JP2000357809A - Photoelectric conversion material, photoelectric conversion element and polymethine dye - Google Patents

Abstract

(57) [Summary] Dye-sensitized photoelectric conversion with high photoelectric conversion characteristics in the visible light region
Element material, photoelectric conversion element using the same, and novel polymer
Provide a tin dye. 【Task】 SOLUTION: The dye represented by the following general formula (I) is used.
Photoelectric conversion material containing semiconductor particles sensitized by sensitization. Embedded image In the general formula (I), R₁Are OH, SH, SeH, TeH,
NR_FiveR₆R represents any of_Five, R₆Is water
Represents an alkyl, an alkyl group, or an aryl group. R_Two~ R_FourIs it
Each represents hydrogen or a substituent, and is linked to each other to form a ring
You may. m represents an integer of 0 to 2. P₁Is cycloal
Represents a ken ring group or a heterocyclic group,₁, Q _TwoAre each
Oxygen, sulfur, selenium, tellurium, NR₇Or cycloalka
A ring group, a cycloalkene ring group or a heterocyclic group;₇
Represents hydrogen, an alkyl group, or an aryl group;₁, Q_Two
At least one is a cycloalkane ring group, a cycloalkene
And a heterocyclic group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photoelectric conversion material using semiconductor fine particles sensitized with a dye, and a photoelectric conversion element using the same. Furthermore, the present invention relates to a polymethine dye used for a photoelectric conversion material, a photoelectric conversion element, and the like.

[0002]

2. Description of the Related Art Photovoltaic power generation is a single-crystal silicon solar cell,
Polycrystalline silicon solar cells, amorphous silicon solar cells, and compound solar cells such as cadmium telluride and indium copper selenide have been put into practical use or subject to major research and development.
It is necessary to overcome problems such as a long energy payback time. On the other hand, many solar cells using an organic material intended to have a large area and a low price have been proposed so far, but have a problem that conversion efficiency is low and durability is poor. Under these circumstances, Nature (Vol.353, 737-
(Pp. 740, 1991) and U.S. Pat. No. 4,492,721 disclose a photoelectric conversion element and a solar cell using semiconductor fine particles sensitized by a dye, as well as materials and manufacturing techniques for producing the same. The proposed battery is a wet solar battery using a titanium dioxide porous thin film spectrally sensitized by a ruthenium complex as a working electrode. The first advantage of this method is that an inexpensive oxide semiconductor such as titanium dioxide can be used without purification to a high degree of purity, so that an inexpensive photoelectric conversion element can be provided. Since the absorption of the dye is broad, it is possible to convert light in almost all wavelength regions of visible light into electricity.

One of the demands for improvement of dye-sensitized photoelectric conversion elements is to use expensive ruthenium complex dyes as sensitizing dyes, and the development of photoelectric conversion elements sensitized by inexpensive organic dyes has been developed. Was desired. Such an example is disclosed in JP-A-11-86916 and European Patent EP09 / 09.
A method using the compound described in 11841A is known, but high photoelectric conversion efficiency has not been obtained.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a dye sensitizer which is inexpensive and has high conversion efficiency by using an organic dye having absorption in the visible light region and capable of efficiently sensitizing semiconductor fine particles. An object of the present invention is to provide a photoelectric conversion element material and a photoelectric conversion element using the same, and to provide a novel organic dye used for them.

[0005]

The above objects have been attained by the following items which specify the present invention and preferable items. (1) A photoelectric conversion material comprising semiconductor fine particles sensitized by a dye represented by the general formula (I).

