A ligand coordinated with a group selected from the group consisting of a halogen atom, a cyano group, an isocyanate group, a cyano group, an alkylthio group, an arylthio group, an alkoxy group and an aryloxy group, Urea and more preferably an acyloxy group, an acylaminooxy group, a dithiocarbamate group, a thiocyanate group, an isothiocyanate group, a cyanate group, an isocyanate group, a cyano group or an arylthio group Or a ligand composed of a halogen atom, 1,3-diketone or thiourea, particularly preferably a ligand coordinated with a group selected from the group consisting of A ligand coordinated with 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 ligand composed of a halogen atom or a 1,3-diketone, Is a ligand coordinated with a group selected from the group consisting of a dithiocarbamate group, a thiocyanate group and an isothiocyanate group, or a ligand composed of 1,3-diketone. When the ligand X contains an alkyl group, an alkenyl group, an alkynyl group, an alkylene group or the like, they may be linear, branched, substituted or unsubstituted. When they contain an aryl group, a heterocyclic group, a cycloalkyl group, etc., they may be substituted or unsubstituted, and may be monocyclic or bicyclic.

When X is a bidentate ligand, X is an acyloxy group, an acylthio group, a thioacyloxy group, a thioacylthio group, an acylaminooxy group, a thiocarbamate group, a dithiocarbamate group, a thiocarbonate A ligand which is coordinated with a group selected from the group consisting of a dithiocarbonate group, a trithiocarbonate group, an acyl group, an alkylthio group, an arylthio group, an alkoxy group and an aryloxy group, It is preferably a ligand composed of a main amide, thiocarbamido, or thiourea. When X is a monovalent ligand, X is a ligand coordinated with 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, , A carbonyl, a dialkyl ketone, and a thiourea.

* Counter ion CI

CI in the general formula (I) represents a counter ion in the case where a counter ion is required for neutralizing the charge. In general, whether a dye is a cation or an anion, or whether it has a net ionic charge depends on the metals, ligands and substituents in the dye.

The dye of the general formula (I) may dissociate and have a negative charge due to the fact that the substituent has a dissociable group. In this case, the charge of the whole dye of formula (I) becomes electrically neutral 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, a tetraalkylammonium ion, a 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, fluoride ion, chloride ion, bromide ion, iodide ion, etc.), substituted arylsulfonate ion (e.g., p-toluenesulfonic acid ion, p-chlorobenzenesulfonic acid ion, (E.g., 1,3-benzene disulfonic acid ion, 1,5-naphthalene disulfonic acid ion, 2,6-naphthalene disulfonic acid ion and the like), alkyl sulfate ion (such as methyl sulfate ion) Ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, picric acid ion, acetic acid ion, trifluoromethanesulfonic acid ion and the like. As the charge balance counter ion, an ionic polymer or another dye having an opposite charge to that of the dye may be used, or a metal complex ion (for example, bisbenzene-1,2-dithiolato nickel (III) It is possible.

* Coupler

The dye having the structure represented by the general formula (I) preferably has at least one suitable interlocking group for the surface of the semiconductor fine particles. More preferably 1 to 6 of these couplers in the dye, and particularly preferably 1 to 4 thereof. (For example, -OP (O) (OH) _2, etc.), a phosphonyl group (for example, -P (O) (OH) ₂ or the like) (a substituent having a dissociative proton) in the dye.

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. When the dye in the following specific examples includes a ligand having a proton-dissociable group, the ligand may dissociate as needed to release protons.

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The dye represented by formula (I) of the present invention can be synthesized with reference to Japanese Laid-Open Patent Publication No. 2001-291534 or the method cited in the publication.

The coloring matter composed of the compound represented by the formula (I) has a maximum absorption wavelength in the solution, preferably in the range of 300 to 1000 nm, more preferably in the range of 350 to 950 nm, 900 nm.

In the photoelectric conversion element and the photoelectrochemical cell of the present invention, by using at least a dye comprising a compound represented by the formula (1) and a dye comprising a compound represented by the formula (I) High conversion efficiency can be ensured.

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

The dye of the present invention may be used at the same time as represented by the following general formula (1) '.

In the 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 represent a heterocyclic group bonded with an aliphatic group, an aromatic group or a carbon atom, and they may be substituted. P ^{1 '} and P ^2' each independently represent a pigment residue. W ^{1 '} represents a counter ion when it is necessary to neutralize the charge.

Examples of the general formula (1) 'include the following.

[Photoelectric conversion element]

(Photoreceptor layer)

Embodiments of the photoelectric conversion element have already been described with reference to Fig. In the present embodiment, the photoconductor layer 2 is composed of a porous semiconductor layer composed of a layer of the semiconductor fine particles 22 to which a dye described below is adsorbed. This dye may be dissociated in some electrolytes. The photoconductor layer 2 may be designed in accordance with the purpose, and may have a multilayer structure.

