WO2013035630A1

WO2013035630A1 - Dye, photoelectric conversion element using same, and photoelectrochemical cell

Info

Publication number: WO2013035630A1
Application number: PCT/JP2012/072076
Authority: WO
Inventors: 木村　睦; 正悟森; 小林　克
Original assignee: 富士フイルム株式会社; 国立大学法人信州大学
Priority date: 2011-09-08
Filing date: 2012-08-30
Publication date: 2013-03-14
Also published as: JP2013067773A; KR20140062511A; JP5706846B2; CN103764768B; CN103764768A

Abstract

A dye which is represented by formula (1): MX₃Lt. (In formula (1), M represents a transition metal that is selected from among ruthenium, osmium, iron, rhenium and technetium; X represents NCS^-, Cl^-, Br^-, I^-, CN^-, NCO^- or H₂O; and Lt represents a ligand that is represented by formula (2).) (In formula (2), each of R¹ and R² represents COOH, PO(OH)₂, PO(OR⁴)(OH) or CO(NHOH); each of R³ and R⁴ represents a specific substituent; La represents a single bond or an arylene group; and each of n1-n3 represents a specific integer.)

Description

Dye, photoelectric conversion element and photoelectrochemical cell using the same

The present invention relates to a dye, a photoelectric conversion element, and a photoelectrochemical cell.

Photoelectric conversion elements are used in various optical sensors, copiers, solar cells and the like. Various types of photoelectric conversion elements have been put to practical use, such as those using metals, semiconductors, organic pigments and dyes, or combinations thereof. In particular, a solar cell using non-depleting solar energy does not require fuel, and full-scale practical use is highly expected as it uses inexhaustible clean energy. Among these, silicon solar cells have been researched and developed for a long time, and are spreading due to the policy considerations of each country. However, silicon is an inorganic material, and its throughput and molecular modification are naturally limited.

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

Patent Document 1 describes a dye-sensitized photoelectric conversion element using semiconductor fine particles sensitized with a ruthenium complex dye by applying this technique. Furthermore, the development of ruthenium complex-based sensitizing dyes continues to improve the photoelectric conversion efficiency (see Patent Documents 2 to 4).

US Pat. No. 5,463,057 Chinese Patent Publication No. 1359901 International Publication No. 2007/091525 Pamphlet International Publication No. 98/50393 Pamphlet

Devices with high photoelectric conversion efficiency have been provided by the techniques of Patent Documents 2 and 3 and the like. However, the present inventor is looking to play a part as a full-fledged source of green energy, and its performance is not sufficient, and development of photoelectric conversion elements that exhibit higher characteristics including improved durability Aimed at.
In view of the present state of the present technical field, an object of the present invention is to provide a photoelectric conversion element, a photoelectrochemical cell, and a dye used for them that achieve high photoelectric conversion efficiency and excellent durability. Furthermore, this invention aims at provision of the novel intermediate compound used for manufacture of the said pigment | dye, its manufacturing method, and the manufacturing method of a pigment | dye using the same.

The above problem has been solved by the following means.
[1] A dye represented by the formula (1) MX ₃ Lt.
[Wherein M represents a transition metal selected from ruthenium, osmium, iron, rhenium, and technetium. X represents NCS ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , CN ⁻ , NCO ⁻ , or H ₂ O. Lt represents the formula (2). ]

[Wherein R ¹ represents COOH, PO (OH) ₂ , PO (OR ⁴ ) (OH), or CO (NHOH). R ² represents COOH, PO (OH) ₂ , PO (OR ⁴ ) (OH), or CO (NHOH). La represents a single bond or an arylene group. R ⁴ represents an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. n1 represents an integer of 1 to 3. n2 and n3 each represents an integer of 1 to 4. R ³ represents an alkyl group having 1 to 30 carbon atoms, or a group represented by the following formula (2-1), (2-2), (2-3), (2-4), or general formula (2-5). Represents a substituent. ]

[Wherein R ¹¹ , R ²¹ , R ³¹ , R ⁴¹ , R ⁴² , and R ⁵¹ represent an alkyl group having 1 to 30 carbon atoms, a heteroaryl group having 1 to 30 carbon atoms, or an aryl having 6 to 30 carbon atoms. And a substituent containing any one of a group and an amino group having 1 to 30 carbon atoms. However, in the formula (2-4), when R ⁴² represents a substituent containing a heteroaryl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an amino group having 1 to 30 carbon atoms, ⁴¹ may be a hydrogen atom. n11 represents an integer of 1 to 5. n21 and n51 each represents an integer of 2 to 6. n31 represents an integer of 1 to 6. * Represents a bond. ]
[2] The dye according to [1], wherein La in the formula (2) is a single bond.
[3] R ³ in the formula (2) is represented by the formula (2-1), (2-2), (2-3), (2-4) or (2-5) [1] Or the pigment | dye as described in [2].
[4] ^{R 3} is the formula of the formula (2) (2-2), according to any one of (2-3), or formula (2-4) [1] to [3] Dyes.
[5] The dye according to any one of [1] to [4], wherein R ³ in the formula (2) is represented by the formula (2-3) or (2-4).
[6] The dye according to any one of [1] to [5], wherein R ^{3 in the} formula (2) is represented by the formula (2-4).
[7] A photoelectric conversion device comprising a photoreceptor layer containing the dye according to any one of [1] to [6] and semiconductor fine particles.
[8] A photoelectrochemical cell using the photoelectric conversion element according to [7].
[9] A process for producing a terpyridine compound of the following formula (2 ′), wherein the substituent Hal of the compound represented by the following formula (3) is substituted with a substituent R ³ of the following formula (2 ′) And a step of substituting R ¹⁰¹ of substituent CO ₂ R ¹⁰¹ of the following formula (3) with H, a method for producing a terpyridine compound.