[0006]

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In the general formula (I), R₁Is OH, SH, Se
H, TeH, NR_FiveR₆R represents any of_Five, R₆
Each independently represents hydrogen, an alkyl group, or an aryl group.
You. R _Two~ R_FourEach independently represents hydrogen or a substituent
Then, they may be connected to each other to form a ring. m is 0-2
Represents an integer. P₁Is a cycloalkene or heterocyclic ring
Represents a group, Q₁, Q_TwoAre independently oxygen, sulfur,
Ren, tellurium, NR₇Or cycloalkane ring group, cyclo
Represents a roalkene ring group or a heterocyclic group;₇Is hydrogen, al
Represents a kill group or an aryl group,₁, Q_TwoAt least
Either is a cycloalkane ring group, a cycloalkene ring group,
Represents any of heterocyclic groups. (2) R in general formula (I)₁Is OH
(1). (3) R in general formula (I)_Two~ R_FourBut each independently water
, An alkyl group, an alkenyl group, a cycloalkyl group,
A reel group or a heterocyclic group (1)
Is the photoelectric conversion material of (2). (4) Q in general formula (I)₁Is a cycloalkane ring group,
A chloroalkene ring group or a heterocyclic group;_Two
Is oxygen. (1) to (3), wherein
Replacement material. (5) The dye represented by the general formula (I) is represented by the general formula (II)
(1)-(4)
Fees.

[0008]

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In the general formula (II), P ₁ and m represent the general formula (I)
Is synonymous with R ₁₂ , R ₁₃ , and R ₁₄ each independently represent hydrogen, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and may be linked to each other to form a ring. Q ₁₁ represents a 5- or 6-membered cycloalkane ring group, cycloalkene ring group or heterocyclic group. (6) In formula (I) or (II), the ring forming P ₁ is a benzene ring, a naphthalene ring, a benzothiazole ring, a benzoxazole ring, a benzoselenazole ring,
A benzotellurazole ring, a 2-quinoline ring, a 4-quinoline ring, a benzimidazole ring, a thiazoline ring, an indolenine ring, an oxadiazole ring, a thiazole ring, or an imidazole ring. (1) to (5). (7) The dye represented by the general formula (II) is represented by the general formula (III-
(5) The photoelectric conversion material according to (6), which is a dye represented by formula (III-2).

[0010]

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In the general formulas (III-1) and (III-2), R
₁₂ , R ₁₃ , R ₁₄ , m, and Q ₁₁ have the same meanings as in formula (II). In the general formula (III-1), Y ₁ represents oxygen, sulfur, selenium, tellurium, CR ₁₇ R ₁₈ , NR ₁₉ , and R ₁₇ , R ₁₈ ,
R ₁₉ independently represents hydrogen, an alkyl group, an alkenyl group, or an aryl group. R ₁₅ represents hydrogen, an alkyl group, an alkenyl group, or an aryl group. R ₁₆ represents a substituent, a
Represents an integer of 0 to 4. When a is 2 or more, R ₁₆ may be the same or different, and may combine with each other to form a ring. In the general formula (III-2), one of Y ₂ and Y ₃ is N
R ₂₁ represents CR ₂₂ , the other represents CR ₂₂ , R ₂₁ represents hydrogen, an alkyl group, an alkenyl group, or an aryl group, and R ₂₂ represents hydrogen or a substituent. Za is a π bond 1 for connecting conjugates.
Represents an individual. R ₂₀ represents a substituent, and b represents an integer of 0 to 4. When b is 2 or more, R ₂₀ may be the same or different,
They may be connected to each other to form a ring. (8) R ₁₆ and R in the general formulas (III-1) and (III-2)
₂₀ and R ₂₂ each independently represent a cyano group, an alkoxycarbonyl group, a carboxyl group, an acyl group, an acyloxy group,
Alkylsulfonyl group, arylsulfonyl group, sulfonic acid group, sulfonamide group, carbamoyl group, amino group, acylamino group, alkyl group, alkenyl group, aryl group, alkoxy group, alkylthio group, aryloxy group, heterocyclic group, phosphonyl group , A phosphoryl group, a hydroxamic acid group, a hydroxyl group, an alkynyl group, a cycloalkyl group, or a halogen atom. (9) The photoelectric conversion material according to (7) or (8), wherein Y ₂ represents NR ₂₁ and Y ₃ represents CR ₂₂ in the general formula (III-2). (10) The photoelectric conversion material according to (7) or (8), wherein Y ₁ is represented by CR ₁₇ R ₁₈ in the general formula (III-1). (11) The photoelectric conversion according to (5) to (10), wherein Q ₁₁ in the general formulas (II), (III-1), and (III-2) is a 5- or 6-membered heterocycle. material. (12) In formula (II), (III -1), the ring formed by Q ₁₁ in (III -2) is, pyrazolidinedione ring, barbituric acid ring, thiobarbituric acid ring, an isoxazolone ring , Pyrazolone ring, pyridone ring, rhodanine ring, pyrrolotriazole ring, pyrazolotriazole ring,
(11) The photoelectric conversion material according to (11), which is any one of a hydantoin ring, a thiohydantoin ring, a thiazolidinedione ring, and an oxazolidinonethione ring. (13) R _{2 to} R ₄ in the general formula (I);
R _{12 to} R ₁₄ in (I), (III-1) and (III-2)
Are hydrogen. (1) to (1)
2) The photoelectric conversion material. (14) R ₁₅ in the general formula (III-1);
The photoelectric conversion materials according to (7) to (13), wherein R ₂₁ in I-2) is an alkyl group. (15) The photoelectric conversion material according to (1) to (14), wherein the semiconductor fine particles sensitized by the dye are titanium oxide fine particles. (16) A photoelectric conversion element comprising a conductive support coated with the photoelectric conversion material according to any one of (1) to (15), a charge transfer layer, and a counter electrode. (17) A polymethine dye represented by the following general formula (IV-1) or (IV-2).