As described above, the photoreceptor layer 2 has high light-receiving sensitivity in that it contains the semiconductor fine particles 22 on which specific coloring matters are adsorbed. When the photoreceptor layer 2 is used as a photo-electrochemical cell 100, And has higher durability.

(Charge moving body)

The electrolyte composition used in the photoelectric conversion element 10 of the present invention may contain, as the redox pair, for example, a combination of iodine and iodide (for example, lithium iodide, tetrabutylammonium iodide, tetramethylammonium iodide, etc.) A combination of a biologen (for example, methylviologen chloride, hexylbiologen bromide, benzyl birogen tetrafluoroborate) and a reducing body thereof, a combination of polyhydroxybenzenes (for example, hydroquinone, naphtho Hydroquinone, etc.) and its oxidized form, a combination of a divalent and trivalent iron complex (e.g., a red blood salt and a sulfur black salt), and the like. The combination of iodine and iodide in these is preferred.

The cation of the iodide salt is preferably a nitrogen-containing aromatic cation of a five-membered ring or a six-membered ring. Particularly, when the compound represented by the general formula (1) is not an iodide salt, the compound represented by the general formula (1) Year), iodine salts such as pyridinium salts, imidazolium salts and triazolium salts are preferably used in combination.

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

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

It is preferable that the solvent is capable of exhibiting excellent ion conductivity because of low viscosity, high ion mobility, high dielectric constant and effective carrier concentration, or both. Such solvents include, but are not limited to, carbonate compounds such as ethylene carbonate and propylene carbonate, heterocyclic compounds such as 3-methyl-2-oxazolidinone, ether compounds such as dioxane and diethyl ether, (Ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, polypropylene glycol dialkyl ether, polypropylene glycol dialkyl ether, etc.) (Ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin and the like), nitrile compounds (acetonitrile, glutaronitrile, methoxyacetonitrile, propionitrile and the like), polyhydric alcohols Benzonitrile, bis-cyanoethyl ether, etc.), esters (such as carboxylic acid (Dimethylsulfoxide (DMSO), sulfolane, etc.), water, a functional electrolytic solution described in Japanese Patent Application Laid-Open No. 2002-110262, Japanese Patent Application Laid- 36332, Japanese Unexamined Patent Application Publication No. 2000-243134, and the electrolyte solvent described in the re-publication WO / 00-54361. These solvents may be used in a mixture of two or more kinds.

As the electrolyte of the present invention, a charge transport layer containing a hole conductive material may be used. As the hole conductor material, 9,9'-spirobifluorene derivatives and the like can be used.

In addition, an electrode layer, a photoconductor layer (photoelectric conversion layer), a charge carrier layer (hole transport layer), a conductive layer, and a counter electrode layer can be sequentially laminated. a hole transporting material functioning as a p-type semiconductor can be used as the hole transporting layer. As the preferable hole transporting layer, for example, an inorganic or organic hole transporting material can be used. Examples of the inorganic hole transporting material include CuI, CuO, NiO and the like. Examples of organic-based hole transporting materials include high-molecular-weight and low-molecular-weight materials, and examples of high molecular weight materials include polyvinylcarbazole, polyamine and organic polysilane. Examples of the low molecular system include triphenylamine derivatives, stilbene derivatives, hydrazone derivatives, and phenamine derivatives. Of these, organic polysilanes are preferred because σ electrons, which are unstimulated along Si of the main chain, contribute to light conduction and have a high hole mobility, unlike conventional carbon-based polymers (Phys. Rev. B, 35 , 2818 (1987)).

(Conductive support)

As shown in Fig. 1, in the photoelectric conversion element of the present invention, a photoconductor layer 2 on which a sensitizing dye 21 is adsorbed is formed on a porous semiconductor fine particle 22 on a conductive support 1. As described later, the photoconductor layer 2 can be produced, for example, by applying a dispersion of semiconductor fine particles to an electrically conductive substrate and drying the same, followed by immersion in the dye solution of the present invention.

As the conductive support 1, it is possible to use a conductive material such as a metal itself or a glass or polymer material having a conductive film layer on its surface. The conductive support 1 is preferably substantially transparent. The substantially transparent means that the light transmittance is 10% or more, preferably 50% or more, and particularly preferably 80% or more. As the conductive support 1, glass or a polymer material coated with a conductive metal oxide may be used. The application amount of the conductive metal oxide at this time is preferably 0.1 to 100 g per 1 m 2 of the glass or the support of the polymeric material. When a transparent conductive support is used, it is preferable that light is incident from the support side. As an example of the polymer material to be preferably used, a polymer material such as tetracetyl cellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate (PAR), polysulfone (PSF), polyester sulfone (PES), polyetherimide (PEI), cyclic polyolefin and phenoxy bromide. The surface of the conductive support 1 may be subjected to a light management function. For example, an antireflection film prepared by alternately laminating a high-refraction film and a low-refractive-index oxide film described in Japanese Patent Application Laid-Open No. 2003-123859, And a light guide function described in Japanese Patent Application Laid-

In addition, a metal support may 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 photoconductor layer 2 on which a sensitizing dye 21 is adsorbed is formed on a porous semiconductor fine particle 22 on a conductive support 1. As described later, the photoconductor layer 2 can be produced, for example, by applying a dispersion liquid of the semiconductor fine particles 22 to the electroconductive substrate 1, drying it, and immersing it in the above-described dye solution. In the present invention, as the semiconductor fine particles, those prepared using the above specific surfactant are applied.