[Wherein n1 represents an integer of 1 to 3. n2 and n3 each represents an integer of 1 to 4. R ³ is an alkyl group having 1 to 30 carbon atoms, or a substituent represented by the formula (2-1), (2-2), (2-3), (2-4), or (2-5) Represents a group. ]

[Wherein R ¹¹ , R ²¹ , R ³¹ , R ⁴¹ , R ⁴² , and R ⁵¹ represent an alkyl group having 1 to 30 carbon atoms, a heteroaryl group having 1 to 30 carbon atoms, or an aryl having 6 to 30 carbon atoms. And a substituent containing any one of a group and an amino group having 1 to 30 carbon atoms. However, in the formula (2-4), when R ⁴² represents a substituent containing a heteroaryl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an amino group having 1 to 30 carbon atoms, ⁴¹ may be a hydrogen atom. n11 represents an integer of 1 to 5. n21 and n51 each represents an integer of 2 to 6. n31 represents an integer of 1 to 6. * Represents a bond. ]

[R ¹⁰¹ represents an alkyl group. Hal represents a halogen atom. n1 represents an integer of 1 to 3. n2 and n3 each represents an integer of 1 to 4. ]
[10] A method of synthesizing a terpyridine compound represented by the following formula (2 ′) and producing a dye represented by the formula (1 ′) MX3Lt ′ having this as a ligand, which comprises the following formula (3) the substituent Hal in the compound represented by) a step of substituting the substituent ^{R 3} of the formula (2 '), a step of substituting the ^{R 101} substituents _CO 2 ^{R 101} in formula (3) in H The manufacturing method of the pigment | dye which goes through.
[Wherein M represents a transition metal selected from ruthenium, osmium, iron, rhenium, and technetium. X represents NCS ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , CN ⁻ , NCO ⁻ , or H ₂ O. Lt ′ represents the formula (2 ′). ]

[R ¹⁰¹ represents an alkyl group. Hal represents a halogen atom. n1 represents an integer of 1 to 3. n2 and n3 each represents an integer of 1 to 4. ]
[11] A terpyridine compound represented by the following formula (3).

[R ¹⁰¹ represents an alkyl group. Hal represents a halogen atom. n1 represents an integer of 1 to 3. n2 and n3 each represents an integer of 1 to 4. ]

In this specification, the carbon-carbon double bond may be any of E type and Z type in the molecule. When a plurality of substituents or ligands are alternatively defined, the respective substituents or ligands may be the same or different from each other. Further, when a plurality of substituents and ligands are close to each other, they may be connected to each other or condensed to form a ring.

The photoelectric conversion element and the photoelectrochemical cell using the dye of the present invention achieve high photoelectric conversion efficiency and are excellent in durability. The terpyridine compound of the present invention is a novel compound and is useful as a raw material for synthesizing the above dye. Furthermore, according to the manufacturing method of this invention, the said pigment | dye and intermediate compound (terpyridine compound) can be manufactured suitably.
The above and other features and advantages of the present invention will become more apparent from the following description and accompanying drawings.

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

The metal complex dye of the present invention has a structure in which terpyridine is coordinated with a central metal, and thus, in a photoelectric conversion element, it exhibits high IPCE even in a long wavelength region exceeding 800 nm and realizes high photoelectric conversion efficiency. And higher durability.
This reason includes unclear points, but can be explained as follows, including estimation. In other words, it is conceivable that the acidic groups added to the two pyridine ligands of terpyridine are adsorbed on the surface of the semiconductor fine particles, and the metal complexes are oriented so as to stand up there. If it does so, it will arrange | position so that the specific functional substituent introduce | transduced into the remaining pyridine ring of a terpyridine structure may protrude, and it will extend to the charge-transfer body layer side. As a result, it is understood that electrons can be effectively taken into the molecule from the side of the functional substituent from the charge transfer layer, and the electrons can be sent to the semiconductor fine particles through the binding group serving as a scaffold. On the other hand, the functional substituents arranged to extend toward the charge transfer layer prevent the proximity of I ₃ ⁻ ions to the semiconductor electrode and prevent the electrons injected into titania from moving to I ₃ ⁻ . It is thought that it shows an action. In addition, the functional substituents extending and arranged on the charge transfer layer side are considered to simultaneously prevent the water molecules from approaching the semiconductor electrode and suppress the detachment of the dye from the surface. As a result, it is considered that both high photoelectric conversion efficiency and improved durability are realized. Hereinafter, the present invention will be described in detail based on preferred embodiments thereof.

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

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

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

[Dye represented by Formula (1)]
The coloring matter of the present invention is represented by the following formula (1).
Formula (1) MX ₃ Lt

・ M
In the formula, M represents a transition metal selected from ruthenium, osmium, iron, rhenium, and technetium. Of these, ruthenium is preferable.

・ X
X represents NCS ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , CN ⁻ , NCO ⁻ , or H ₂ O.

・ Lt
Lt is a ligand represented by the following formula (2).