[0012]

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In the general formula (IV-1) or (IV-2), R
_{12, R 13, R 14,} R 15, R 21, m, a, b, Y 1, Za
Has the same meaning as in formulas (II), (III-1) and (III-2). One of Y ₁₂ and Y ₁₃ is NR ₂₁ and the other is C
R ₂₃ represents R ₂₃ and R ₂₄ and R ₂₅ each independently represent a cyano group, an alkoxycarbonyl group, a carboxyl group, an acyl group, an acyloxy group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonic acid group, a sulfonamide group, a carbamoyl group, an amino group; Group, acylamino group, alkyl group, alkenyl group, aryl group, alkoxy group, alkylthio group,
Represents an aryloxy group, a heterocyclic group, a phosphonyl group, a phosphoryl group, a hydroxamic acid group, a hydroxyl group, an alkynyl group, a cycloalkyl group, or a halogen atom. a is 2
In the above, R ₂₄ may be the same or different, and may be connected to each other to form a ring. When b is 2 or more, R ₂₅ may be the same or different, and may combine with each other to form a ring. R ₂₃ has the same meaning as hydrogen or R ₂₄ and R ₂₅ . Q ₂₁ is,
Pyrazolidinedione ring group, barbituric acid ring group, thiobarbituric acid ring group, isoxazolone ring group, pyrazolone ring group, pyridone ring group, rhodanine ring group, pyrrolotriazole ring group, pyrazolotriazole ring group, hydantoin ring Group, thiohydantoin ring group, thiazolidinedione ring group,
Represents an oxazolidinonethione ring group.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION

The dye of the present invention represented by formula (I) will be described below in detail. When the compound of the present invention contains an alkyl group, an alkenyl group, an alkynyl group, an alkylene group, etc., they may be linear or branched, and may be substituted or unsubstituted. When the compound of the present invention contains an aryl group, a heterocyclic group, a cycloalkyl group, etc., they may be substituted or unsubstituted, and may be monocyclic or condensed.

In the general formula (I), R ₁ is OH, SH, Se
H, TeH, or NR ₅ R ₆ , preferably OH, NR ₅ R ₆ , and more preferably OH.
R ₅ and R ₆ are each independently hydrogen or an alkyl group (preferably having 1 to 20 carbon atoms (hereinafter referred to as C number), such as methyl, ethyl, n-propyl, i-propyl, t-butyl, n-butyl, 2-ethylhexyl, benzyl, 2-
Ethoxyethyl, 1-carboxylmethyl, 2-carboxylethyl, 3-carboxylpropyl, 3-sulfopropyl, 4-sulfobutyl, 2-phosphorylethyl,
2-phosphonylethyl), an aryl group (preferably having 6 to 20 carbon atoms, for example, phenyl, 2-naphthyl, 4-carboxylphenyl, 3-sulfophenyl, 4-methoxyphenyl), and hydrogen or an alkyl group is preferable.