(Semiconductor fine particle dispersion)

In the present invention, a semiconductor fine particle dispersion in which the content of solids other than the semiconductor fine particles is 10% by mass or less based on the total amount of the semiconductor fine particle dispersion is applied to the conductive support 1 and is suitably heated to obtain a porous semiconductor fine particle coating layer have.

As a method for producing the semiconductor fine particle dispersion, there can be used a method in which, in addition to a sol-gel method, a semiconductor is precipitated as fine particles in a solvent to be used as it is in a solvent, a method in which fine particles are irradiated with ultrasonic waves to be pulverized with ultrafine particles, And grinding and grinding by mechanical grinding. As the dispersion solvent, one or more of water and various organic solvents may 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 and acetonitrile.

When dispersed, a small amount of a polymer such as polyethylene glycol, hydroxyethylcellulose, carboxymethylcellulose, a surfactant, an acid, or a chelating agent may be used as a dispersion aid, if necessary. However, it is preferable that most of these dispersion assisting agents are removed by a filtration method, a separation membrane method, or a centrifugal separation method before the step of forming a film on the conductive support. In the semiconductor fine particle dispersion, the solid content other than the semiconductor fine particles may be 10 mass% or less of the total dispersion. This concentration is preferably 5% or less, more preferably 3% or less, particularly preferably 1% or less. , More preferably 0.5% or less, and particularly preferably 0.2%. That is, the solids other than the solvent and the semiconductor fine particles in the semiconductor fine particle dispersion can be made to be 10 mass% or less of the whole semiconductor micro dispersion. It is preferable that it is composed substantially only of the semiconductor fine particles and the dispersion solvent.

If the viscosity of the semiconductor microparticle dispersion is too high, the dispersion may aggregate to form a film. Conversely, if the viscosity of the semiconductor microparticle dispersion is too low, the liquid may flow and the film formation may not be possible. Therefore, the viscosity of the dispersion is preferably 10 to 300 N · s / m 2 at 25 ° C. And more preferably 50 to 200 N · s / m 2 at 25 ° C.

As a method of applying the semiconductor fine particle dispersion, a roller method, a dipping method, or the like can be used as an application system method. As the metering method, an air knife method, a blade method, or the like can be used. The wire bar method disclosed in Japanese Patent Laid-Open Publication No. 58-4589, the slide hopper method described in U.S. Patent No. 2681294, etc., the extrusion method, A curtain method and the like are preferable. It is also preferable to use a general-purpose machine for application by a spin method or a spray method. The wet printing method is preferably a concave plate, a rubber plate, a screen printing, or the like, including three printing methods of relief, offset and gravure. Among them, a preferable film-forming method is selected depending on the liquid viscosity and the wet thickness. In addition, since the dispersion of the semiconductor fine particles of the present invention has high viscosity and viscosity, the cohesive force is sometimes high, and sometimes the coating is not well fused with the support at the time of coating. In such a case, the surface is cleaned and hydrophilized by the UV ozone treatment, whereby the bonding force between the applied semiconductor fine particle dispersion and the surface of the conductive support 1 is increased, and the application of the semiconductor fine particle dispersion becomes easy.

A preferable thickness of the entire semiconductor fine particle layer is 0.1 mu m to 100 mu m. The thickness of the semiconductor fine particle layer is also preferably 1 mu m to 30 mu m, more preferably 2 mu m to 25 mu m. The supported amount of the semiconductor fine particles per 1 m 2 of the support is preferably 0.5 g to 400 g, more preferably 5 g to 100 g. The method of applying the fine particle dispersion to form a film is not particularly limited, and a known method may be appropriately applied.

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 dyes 21 to the semiconductor fine particles 22, it is preferable to immerse the semiconductor fine particles 22 dried for a long time in the dye solution for dye adsorption comprising the solution and the dye related to the present invention. The solution used for the coloring matter adsorbing dye solution can be used without particular limitation as long as it is a solution capable of dissolving 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 them, ethanol and toluene can be preferably used.

The amount of the sensitizing dye 21 to be used is preferably 0.01 mmol to 100 mmol, more preferably 0.1 mmol to 50 mmol, and particularly preferably 0.1 mmol to 10 mmol, per 1 m 2 of the support. In this case, the use amount of the sensitizing dye 21 according to the present invention is preferably 5 mol% or more.

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, per 1 g of the semiconductor fine particles.

By using such a small amount of color, the effect of increasing or decreasing in the semiconductor can be sufficiently obtained. On the other hand, if the amount of dye is small, the effect of increasing and decreasing becomes insufficient, and if the amount of dye is excessively large, the dye not adhered to the semiconductor floats to cause the decrease and decrease effect.