・ R ¹
In the formula, R ¹ represents COOH, PO (OH) ₂ , PO (OR ⁴ ) (OH), or CO (NHOH). The substitution position of La—R ¹ is not particularly limited, but from the viewpoint of the orientation of the dye during adsorption, the 3-position or 4-position is preferred, and the 4-position is more preferred. R ⁴ represents an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. Preferable examples of the alkyl group and the aryl group include the following examples of the substituent T.

・ R ²
R ² represents COOH, PO (OH) ₂ , PO (OR ⁴ ) (OH), or CO (NHOH). The substitution position of R ² is not particularly limited, but from the viewpoint of the orientation of the dye during adsorption, the 3-position or 4 is preferred, and the 4-position is more preferred. R ⁴ represents an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. Preferable examples of the alkyl group and the aryl group include the following examples of the substituent T.

・ R ³
R ³ is an alkyl group having 1 to 30 carbon atoms, or represented by the following formula (2-1), (2-2), (2-3), (2-4) or formula (2-5) Represents a substituent. Among them, R ^{3 in the} formula (2) is more preferably represented by (2-1), (2-2), (2-3), (2-4) or the formula (2-5). Preferably, the general formula (2-2), (2-3), or the formula (2-4) is more preferable, the formula (2-3) or the formula (2-4) is more preferable, The formula (2-4) is particularly preferable.

R ¹¹ , R ²¹ , R ³¹ , R ⁴¹ , R ⁴² , R ⁵¹
R ¹¹ , R ²¹ , R ³¹ , R ⁴¹ , R ⁴² , and R ⁵¹ are each an alkyl group having 1 to 30 carbon atoms, a heteroaryl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and carbon Represents a substituent containing a group selected from an amino group of 1 to 30; In addition, the following examples of the substituent T are mentioned as a preferable thing of the said alkyl group, an aryl group, heteroaryl group, and an amino group. ^However, if ^{R 42} is a heteroaryl group, an aryl group, an amino ^{group, R 41} may be hydrogen atoms. Both R ⁴¹ and R ⁴² preferably have the substituents exemplified before the above proviso.

R ¹¹ , R ²¹ , R ³¹ , R ⁴¹ , R ⁴² , R ⁵¹ are preferably an alkyl group having 1 to 30 carbon atoms, a heteroaryl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, Of the amino group having 1 to 30 carbon atoms, an alkyl group having 3 to 30 carbon atoms, a heteroaryl group having 1 to 30 carbon atoms substituted by an alkyl group having 3 to 30 carbon atoms, and an alkyl group having 3 to 30 carbon atoms Substituted aryl group having 6 to 30 carbon atoms, heteroaryl group having 1 to 30 carbon atoms substituted by alkoxy group having 3 to 30 carbon atoms, aryl having 6 to 30 carbon atoms substituted by alkoxy group having 3 to 30 carbon atoms Group, an amino group substituted by an aryl group having 6 to 30 carbon atoms, or an amino group substituted by an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 4 to 30 carbon atoms, 30 a C1-C30 heteroaryl group substituted with a kill group, C6-C30 aryl group substituted with a C4-C30 alkyl group, C1-C30 alkoxy group substituted with a C1-C30 alkyl group An aryl group having 6 to 30 carbon atoms substituted by a 30 heteroaryl group or an alkoxy group having 4 to 30 carbon atoms, and particularly preferably an alkyl group having 4 to 30 carbon atoms or an alkoxy group having 4 to 30 carbon atoms. A substituted aryl group having 6 to 30 carbon atoms.

・ N11, n21, n31, n51
n11 represents an integer of 1 to 5. n11 is preferably an integer of 1 to 3, more preferably 1 or 2.
n21 represents an integer of 2 to 6. n21 is preferably an integer of 2 to 4, more preferably 2 or 3.
n31 represents an integer of 1 to 6. n31 is preferably an integer of 1 to 3, and more preferably 1 or 2.
n51 represents an integer of 2 to 6.

* Represents a bond.

In the dye of the present invention, R ³ is presumed to contribute to improvement in durability and open circuit voltage (Voc) in the photoelectric conversion element. When R ¹ and R ² are used as scaffolds and the complex dye is arranged in an upright manner, R ³ is extended toward the charge transfer layer side. For this reason, the functional substituents arranged so as to extend to the charge transfer layer side so that this R ³ protects its own scaffold is prevented from approaching the I ₃ ⁻ ions to the semiconductor electrode, and is injected into titania. electrons I ₃ ^- prevent migration into. By doing so, it is considered that the decrease in Voc is prevented. In addition, when donor properties are imparted to R ³ , it is considered that the LUMO level of the dye molecule may be appropriately increased. As a result, it is expected that the electron injection effect is increased and the open current (Jsc) is increased. In addition, functional substituents extending and arranged on the charge transfer layer side are thought to improve durability by preventing water molecules from approaching the semiconductor electrode and suppressing detachment of the dye from the surface. It is done. From this point of view, the substitution position of R ³ is preferably the 4th or 5th position (see the above formula (2)) and the 5th position is more preferred so that the association of the dyes is prevented and the parallel adsorption is more orderly.

・ La
La represents a single bond or an arylene group. When La is an arylene group, it is preferably a phenylene group or a thienylene group. La is particularly preferably a single bond.

・ N1 to n3
n1 represents an integer of 1 to 3. n2 and n3 each represents an integer of 1 to 4.

[Method for producing terpyridine compound]
In the present invention, when the terpyridine compound represented by the formula (2 ′) is synthesized and a dye represented by the following formula (1) having this as a ligand is produced, the terpyridine compound represented by the following formula (3) is used. going through the step of substituting substituents Hal of the compounds in the substituent ^{R 3} of formula (2 '), and a step of substituting the ^{R 101} substituents _CO 2 ^{R 101} in formula (3) in H Is preferred.