In the general formula (I), R _{2 to} R ₄ each independently represent hydrogen or a substituent, preferably hydrogen, an alkyl group (preferable examples are the same as R ₅ and R ₆ ), and an alkenyl group (preferably C2-20, for example, allyl, vinyl, oleyl), cycloalkyl group (preferably C3-2)
0, for example, cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl), an aryl group (preferable examples are the same as R ₅ and R ₆ ), a heterocyclic group (preferably having 1 to 20, for example, 4-pyridyl) 2-pyridyl,
1-imidazolyl, 1-oxazolyl, 1-thiazolyl), preferably hydrogen, an alkyl group or an alkenyl group, more preferably hydrogen. R _{2 to} R ₄ may be linked to each other to form a ring. In the general formula (I), m
Represents 0, 1 or 2, and is more preferably 0 or 1.

In the general formula (I), P ₁ represents a cycloalkene ring group (preferably having a C number of 3 to 40) or a heterocyclic group (preferably having a C number of 1 to 40). It may ring. P ₁ is more preferably a heterocyclic group. The ring forming P ₁ is a cyclopropene ring, cyclopentadiene ring, cyclohexadiene ring, benzocyclohexadiene ring, benzothiazole ring, benzoxazole ring, benzoselenazole ring, benzotellurazole ring, 2-quinoline ring, 4-quinoline Ring, benzimidazole ring, thiazoline ring, indolenine ring, oxadiazole ring, thiazole ring, imidazole ring, more preferably, any of which may be substituted or condensed, benzothiazole ring, benzoxazole ring, benzo A selenazole ring, a benzotellurazole ring, a 2-quinoline ring, a 4-quinoline ring, a benzimidazole ring, and an indolenine ring, and more preferably, a benzothiazole ring or a benzoxazole which may be substituted or condensed. Ring, benzimidazole ring, a Is a Dorenin ring, particularly preferably an indolenine ring. In the present invention, the cycloalkene ring group is represented by a cyclic hydrocarbon ring, has at least one double bond in the ring portion, and has a hydrocarbon ring structure in which ＯO or the like can be bonded to a ring carbon atom. Further, the ring refers to a ring represented by a ring group in which an aromatic ring (such as a benzene ring) may be condensed or may have a substituent.

In the general formula (I), Q ₁ and Q ₂ each independently represent oxygen, sulfur, selenium, tellurium, NR ₇ or a cycloalkane ring group, a cycloalkene ring group or a heterocyclic group, preferably oxygen, Represents sulfur, NR ₇ or a cycloalkane ring group, a cycloalkene ring group, or a heterocyclic group, more preferably represents an oxygen or cycloalkane ring group, a cycloalkene ring group, or a heterocyclic group, and further preferably represents an oxygen or heterocyclic group. Represents At least _{one of} Q ₁ and Q ₂ represents a cycloalkane ring group, a cycloalkene ring group or a heterocyclic group, and preferably at least one of them represents a heterocyclic group. R ₇ represents a hydrogen, an alkyl group, or an aryl group (preferable examples are the same as R ₅ and R ₆ ), but it is preferably a hydrogen or an alkyl group.