(The main pole)

The counter electrode 4 serves as a positive electrode of a photoelectrochemical cell. The counter electrode 4 is generally the same as the above-described conductive support 1, but a counter electrode support is not necessarily required in a configuration in which the strength is sufficiently maintained. However, the side having the support is advantageous in terms of hermeticity. Examples of the material of the counter electrode 4 include platinum, carbon, and a conductive polymer. Preferred examples include platinum, carbon, and conductive polymers.

As the structure of the counter electrode 4, a structure having a high current collecting effect is preferable. A preferable example is JP-A-10-505192 and the like.

(Light receiving electrode)

The light receiving electrode 5 may be of a tandem type in order to increase the utilization ratio of the incident light. Preferable examples of the configuration of the tandem type include the examples described in JP-A-2000-90989 and JP-A-2002-90989.

The light management function for efficiently performing light scattering and reflection within the layer of the light receiving electrode 5 may be formed. Preferably those described in Japanese Patent Application Laid-Open No. 2002-93476.

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 reverse current caused by direct contact between the electrolyte and the electrode. A preferable example is JP-A-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-2001-283941.

Examples of sealing methods for cells and modules include a method of using an aluminum alkoxide in a polyisobutylene thermosetting resin, a novolac resin, a photocurable (meth) acrylate resin, an epoxy resin, an ionomer resin, a glass frit, And a method of laser melting the melting point glass paste. In the case of using glass frit, powder glass may be mixed with an acrylic resin to be a binder.

Example 1

1. Preparation of coloring matter

Hereinafter, the method for preparing a coloring matter of the present invention will be described in detail by way of examples, but the starting material, the dye intermediate and the preparation route are not limited thereto.

(1) Preparation Example 1

(Preparation of Exemplified Compound 121)

The dye 121 was prepared according to the scheme shown below.

[Chemical Formula 39]

(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 7-mL of 1-butanol and 10 mL of toluene, and the mixture was heated and stirred at 90 DEG C for 5 hours. Thereafter, the reaction solution was concentrated, and the obtained 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, added with triethylamine, and the mixture was heated and stirred at 90 캜 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 ice-cooled. Thereto was added 0.04 g of tetrakis (triphenylphosphine) palladium (0) and the reaction was carried out 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 121. [ The identification was carried out by Millimass, and the following results were obtained.

Mass found (m / z); (M + H) < ⁺ & gt ^; : 1180.7051

Mass calculated (m / z); (M + H) < ⁺ & gt ^; : 1180.7058 (C ₇₁ H ₉₈ N ₅ O ₈ S)

(2) Preparation Example 2

(Preparation of coloring matter 19)

The dye 19 was prepared according to the scheme shown below.

(40)

(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, added with triethylamine, and the mixture was heated and stirred at 87 占 폚 for 4 hours. Thereafter, the reaction solution was concentrated, and the obtained 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 ice-cooled. 0.06 g of tetrakis (triphenylphosphine) palladium (0) was added thereto, and the reaction was carried out for 4 hours. Thereafter, the reaction solution was concentrated, and the obtained residue was purified by column chromatography to obtain 0.25 g of Compound 19. The identification was carried out by Millimass, and the following results were obtained.

Mass found (m / z); (M + H) < ⁺ & gt ^; : 1210.6797

Mass calculated (m / z); (M + H) < ⁺ & gt ^; : 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.

(41)

(3-1) Synthesis of Compound 3-3

1.08 g of the compound 3-1, 1.04 g of the 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 the mixture was heated and stirred at 100 DEG C for 6 hours. Thereafter, the reaction solution was concentrated, and the obtained 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 the compound 3-3 and 0.10 g of the compound 3-4 were mixed in a mixed solvent of 5-mL of 1-butanol and 5 mL of toluene, and the mixture was heated and stirred at 90 DEG C for 3 hours. Thereafter, water and ethyl acetate were added to the reaction solution, and the mixture was subjected to extraction and separation, and the ethyl acetate layer was concentrated. The residue thus obtained was purified by column chromatography to obtain 0.13 g of 67. The identification was carried out by Millimass, and the following results were obtained.

Mass found (m / z); (M + H) < ⁺ & gt ^; : 1773.9112

Mass calculated (m / z); (M + H) < ⁺ & gt ^; : 1773.9116 (C ₁₀₇ H ₁₃₃ N ₆ O ₁₁ S ₃ )

The dye of formula (1) of the present invention used in the experiment was prepared by the same method. The coloring matter represented by the formula (I) of the present invention was prepared by referring to Japanese Patent No. 4576494 or the method cited in the publication.