In the formula, n1 represents an integer of 1 to 3. n2 and n3 each represents an integer of 1 to 4. R ³ is an alkyl group having 1 to 30 carbon atoms, or represented by the formula (2-1), (2-2), (2-3), (2-4), or (2-5). Represents a substituent. The preferable one is also as defined above.

R ¹⁰¹ represents an alkyl group, and is preferably a methyl group, an ethyl group, or a propyl group.
Hal represents a halogen atom, preferably fluorine, chlorine or bromine, more preferably bromine. n1 represents an integer of 1 to 3. n2 and n3 each represents an integer of 1 to 4.

For details including the above-described substitution step, reference can be made to the procedures described in Examples below. Substitution reaction of substituents Hal and given organic group R ³ is, Suzuki reaction, Stille coupling can be used cross-coupling, such as Negishi coupling. The reaction of substituting the alkyl group R ¹⁰¹ with a hydrogen atom to form a carboxyl group may be performed by a normal hydrolysis reaction.

The dye represented by the formula (1) has a maximum absorption wavelength in an ethanol solution of preferably 500 to 700 nm, more preferably 550 to 650 nm.
Although the preferable specific example of the pigment | dye represented by Formula (1) of this invention below is shown, this invention is not limited to this.

Formula (6-1)
Dye 606 (R ⁶¹ : -C ₆ H ₁₃ , R ⁶² : H)
^{_{_{^{· Dye607 (R 61: -C 6}}}} H 13, R 62: -C 6 H 13)
^{^{· Dye608 (R 61: H,}} R 62: H)
Dye 609 (R ⁶¹ : H, R ⁶² : -C ₆ H ₁₃ )
Formula (6-2)
Dye 610 (R ⁶¹ : -C ₆ H ₁₃ , R ⁶² : H)
^{_{_{^{· Dye611 (R 61: -C 6}}}} H 13, R 62: -C 6 H 13)
^{^{· Dye612 (R 61: H,}} R 62: H)
Dye 613 (R ⁶¹ : H, R ⁶² : -C ₆ H ₁₃ )

The synthesis of the dye composed of the compound represented by the general formula (1) can be performed with reference to the methods described in Examples below.

In addition, in this specification, about the display of a compound (a complex and a pigment | dye are included), it uses for the meaning containing the said compound itself, its salt, and its ion. Moreover, it is the meaning including the derivative modified with the predetermined form in the range with the desired effect. Further, in the present specification, a substituent (including a linking group) for which substitution / non-substitution is not specified means that the group may have an arbitrary substituent. This is also synonymous for compounds that do not specify substitution / non-substitution. Preferred substituents include the following substituent T.

Examples of the substituent T include the following.
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1-ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl A group (preferably an alkenyl group having 2 to 20 carbon atoms such as vinyl, allyl, oleyl and the like), an alkynyl group (preferably an alkynyl group having 2 to 20 carbon atoms such as ethynyl, butadiynyl, phenylethynyl and the like), A cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, etc.), an aryl group (preferably an aryl group having 6 to 26 carbon atoms, for example, Phenyl, 1-naphthyl, 4-methoxyphenyl, -Chlorophenyl, 3-methylphenyl, etc.), heterocyclic groups (preferably heterocyclic groups having 2 to 20 carbon atoms, such as 2-pyridyl, 4-pyridyl, 2-imidazolyl, 2-benzimidazolyl, 2-thiazolyl, 2 -Oxazolyl etc.), an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, such as methoxy, ethoxy, isopropyloxy, benzyloxy etc.), an aryloxy group (preferably an aryloxy group having 6 to 26 carbon atoms) For example, phenoxy, 1-naphthyloxy, 3-methylphenoxy, 4-methoxyphenoxy, etc.), alkoxycarbonyl groups (preferably alkoxycarbonyl groups having 2 to 20 carbon atoms, such as ethoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.) ), Amino group (preferably carbon Amino groups having 0 to 20 atoms, such as amino, N, N-dimethylamino, N, N-diethylamino, N-ethylamino, anilino, etc., sulfonamido groups (preferably sulfonamido having 0 to 20 carbon atoms) A group such as N, N-dimethylsulfonamide, N-phenylsulfonamide, etc., an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms such as acetyloxy, benzoyloxy, etc.), a carbamoyl group (preferably A carbamoyl group having 1 to 20 carbon atoms, such as N, N-dimethylcarbamoyl, N-phenylcarbamoyl, etc.), an acylamino group (preferably an acylamino group having 1 to 20 carbon atoms, such as acetylamino, benzoylamino, etc.) , Cyano group, or halogen atom (eg fluorine atom, chlorine atom, bromine) Atoms, iodine atoms, etc.), more preferably alkyl groups, alkenyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, alkoxycarbonyl groups, amino groups, acylamino groups, cyano groups or halogen atoms, Particularly preferred are an alkyl group, an alkenyl group, a heterocyclic group, an alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group, and a cyano group. A plurality of substituents T may be bonded to each other to form a ring structure.