In the present invention, the cycloalkane ring group is represented by a cyclic hydrocarbon ring, has no unsaturated bond in the ring portion, and has a hydrocarbon ring structure in which ＝ O or the like can be bonded to a ring carbon atom. The ring refers to a ring represented by a ring in which an aromatic ring (such as a benzene ring) may be condensed or may have a substituent. The cycloalkane ring preferably has 3 to 40 carbon atoms, preferably a 5- or 6-membered ring, and more preferably a 4,4-dimethylcyclohexane-2,6-dione ring, an indandione ring or the like. As the cycloalkene ring, a C number of 3 to 40
Are preferable, and a 6-membered ring is preferable, and an oxocyclohexadiene ring, an oxobenzocyclohexadiene ring and the like are preferable. The hetero ring is preferably a C 1-40 ring, preferably a 5- or 6-membered ring, and a pyrazolidinedione ring, a barbituric acid ring, a thiobarbituric acid ring, an isoxazolone ring, a pyrazolone ring, a pyridone ring, and a rhodanine ring. More preferably form a pyrrolotriazole ring, a pyrazolotriazole ring, an indandione ring, a hydantoin ring, a thiohydantoin ring, a thiazolidinedione ring, an oxazolidinonethione ring, and a pyrazolidinedione ring, a pyrazolone ring, a rhodanin ring, and indandione. It is more preferable to form a ring, a thiazolidinedione ring or an oxazolidinonethione ring, and it is particularly preferable to form a pyrazolidinedione ring, a pyrazolone ring or a rhodanine ring. less than,
Preferred examples when Q ₁ and Q ₂ are a cycloalkane ring group, a cycloalkene ring group or a heterocyclic group will be specifically shown, but the present invention is not limited thereto.

[0021]

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[0022]

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In the general formula (I), Q ₁ is a heterocyclic group,
Preferably, Q ₂ is oxygen.

The dye represented by the general formula (I) is
More preferably, it is represented by I). In the general formula (II),
P₁, M have the same meanings as in formula (I). General formula (II)
Medium, R₁₂, R₁₃, R₁₄Is independently hydrogen or alkyl
Group, alkenyl group, cycloalkyl group, aryl group,
Represents a telocyclic group (preferable examples are R _Two~ R_FourSame), good
More preferably, it represents hydrogen, an alkyl group, or an alkenyl group, and more
It preferably represents hydrogen. R₁₂~ R₁₄Are connected to each other
May be formed.

In the general formula (II), Q ₁₁ represents a 5- or 6-membered ring Q ₁₁ represents a 5- or 6-membered cycloalkane ring group, a cycloalkene ring group or a heterocyclic group (preferable examples are Q ₁ and the same).

The dye represented by formula (II) is more preferably represented by formula (III-1) or (III-2). General formulas (III-1), (III-2)
In the formula, R ₁₂ , R ₁₃ , R ₁₄ , m, and Q ₁₁ have the same meanings as in formula (II).

In the general formula (III-1), Y ₁ represents oxygen, sulfur, selenium, tellurium, CR ₁₇ R ₁₈ , NR ₁₉ , preferably oxygen, sulfur, CR ₁₇ R ₁₈ , NR ₁₉ , Preferably represents sulfur, CR ₁₇ R ₁₈ , most preferably CR
Representing a ₁₇ R _18. In the general formula (III-1), R ₁₇ , R ₁₈ , R
₁₉ is each independently hydrogen, an alkyl group, an alkenyl group,
Represents an aryl group (preferred examples are the same as R _{2 to} R ₄ ),
More preferably, it is an alkyl group. General formula (III-
In 1), R ₁₅ represents hydrogen, an alkyl group, an alkenyl group, or an aryl group (preferable examples are the same as R _{2 to} R ₄ ), more preferably an alkyl group or an aryl group, and more preferably an alkyl group. More preferred.