(Measurement of maximum absorption wavelength of dye)

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

Example 2

1. Preparation of titanium dioxide dispersion

15 g of titanium dioxide fine particles (Degussa P-25, manufactured by Nippon Aerosil Co., Ltd.), 45 g of water and a dispersing agent (Triron X (trade name), manufactured by Aldrich Chemical Co., Ltd.) were placed in a 200 ml stainless- -100) and 30 g of zirconia beads having a diameter of 0.5 mm (manufactured by NIKKATO CO., LTD.) Were put and dispersed for 2 hours at 1500 rpm using a sand grinder mill (manufactured by Imax). The zirconia beads were separated by filtration from the obtained dispersion. The average particle diameter of the titanium dioxide fine particles in the obtained dispersion was 2.5 占 퐉. The particle diameter was measured by a masterizer manufactured by MALVERN.

2. Manufacture of electrode 1A

A conductive glass plate (trade name: TCO Glass-U, product of Asahi Glass Co., Ltd., surface resistance: about 30 Ω / m 2) of 20 mm × 20 mm coated with tin oxide doped with fluorine was prepared, (A portion having a width of 3 mm from the end), and then the above dispersion was applied using a glass rod on the conductive layer. After the application of the dispersion liquid, 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 (Muffel FP-32 type manufactured by Yamato Scientific Co., Ltd.) and fired at 450 캜 for 30 minutes. The semiconductor coated glass plate was taken out and cooled, and then immersed in an ethanol solution (concentration: 2 x 10 ^-4 mol / l) of the dye shown in the table for 1 hour. The semiconductor-coated glass plate on which the dye was adsorbed was immersed in 4-tert-butylpyridine for 15 minutes, washed with ethanol, and naturally dried to obtain a titanium oxide fine particle layer (electrode A) adsorbing dye. The thickness of the dye-sensitized titanium oxide fine particle layer of the electrode A was 10 占 퐉, and the coating amount of the titanium oxide fine particles was 20 g / m2. The adsorption amount of the dye was in the range of 0.1 to 10 mmol / m 2 depending on the kind thereof.

3. Manufacture of photoelectrochemical cell

A solution containing 0.5 mol / l of iodine salt electrolyte of 1-methyl-3-hexylimidazolium and 0.05 mol / l of iodine was prepared using acetonitrile as a solvent. To this solution, a nitrogen-containing polymer compound (1-1) was added so as to have a weight composition ratio of 10 wt% when the solvent + nitrogen-containing polymer compound + salt was changed to 100 wt%, and the reactive nitrogen (1-2) in an amount such that the molar ratio of the former electron moiety to the atom was 0.5 were mixed to obtain a homogeneous reaction solution.

(42)

(43)

On the other hand, the platinum thin film side of the counter electrode made of a glass plate on which platinum was vapor-deposited via a spacer was formed on the dye-sensitized TiO ₂ fine particle layer formed on the conductive glass plate, and the conductive glass plate and the platinum-deposited glass plate were 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 phenomenon. Subsequently, the mixture was heated at 80 占 폚 for 30 minutes to effect crosslinking reaction.

Thus, as shown in Fig. 1, the conductive support 1 (having a conductive layer formed on a glass transparent substrate), the photoconductor layer 2, the charge carrier layer 3, A photoelectrochemical cell of the present invention in which a counter electrode 4 made of platinum and a glass transparent substrate (not shown) were stacked in this order was obtained.

3-1. Measurement of IPCE (quantum yield)

The IPCE at 400 to 900 nm of the produced photoelectrochemical cell was measured by an IPCE measuring apparatus manufactured by PECEL. The IPCE at 850 nm of each photoelectrochemical cell is shown in the following table.

3-2. Measurement of photoelectric conversion efficiency

Light of 500 W xenon lamp (manufactured by Ushio Inc.) was passed through an AM 1.5 filter (manufactured by Oriel) and a sharp-cut filter (KenkoL-37, trade name) to generate simulated sunlight not containing ultraviolet rays . The intensity of this light was 70 mW / cm 2. The simulated sunlight was irradiated to the photoelectrochemical cell manufactured as described above at 50 DEG C, and the generated electricity was measured with a current voltage measuring apparatus (type of Keithley SMU238). The initial cell performance results were: conversion efficiency (3.5% or more: AA, 2.5% to less than 3.5%: A, 2.0% to less than 2.5%: B, less than 2.0%: C) Opening voltage (V), 0.6 or more for fill factor: AA, 0.45 or more and less than 0.6: A, 0.3 or more and less than 0.45: B or less than 0.3: C).

In addition, the rate of decrease in conversion efficiency after 1000 hours of dark storage at 85 ° C and the rate of decrease in conversion efficiency after 500 hours of continuous light irradiation were also measured. The results of this durability test were evaluated as AA when the reduction rate after the test was less than 10%, A when the ratio was less than 10% and less than 25%, B when the difference was less than 40% and less than 40% These results are shown in the following table.

S-1, S-2 and S-3 were used as coloring matters in the sample numbers c11, c12 and c13, respectively. S-2 corresponds to the dye disclosed in Japanese Patent Application Laid-Open No. 2009-242379, and S-1 and S-3 correspond to the coloring matters S-14 and S-18 disclosed in Japanese Patent Application Laid-Open No. 2000-195570.