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

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

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

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

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

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

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

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

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

As the conductive support 1, a glass or a polymer material having a conductive film on the surface can be used as the support itself, such as metal. The conductive support 1 is preferably substantially transparent. Substantially transparent means that the light transmittance is 10% or more, preferably 50% or more, particularly preferably 80% or more. As the conductive support 1, a glass or polymer material coated with a conductive metal oxide can be used. The coating amount of the conductive metal oxide at this time is preferably 0.1 to 100 g per 1 m ² of glass or polymer material support. When a transparent conductive support is used, light is preferably incident from the support side. As an example of a polymer material preferably used, tetraacetylcellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), Examples include polyarylate (PAR), polysulfone (PSF), polyethersulfone (PES), polyetherimide (PEI), cyclic polyolefin, and brominated phenoxy. On the conductive support 1, a surface may be provided with a light management function. For example, an antireflection film in which high refractive films and low refractive index oxide films described in JP-A-2003-123859 are alternately laminated, The light guide function described in JP-A-2002-260746 is improved.

In addition to this, a metal support can also be preferably used. Examples thereof include titanium, aluminum, copper, nickel, iron, and stainless steel. These metals may be alloys. More preferably, titanium, aluminum, and copper are preferable, and titanium and aluminum are particularly preferable.

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

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

In addition to the sol-gel method, semiconductor fine particle dispersions can be prepared by depositing fine particles in a solvent and using them as they are when synthesizing semiconductors. And a method of mechanically pulverizing and crushing using a mill or a mortar. As the dispersion solvent, one or more of water and various organic solvents can be used. Examples of the organic solvent include alcohols such as methanol, ethanol, isopropyl alcohol, citronellol and terpineol, ketones such as acetone, esters such as ethyl acetate, dichloromethane, acetonitrile and the like.

When dispersing, if necessary, for example, a polymer such as polyethylene glycol, hydroxyethyl cellulose, carboxymethyl cellulose, a surfactant, an acid, or a chelating agent may be used in a small amount as a dispersion aid. However, most of these dispersing aids are preferably removed by a filtration method, a method using a separation membrane, a centrifugal method or the like before the step of forming a film on a conductive support. In the semiconductor fine particle dispersion, the solid content other than the semiconductor fine particles can be 10% by mass or less of the total dispersion. This concentration is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less. More preferably, it is 0.5% or less, and particularly preferably 0.2%. That is, in the semiconductor fine particle dispersion, the solid content other than the solvent and the semiconductor fine particles can be 10% by mass or less of the entire semiconductor fine dispersion. It is preferable to consist essentially of semiconductor fine particles and a dispersion solvent.

If the viscosity of the semiconductor fine particle dispersion is too high, the dispersion will aggregate and cannot be formed into a film. Conversely, if the viscosity of the semiconductor fine particle dispersion is too low, the liquid will flow and cannot be formed into a film. is there. Therefore, the viscosity of the dispersion is preferably 10 to 300 N · s / m ² at 25 ° C. More preferably, it is 50 to 200 N · s / m ² at 25 ° C.

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

The preferred thickness of the entire semiconductor fine particle layer is 0.1 μm to 100 μm. The thickness of the semiconductor fine particle layer is further preferably 1 μm to 30 μm, and more preferably 2 μm to 25 μm. The amount of the semiconductor fine particles supported per 1 m ² of the support is preferably 0.5 g to 400 g, more preferably 5 g to 100 g. The method for forming the film by applying the fine particle dispersion is not particularly limited, and a known method may be applied as appropriate.

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

In order to adsorb the sensitizing dye 21 to the semiconductor fine particles 22, it is preferable to immerse the well-dried semiconductor fine particles 22 in a dye adsorbing dye solution composed of the solution and the dye according to the present invention for a long time. The solution used for the dye solution for dye adsorption can be used without particular limitation as long as it can dissolve the sensitizing dye 21 according to the present invention. For example, ethanol, methanol, isopropanol, toluene, t-butanol, acetonitrile, acetone, n-butanol and the like can be used. Among these, ethanol and toluene can be preferably used.

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

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

By using such a dye amount, a sensitizing effect in a semiconductor can be sufficiently obtained. On the other hand, when the amount of the dye is small, the sensitizing effect is insufficient, and when the amount of the dye is too large, the dye not attached to the semiconductor floats and causes the sensitizing effect to be reduced.

(Counter electrode)
The counter electrode 4 functions as a positive electrode of the photoelectrochemical cell. The counter electrode 4 is usually synonymous with the conductive support 1 described above, but a support for the counter electrode is not necessarily required in a configuration in which the strength is sufficiently maintained. However, having a support is advantageous in terms of hermeticity. Examples of the material for the counter electrode 4 include platinum, carbon, and conductive polymer. Preferable examples include platinum, carbon, and conductive polymer.

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

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

A light management function for efficiently performing light scattering and reflection inside the layer of the light receiving electrode 5 may be provided. Preferable examples include those described in JP-A-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 due to direct contact between the electrolyte and the electrode. Preferable examples include Japanese Patent Application Laid-Open No. 06-507999.

In order to prevent contact between the light receiving electrode 5 and the counter electrode 4, it is preferable to use a spacer or a separator. A preferable example is JP-A-2001-283941.

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

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

Example 1 Synthesis Example of Dye Intermediate I-1 was synthesized by the route shown in Scheme 1.

(1) Synthesis of I-1-3 8 g (33.7 mmol) of 2,5-dibromopyridine (I-1-1) and 337 ml of toluene were stirred at −40 ° C. in a nitrogen atmosphere. To this was added 21.4 ml (1.02 eq) of a 1.6M hexane solution of n-butyllithium, and the mixture was stirred for 40 minutes. After adding 9.38 ml (3.0 eq) of N, N-dimethylacetamide, the mixture was stirred. The temperature was raised slowly to 20 ° C. Saturated aqueous ammonium chloride was added to quench the reaction. After extraction and liquid separation, purification was performed by column chromatography to obtain 6.74 g (yield 100%) of 2-acetyl-5-bromopyridine (Compound I-1-2) as a white solid.
Sodium hydroxide (4.73 g, 3.0 eq) was dissolved in 394 ml of methanol with heating, and the mixture was cooled and stirred at 0 ° C. to give 7.88 g (39.4 mmol) of 2-acetyl-5-bromopyridine (Compound I-1-2). ) And 3.26 ml of 2-furaldehyde, and the mixture was stirred at 0 ° C. for 5 hours. The solvent was concentrated under reduced pressure, extracted and separated with dichloromethane, and purified by column chromatography to obtain 8.24 g (yield 75%) of Compound I-1-3 as a yellow solid. The structure was confirmed by NMR spectrum.

(2) Synthesis of I-1-6 10 g (66.1 mmol) of Compound I-1-4, 43.6 ml (5 eq) of paraaldehyde, and 165 ml of acetonitrile were mixed and stirred at room temperature. Iron sulfate heptahydrate 305 mg (0.0166 eq), trifluoroacetic acid 4.9 ml (1 eq), and t-butyl peroxide were added, and the mixture was heated to reflux at 130 ° C. for 4 hours. After cooling and concentration under reduced pressure, a saturated aqueous sodium carbonate solution was added, extracted and separated with ethyl acetate, and purified by column chromatography to yield 6.77 g of Compound I-1-5 as a yellow solid (53% yield) Got. The structure was confirmed by NMR spectrum.
Compound I-1-5 6.77 g (35.0 mmol), iodine 8.89 g (1 eq), and 23.3 ml of pyridine were mixed and heated to reflux at 130 ° C. for 2 hours. After cooling, methanol was added and the mixture was concentrated under reduced pressure, recrystallized with methanol, filtered and dried to obtain 10.2 g (yield 73%) of a gray solid of Compound I-1-6. The structure was confirmed by NMR spectrum.

(3) Synthesis of I-1 To 1.08 g (3.88 mmol) of Compound I-1-3, ammonium acetate, 2.31 g (1.5 eq) of Compound I-1-6, and 39 ml of methanol were added and heated for 17 hours. Refluxed. After evaporating the solvent under reduced pressure, the residue was purified by column chromatography to obtain 743 mg (43% yield) of Compound I-1-7 solid. The structure was confirmed by NMR spectrum.
1 g (2.22 mmol) of compound I-1-7, 22 ml of pyridine, and 11 ml of water were mixed, and 1.75 g (5 eq) of potassium permanganate was added thereto while stirring, and the mixture was stirred at room temperature for 7 hours. Excess potassium permanganate was reduced with sodium thiosulfate, 2M aqueous sodium hydroxide solution was added, and the filtrate obtained by filtering the crystals was concentrated under reduced pressure. The residue was dissolved in aqueous sodium hydroxide solution, diluted aqueous hydrochloric acid solution was added, and the precipitated solid was filtered and dried to obtain compound I-1-8, and the entire amount was used as it was in the next step reaction.
14 ml of ethanol was added to compound I-1-8 and stirred, 296 μl (4 eq) of concentrated sulfuric acid was added, and the mixture was heated to reflux with stirring for 42 hours. Concentrate under reduced pressure, extract and separate with ethyl acetate and water, filter the organic layer, and purify by column chromatography to obtain 185 mg of Compound I-1 solid (37% yield from Compound I-1-7). succeeded in. The structure was confirmed by NMR spectrum (melting point: 146 ° C.).

Dye104 was synthesized by the route shown in Scheme 2.

Compound I-1 1.5 g, Compound D-5-1 0.95 g, tetrakistriphenylphosphine palladium (0) 110 mg, potassium carbonate 0.69 g, water 2.8 ml, toluene 3 ml and tetrahydrofuran 5 ml were mixed for 12 hours. The mixture was heated to reflux, treated according to a conventional method, and purified by column chromatography to obtain 0.816 g (yield 46%) of Compound D-5-2 as a solid.
The total amount of compound D-5-2 and 0.79 g of ruthenium chloride trihydrate were heated to reflux in ethanol for 3 hours to obtain 0.56 g (yield 49%) of compound D-5-3. .
Compound D-5-3 0.55 g, ammonium thiocyanate 1.87 g, and a mixed solvent of DMF and water were stirred at 130 ° C. for 4 hours. The solid of compound D-5-4 was taken out by post-treatment.
To the total amount of the obtained compound D-5-4, 13.2 g of triethylamine was added, and the mixture was stirred in a mixed solvent of DMF and water at 130 ° C. for 24 hours. Next, 0.25 g of tetrabutylammonium thiocyanate was added and further stirred. By post-treatment and purification, 536 mg of Dye 104 solid (yield 72% from compound D-5-3) was obtained (melting point: 250 ° C. or higher).

Other Dye 101 to 613 were synthesized by a method similar to Dye104.