(44)

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

Example 3

An electrolytic solution was prepared by dissolving 0.1 mol / l lithium iodide, 0.05 mol / l iodine and 0.62 mol / l dimethylpropyl imidazolium iodide using acetonitrile as a solvent. Hereinbelow, the benzimidazole-based compounds No. 1 to No. 8 shown below were separately added and dissolved to give a concentration of 0.5 mol / l, respectively.

[Chemical Formula 45]

A conductive film was formed by sputtering tin oxide doped with fluorine as a transparent conductive film on a glass substrate. An aqueous solution of anatase-type titanium oxide (P-25 (trade name) manufactured by Nippon Aerosil Co., Ltd.) was added to a dispersion containing anatase type titanium oxide particles (100 ml of a mixed solvent of water and acetonitrile in a volume ratio of 4: 32 g) were mixed and dispersed and mixed uniformly using a mixing / conditioner type mixing conditioner. The resultant was then sintered at 500 캜 to form a photosensitive layer having a thickness of 15 탆. The benzimidazole compound electrolytes of the above No. 1 to No. 8 were dropped into the photosensitive layer.

A frame-shaped spacer (thickness: 25 mu m) made of a polyethylene film was placed thereon and covered with a platinum counter electrode to prepare 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 obtained open-circuit voltage and photoelectric conversion efficiency are shown in the table. An open-circuit voltage of 6.3 V or more was indicated as AA, a voltage of 6.0 V or more and less than 6.3 V as A, a voltage of 5.7 V or more and less than 6.0 V as B, and a voltage of less than 5.7 V as C. The conversion efficiency was AA, A having less than 2.5% and less than 3.5%, B having less than 2.0% and less than 2.5%, and C having less than 2.0%.

From the results of the above table, it can be seen that the conversion efficiency of the dye of the present invention is high.

Example 4

(1) Formation of first photoelectric conversion layer

4.0 g of commercially available titanium oxide particles (manufactured by Teika, average particle diameter 30 nm) and 20 ml of diethylene glycol monomethyl ether were dispersed for 6 hours by means of a paint shaker using hard glass beads to prepare a titanium oxide suspension. Next, this titanium oxide suspension was applied to a glass plate previously provided with a tin oxide conductive layer by using a doctor blade, preliminarily dried at 100 ° C for 30 minutes, and then baked in an electric furnace at 500 ° C for 40 minutes to obtain a titanium oxide film.

Separately, Ru-1 was dissolved in ethanol.

(46)

The concentration of this dye was 3 × 10 ^-4 mol. Next, the above-mentioned glass plate on which titanium oxide film was formed was placed in this solution, dye adsorption was carried out at 60 DEG C for 720 minutes, and the resultant was dried to obtain the first photoelectric conversion layer (sample A) of the present invention.

(2) Formation of second photoelectric conversion layer

4.0 g of commercially available nickel oxide particles (Kishida Chemical Co., average particle diameter 100 nm) and 20 ml of diethylene glycol monomethyl ether were dispersed for 8 hours in a paint shaker using glass beads to obtain a nickel oxide suspension. Then, the titanium oxide suspension was coated on a glass plate with a tin oxide conductive layer using a doctor blade, preliminarily dried at 100 占 폚 for 30 minutes, and then baked at 300 占 폚 for 30 minutes to obtain a nickel oxide film.

Separately, the dye and comparative dye S-1 of the present invention were respectively dissolved in dimethylsulfoxide.

The concentration of this dye was 0.5 × 10 ^-4 mol. Next, the glass plate on which the titanium oxide film was formed was placed in this solution, dye adsorption was carried out at 40 占 폚 for 70 minutes, and the resultant was dried to obtain the second photoelectric conversion layer (sample B) of the present invention.

(3) Place the sample B on the sample A described above. A liquid electrolyte was sandwiched between these two electrodes, the side surface was sealed with a resin, and a lead wire was attached to the substrate to manufacture a photoelectric conversion element (element structure C) of the present invention. The liquid electrolyte was prepared by dissolving tetrapropylammonium iodide and iodine in a mixed solvent of acetonitrile / ethylene carbonate (volume ratio = 1: 4) such that each concentration was 0.46 mol / L and 0.06 mol / L, respectively .

In addition, a transparent conductive glass plate having platinum as a counter electrode and having the sample A as one electrode was used. A liquid electrolyte was sandwiched between the two electrodes, the side surface was sealed with a resin, and a lead wire was attached thereto to manufacture a photoelectric conversion element (element structure D) of the present invention.

The obtained photoelectric conversion elements (element configurations C and D) were irradiated with light of 1000 W / m < 2 > intensity with a solar simulator. The conversion efficiencies are shown in the following table, with A having 6.5% or more, AA having 6.0% or more and less than 6.5%, B having 5.0% or more and less than 6.0%, and C having less than 5.0%.