Example 2 Initial Performance Evaluation of Photovoltaic Cell Disol on the conductive surface side of 20 mm × 20 mm transparent conductive glass having a fluorine-doped tin oxide layer (manufactured by Nippon Sheet Glass Co., Ltd., surface resistance of about 10 Ω / cm ² ) DSL 18NR-T made by the company was applied by screen printing. After coating, the film was dried at 25 ° C. for 30 minutes and baked on a hot plate at 500 ° C. for 30 minutes. The coating amount of titanium dioxide was 15.5 g / m ² and the film thickness was 9 μm. Similarly, printing and baking were performed using Dersol WER2-0 to form a scattering layer having a thickness of 4 μm. After the calcination, the mixture is cooled and immersed in 0.2 mmol / l (solvent: 1: 1 mixture of ethanol and acetonitrile) of the metal complex dye of the present invention and comparative dyes (A) and (B) for 20 hours, respectively. did. The structures of the comparative dyes (A) and (B) are shown below. Subsequently, the dyed titanium dioxide electrode was washed successively with ethanol and acetonitrile and dried in a dark place under a nitrogen stream to produce a titanium dioxide electrode. The comparative dye A is a ruthenium complex dye described in International Publication No. 98/50393 pamphlet.

The dye-sensitized TiO ₂ electrode substrate (20 mm × 20 mm) produced as described above was superposed on a platinum-deposited glass having the same size. Next, an electrolytic solution A (a solution in which 1,3-dimethylimidazolium iodide (0.65 mol / l) and iodine (0.05 mol / l) are dissolved in acetonitrile) is used in the gap between the two glasses by utilizing capillary action. Was introduced into the TiO ₂ electrode to obtain each photovoltaic cell shown in Table 1. As shown in FIG. 1, according to this example, a conductive support layer 1 made of conductive glass, a photosensitive layer 2 made of a dye sensitized 21 and a titania semiconductor layer 22, a charge transfer layer 3 made of the above electrolyte, and platinum. The counter electrode conductive layer substrate 4 made of the above was laminated in order and a photovoltaic cell sealed with an epoxy sealant was produced.

[Evaluation of long wavelength IPCE]
When the monochromatic light conversion efficiency (IPCE) of 400 to 900 nm of each of the above photovoltaic cells was measured at an interval of 10 nm using an IPCE (Incident Photo to Current Conversion Efficiency) measuring device manufactured by Optel, all the photovoltaic cells had a wavelength of 550 to 650 nm. A curve having a maximum value of IPCE in the wavelength range and gradually attenuated on the longer wavelength side than 700 nm is shown. Table 1 shows values obtained by standardizing the IPCE value (IPCE (%) = (number of generated electrons / number of irradiated photons) × 100) at 850 nm of each photovoltaic cell with the IPCE at the peak wavelength as 100. It can be said that a photovoltaic cell having a larger value has a higher conversion efficiency of long-wavelength light and is suitable for the object of the present invention.

[Evaluation of conversion efficiency]
A silver paste was applied to the end of the conductive glass of each of the photovoltaic cells to form a negative electrode, and the negative electrode and platinum-deposited glass (positive electrode) were connected to a current-voltage measuring device (Keutley SMU238 type). These photocells are irradiated with simulated solar light generated by passing light from a 500 W xenon lamp (manufactured by USHIO ELECTRIC CO., LTD.) Through an AM1.5 filter (AM1.5 manufactured by Oriel) while generating current. Was measured. The intensity of light was 100 mW / cm ² on the vertical plane. Table 1 shows the solar cell characteristics (short-circuit current density (Jsc), open-circuit voltage (Voc), form factor (FF), and conversion efficiency (η)) of each photovoltaic cell.

From Table 1, the photovoltaic cells 101 to 110 of the present invention have higher IPCE at 850 nm than the photovoltaic cells C11 and C12 using the comparative dyes (A) and (B), and are excellent in sensitizing efficiency of long-wavelength light. I understand. Moreover, according to this invention, it turns out that a performance improvement is seen in all of an open circuit voltage, a short circuit current, and conversion efficiency, maintaining a form factor in the favorable range.

(Embodiment 3) Durability Evaluation of Photovoltaic Cell The electrolytic solution was electrolytic solution B (3-methoxypropionitrile, 1,3-dimethylimidazolium iodide (0.65 mol / l), N-methylbenzimidazole (0.5 mol) / L) and iodine (0.1 mol / l dissolved solution), and each photovoltaic cell was prepared in the same manner as in Example 2. Table 2 shows the rate of decrease in conversion efficiency after storage of these photovoltaic cells at 80 ° C. for 300 hours in the dark.

Table 2 shows that the photovoltaic cell using the dye of the present invention has very high temperature durability.

Further, the dyes Dye 608 to 610 and Dye 612 and 613 were used in the same manner as in Example 1 to confirm the excellent effect of the present invention.
Based on the above results, the metal complex dye of the present invention is excellent in the ability to absorb long-wavelength light, and the photoelectric conversion element including the semiconductor fine particles adsorbing the metal complex dye has a wide wavelength range from the visible light region to the infrared region. High photoelectric conversion characteristics were shown. Moreover, high temperature durability was very high. A photovoltaic cell comprising such a photoelectric conversion element is extremely effective as a solar cell.

While this invention has been described in conjunction with its embodiments, we do not intend to limit our invention in any detail of the description unless otherwise specified and are contrary to the spirit and scope of the invention as set forth in the appended claims. I think it should be interpreted widely.
This application claims priority based on Japanese Patent Application No. 2011-195638 filed in Japan on September 8, 2011 and Japanese Patent Application No. 2012-074832 filed on March 28, 2012 in Japan. Which are hereby incorporated by reference herein as part of their description.

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

Claims

Dye represented by the formula (1) MX 3 Lt.
[Wherein M represents a transition metal selected from ruthenium, osmium, iron, rhenium, and technetium. X represents NCS − , Cl − , Br − , I − , CN − , NCO − , or H 2 O. Lt represents the formula (2). ]

[Wherein R 1 represents COOH, PO (OH) 2 , PO (OR 4 ) (OH), or CO (NHOH). R 2 represents COOH, PO (OH) 2 , PO (OR 4 ) (OH), or CO (NHOH). La represents a single bond or an arylene group. R 4 represents an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. n1 represents an integer of 1 to 3. n2 and n3 each represents an integer of 1 to 4. R 3 represents an alkyl group having 1 to 30 carbon atoms, or a group represented by the following formula (2-1), (2-2), (2-3), (2-4), or general formula (2-5). Represents a substituent. ]

[Wherein R 11 , R 21 , R 31 , R 41 , R 42 , and R 51 represent an alkyl group having 1 to 30 carbon atoms, a heteroaryl group having 1 to 30 carbon atoms, or an aryl having 6 to 30 carbon atoms. And a substituent containing any one of a group and an amino group having 1 to 30 carbon atoms. However, in the formula (2-4), when R 42 represents a substituent containing a heteroaryl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an amino group having 1 to 30 carbon atoms, 41 may be a hydrogen atom. n11 represents an integer of 1 to 5. n21 and n51 each represents an integer of 2 to 6. n31 represents an integer of 1 to 6. * Represents a bond. ]
The dye according to claim 1, wherein La in the formula (2) is a single bond.
The R 3 in the formula (2) is represented by the formula (2-1), (2-2), (2-3), (2-4) or (2-5). The described dyes.
The dye according to any one of claims 1 to 3, wherein R 3 in the formula (2) is represented by the formula (2-2), (2-3), or (2-4).
The dye according to any one of claims 1 to 4, wherein R 3 in the formula (2) is represented by the formula (2-3) or (2-4).
The dye according to any one of claims 1 to 5, wherein R 3 in the formula (2) is represented by the formula (2-4).
A photoelectric conversion device comprising a photoreceptor layer containing the dye according to any one of claims 1 to 6 and semiconductor fine particles.
A photoelectrochemical cell using the photoelectric conversion element according to claim 7.
A method for producing a terpyridine compound of the following formula (2 ′), wherein a substituent Hal of a compound represented by the following formula (3) is substituted with a substituent R 3 of the following formula (2 ′); A method for producing a terpyridine compound via a step of substituting R 101 of substituent CO 2 R 101 of formula (3) with H.

[Wherein n1 represents an integer of 1 to 3. n2 and n3 each represents an integer of 1 to 4. R 3 is an alkyl group having 1 to 30 carbon atoms, or a substituent represented by the formula (2-1), (2-2), (2-3), (2-4), or (2-5) Represents a group. ]

[Wherein R 11 , R 21 , R 31 , R 41 , R 42 , and R 51 represent an alkyl group having 1 to 30 carbon atoms, a heteroaryl group having 1 to 30 carbon atoms, or an aryl having 6 to 30 carbon atoms. And a substituent containing any one of a group and an amino group having 1 to 30 carbon atoms. However, in the formula (2-4), when R 42 represents a substituent containing a heteroaryl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an amino group having 1 to 30 carbon atoms, 41 may be a hydrogen atom. n11 represents an integer of 1 to 5. n21 and n51 each represents an integer of 2 to 6. n31 represents an integer of 1 to 6. * Represents a bond. ]

[R 101 represents an alkyl group. Hal represents a halogen atom. n1 represents an integer of 1 to 3. n2 and n3 each represents an integer of 1 to 4. ]
A method for producing a dye represented by the formula (1 ′) MX 3 Lt ′ having the terpyridine compound represented by the following formula (2 ′) as a ligand and having the terpyridine compound as a ligand. a step of substituting substituents Hal of the compound represented in the substituent R 3 of the formula (2 '), and a step of substituting the R 101 substituents CO 2 R 101 in formula (3) in H A method for producing a dye passing through.
[Wherein M represents a transition metal selected from ruthenium, osmium, iron, rhenium, and technetium. X represents NCS − , Cl − , Br − , I − , CN − , NCO − , or H 2 O. Lt ′ represents the formula (2 ′). ]

[Wherein n1 represents an integer of 1 to 3. n2 and n3 each represents an integer of 1 to 4. R 3 is an alkyl group having 1 to 30 carbon atoms, or a substituent represented by the formula (2-1), (2-2), (2-3), (2-4), or (2-5) Represents a group. ]

[Wherein R 11 , R 21 , R 31 , R 41 , R 42 , and R 51 represent an alkyl group having 1 to 30 carbon atoms, a heteroaryl group having 1 to 30 carbon atoms, or an aryl having 6 to 30 carbon atoms. And a substituent containing any one of a group and an amino group having 1 to 30 carbon atoms. However, in the formula (2-4), when R 42 represents a substituent containing a heteroaryl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an amino group having 1 to 30 carbon atoms, 41 may be a hydrogen atom. n11 represents an integer of 1 to 5. n21 and n51 each represents an integer of 2 to 6. n31 represents an integer of 1 to 6. * Represents a bond. ]

[R 101 represents an alkyl group. Hal represents a halogen atom. n1 represents an integer of 1 to 3. n2 and n3 each represents an integer of 1 to 4. ]
A terpyridine compound represented by the following formula (3).

[R 101 represents an alkyl group. Hal represents a halogen atom. n1 represents an integer of 1 to 3. n2 and n3 each represents an integer of 1 to 4. ]