From the above table, it can be seen that the dye of the present invention has excellent photoelectric conversion efficiency and is effective also in this system.

Example 5

(Fabrication of photoelectric conversion element)

The photoelectric conversion element shown in Fig. 1 was manufactured as follows.

Tin oxide doped with fluorine was formed as a transparent conductive film on a glass substrate by sputtering, and this was scribed with a laser to divide the transparent conductive film into two portions.

Subsequently, 32 g of anatase-type titanium oxide (P-25 (trade name), manufactured by Nippon Aerosil Co., Ltd.) was mixed with 100 ml of a mixed solvent of water and acetonitrile in a volume ratio of 4: 1, Using a conditioner, they were uniformly dispersed and mixed to obtain a dispersion of semiconductor fine particles. This dispersion was applied to a transparent conductive film and heated at 500 캜 to prepare a light receiving electrode.

Thereafter, a dispersion liquid containing silica particles and rutile titanium oxide in a ratio of 40: 60 (by mass) was similarly prepared. The dispersion liquid was applied to the light receiving electrode and heated at 500 DEG C to form an insulating porous body. Subsequently, a carbon electrode was formed as a counter electrode.

Next, the glass substrate on which the above-described insulating porous body was formed was immersed in an ethanol solution of a sensitizing dye (multiple or mixed) described in the following table for 1 hour. The glass in which the sensitizing dye was dissolved was immersed in a 10% ethanol solution of 4-tert-butylpyridine for 30 minutes, washed with ethanol and air-dried. The thickness of the photosensitive layer thus obtained was 10 占 퐉, and the application amount of the semiconductor fine particles was 20 g / m2. 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)

Light of 500 W xenon lamp (manufactured by Ushio) was passed through an AM 1.5 G filter (manufactured by Oriel) and a sharp-cut filter (Kenko L-42, trade name) to generate simulated sunlight not containing ultraviolet rays. 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 by a current voltage measurement device (Kisley 238 type, trade name). The results of measuring the conversion efficiency of the photoelectrochemical cell thus obtained are shown in the following table. The results were rated as AA when the conversion efficiency was 7.5% or more, A with 7.2% or more and less than 7.5%, B with 6.9% or more and less than 7.2%, and C with less than 6.9%.

Absorption solution concentration Color 1: 1 × 10 ^-4 ㏖ / ℓ

Coloring matter 2: 0.2x10 < ^-4 > mol / l

As is apparent from Table 5, the conversion efficiency of samples (electrochemical cells) produced using the dye of the present invention was as high as 7.5% or more. On the other hand, all of the samples of Comparative Examples were insufficient in conversion efficiency of less than 7.2%.

While the invention has been described in conjunction with the embodiments thereof, it is to be understood that the invention is not to be limited by any of the details of the description, unless specifically stated otherwise, and that the invention is broadly construed I think it should be interpreted.

The present application claims priority based on Japanese Patent Application No. 2011-138967 filed in Japan on June 22, 2011 and Japanese Patent Application No. 2011-164425 filed in Japan on Jul. 27, 2011, all of which are incorporated herein by reference in their entirety Incorporated herein by reference in its entirety.

1 conductive support
2 photoconductor layer
21 colors
22 semiconductor particulate
3 charge carrier layer
Four major poles
5 light receiving electrode
6 circuits
10 Photoelectric converter
100 photochemical cell

Claims (14)

1. A photoelectric conversion element comprising a laminate structure including a photoconductor having a semiconductor fine particle layer on which a dye is adsorbed, a charge carrier, and a counter electrode on a conductive support,
Wherein at least one species of the dye has a structure represented by the following formula (1).
[Chemical Formula 1]

(In the formula, represents the Q is aromatic ring. X ^1, X ² represents a sulfur atom, a selenium atom, an oxygen atom, or ^{CR 1 R 2. R 1,} R 2 represents an alkyl group. R, R 'is an alkyl group Or an aromatic group, P ¹ represents an atomic group represented by the following formula P11 or P ¹² , P ² represents an atomic group necessary for forming a polymethine dye, provided that P ¹ and P ² are different from each other And W ¹ represents the counter ion when necessary to neutralize the charge.
(2)

(In the formula, R ^5, R ^6, R ^10, R ¹¹ is a case of having an acidic group represents an a aromatic ring which if having an aliphatic group, or an acid with a. R ^7, R ¹² is a sulfur atom or the formula R ^A represents ^{a. R 3, R 4, R} 8 represents a hydrogen atom or a substituent. R ⁹ is an oxygen atom or a substituent. n21 represents an integer of 0 or more. n22, n31 represents 0 or 1.)
(3)

(R ¹³ and R ¹⁴ in the formula R ^A represent a cyano group or an acidic group.) The method according to claim 1,
Wherein P ¹ is the following formula P11-1 or P12-1.
[Chemical Formula 4]

(Wherein R ³ , R ⁴ , R ⁶ , R ⁸ , R ⁹ , R ¹¹ and n ²¹ have the same meanings as in formulas P ¹¹ and P 12) The method according to claim 1,
And n22 and n31 are zero. The method according to claim 1,
Wherein P ¹ is represented by the following formula (P11-2) or (P12-2).
[Chemical Formula 5]

(Wherein R ³ , R ⁴ , R ⁵ , R ⁸ , R ⁹ , R ¹⁰ and n ²¹ have the same meanings as P 11 and P 12) The method according to claim 1,
And n21 is 0 or 1. 2. The photoelectric conversion element according to claim 1, The method according to claim 1,
And R ⁹ is represented by the following formula: R 91 or R 92.
[Chemical Formula 6]

(Wherein R92, R ¹⁵ represents a hydrogen atom or an alkyl group.) The method according to claim 1,
And R < ⁹ > is an oxygen atom. The method according to claim 1,
Wherein the group of atoms forming P < ² > is represented by the following formula (P21) or (P22).
(7)

^{(Wherein, R 21, R 22, R} 23 represents a hydrogen atom or a substituent. Ar ¹ is a σp value is aromatic ring group or the σp value having a substituent not more than 0 in the Hammett Chick (則) substituent or less 0 And n41 represents an integer of 0 or more.) In the formula, R < ¹ > 9. The method of claim 8,
And Ar ¹ is represented by the following formula: R ^C1 , R ^C2 , R ^C3 , or R ^C4 .
[Chemical Formula 8]

(Wherein R ^C1 ~ R ^C4, Y represents a S, NR ^24, or _{^{C (R 25) 2. R}} 24 represents an alkyl group. R ²⁵ represents a substituent. A represents an aromatic ring. R ²⁶ ~ R ²⁹ represents a hydrogen atom or a substituent. E represents an ^{S, NR 30, O. R} 30 represents an alkyl group. D represents the σp value of the substituent less than or equal to zero in the Hammett law. B represents an aromatic ring. X represents SR ^e , OR ^e or NR ^e ₂ , 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, , In the formulas P21 and P22, they may be connected to each other via a methine chain, or they may be double bonds to be directly connected, where k is a positive integer. The method according to claim 1,
In the dye represented by the formula (1), P ¹ is an electron acceptor, P ² is a donor, and the dye is a donor / acceptor molecule. The method according to claim 1,
Wherein the photoconductor further has a dye represented by the following formula (I).
_{^{Mz (LL 1) m1 (LL}} 2) m2 (X) m3 · CI: formula (I)
[In the formula (I), Mz represents a metal atom. LL ¹ represents a 2-position ligand represented by the following formula LL ¹ . LL ² represents a 2-left or 3-position ligand represented by the following formula LL2. X represents a 1-left or 2-position ligand. m1 represents an integer of 0 to 3; m2 represents an integer of 1 to 3; and m3 represents an integer of 0 to 2. CI represents the counter ion when counter ions are required to neutralize charge.]
[Chemical Formula 9]

(In the formula LL1, R ⁵¹ and R ^{52 each} represent an acidic group, R ⁵³ and R ^{54 each} represent a substituent, R ⁵⁵ and R ^{56 each} represent an alkyl group or an aromatic ring group, and d1 and d2 represent an integer of 0 to 5 . L ¹ and L ² represents a conjugated chain. a1 and a2 represents an integer of 0 to 3. d3 represents 0 or 1. b1 and b2 represents an integer of 0 to 3.)
[Chemical formula 10]

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

(In the formula, represents the Q is aromatic ring. X ^1, X ² represents a sulfur atom, a selenium atom, an oxygen atom, or ^{CR 1 R 2. R 1,} R 2 represents an alkyl group. R, R 'is an alkyl group Or an aromatic group, P ¹ represents an atomic group represented by the following formula P11 or P ¹² , P ² represents an atomic group necessary for forming a polymethine dye, provided that P ¹ and P ² are different from each other And W ¹ represents the counter ion when necessary to neutralize the charge.
[Chemical Formula 12]

(In the ^{formula, R 5, R 6, R} 10, R 11 represents an aliphatic group or an aromatic ring. R ^7, R ¹² denotes a sulfur atom or the formula ^{R A. R 3, R 4} , R 8 is hydrogen N21 represents an integer of 0 or more, and n22 and n31 represent 0 or 1.) In the formula, R < ⁹ > represents an oxygen atom or a substituent.
[Chemical Formula 13]

(R ¹³ and R ¹⁴ in the formula R ^A represent a cyano group or an acidic group.) 9. The method of claim 8,
The structure formed by the formula P21 or P22 together with the mother nucleus of the formula (1) is represented by the following formula (1-1-1), formula (1-1-2), formula (1-2-1) 2-2). ≪ / RTI >

^{(Wherein, Q, P 1, X 1} , X 2, R, R ', W 1, Ar 1, n41 represents the above formula (1) and P21 with the same ^{meaning. R 210, R 211, R} 212, R ²²⁰ and R ²²¹ represent a hydrogen atom or a substituent.

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