In the general formula (III-1), R ₁₆ represents a substituent, preferably a cyano group or an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, for example, ethoxycarbonyl,
-Ethylhexyloxycarbonyl, cyclohexyloxycarbonyl), carboxyl group, acyl group (preferably having 1 to 20, for example, acetyl, benzoyl), acyloxy group (preferably having 1 to 20, for example, acetyloxy, benzoyloxy), alkyl A sulfonyl group (preferably having 1 to 20 carbon atoms such as methanesulfonyl,
i-butanesulfonyl), arylsulfonyl group (preferably having 6 to 26 carbon atoms, such as benzenesulfonyl,
Methoxybenzenesulfonyl), sulfonic acid group (-SO
₃ H), a sulfonamide group (preferably having a C number of 0 to 20,
For example, N, N-dimethylsulfonamide, N-phenylsulfonamide), a carbamoyl group (preferably having a C number of 1)
To 20, for example, N, N-dimethylcarbamoyl, N-phenylcarbamoyl), an amino group (preferably having a C number of 0 to 0)
20, for example, amino, N, N-dimethylamino, anilino), an acylamino group (preferably having 1 to 20, for example, acetylamino, benzoylamino), an alkyl group (preferably having 1 to 20, for example, methyl, ethyl, i
Propyl, t-butyl), an alkenyl group (preferably having 2 to 20 carbon atoms such as vinyl, allyl, oleyl), an aryl group (preferably having 6 to 26 carbon atoms such as phenyl,
1-naphthyl, 4-methoxyphenyl, 2-chlorophenyl, 3-methylphenyl, 4-carboxylphenyl, 3-sulfophenyl), alkoxy group (preferably having 1 to 20 carbon atoms, for example, methoxy, i-propoxy), alkylthio group (Preferably C 1-20, for example, methylthio), an aryloxy group (preferably C 6-26,
For example, phenoxy, 2-naphthyloxy), a heterocyclic group (preferably having 2 to 20 carbon atoms, for example, 2-thiazolyl, 2
-Oxazolyl), a phosphonyl group (e.g.
0, for example, -PO (OH) ₂ , -PO (OC
₂ H _{5) 2),} a phosphoryl group (preferably having a C number of 0 to 2
0, for example, -OPO (OH) ₂ , -OPO (OC
₂ H _{5) 2),} a hydroxamic acid group (preferably a C number of 1 to
20, for example -CONHOH, -CON (CH ₃₎ O
H), a hydroxyl group, an alkynyl group (preferably having a C number of 2 to 20, for example, ethynyl, 2-phenylethynyl),
Represents a cycloalkyl group (preferably having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl or cyclohexyl) or a halogen atom (such as fluorine, chlorine, bromine or iodine), and more preferably a cyano group, an alkoxycarbonyl group, a carboxyl group, or an acyloxy group. Group, alkylsulfonyl group, arylsulfonyl group, sulfonic acid group, sulfonamide group, carbamoyl group, alkyl group, alkenyl group, alkoxy group, heterocyclic group, phosphonyl group, phosphoryl group, hydroxamic acid group, hydroxyl group, halogen atom And more preferably a cyano group, an alkoxycarbonyl group, a carboxyl group, an acyloxy group, a sulfonic acid group, an alkyl group, an alkenyl group, a phosphonyl group, a phosphoryl group, a hydroxyl group, or a halogen atom.

In the general formula (III-1), a represents an integer of 0 to 4, and when a is 2 or more, R ₁₆ may be the same or different and may combine with each other to form a ring. . The ring to be formed is preferably a benzene ring (the ring may be further substituted), and is represented by the chemical formulas 19 and 20 in which two compound structures of the present invention are symmetrically bonded via a benzene ring. Such a structure is also preferable.

In the general formula (III-2), Y_Two, Y_ThreeWhich way
Karakara NR_{twenty one}And the other CR_{twenty two}And Y_TwoIs NR
_{twenty one}And Y_ThreeIs CR_{twenty two}It is more preferable to represent Za is
Represents one π bond for connecting conjugates, ie
Is a 4-quinoline ring or 1-iso
It is called a quinoline ring, and a 4-quinoline ring is better.
Is more preferable. In the general formula (III-2), R_{twenty one}Is hydrogen, al
Represents a kill group, an alkenyl group, or an aryl group (preferred examples
Is R_Two~ R_FourSame as above), preferably an alkyl group or
Represents a reel group, and more preferably represents an alkyl group. one
In the general formula (III-2), R₂₀Represents a substituent independently
And a preferred example is R ₁₆Is the same as b is an integer from 0 to 4
And when b is 2 or more, R₂₀May be the same or different
Alternatively, they may be connected to each other to form a ring. Ring formed
Is preferably a benzene ring. , R_{twenty two}Is hydrogen or R₂₀
And a preferred example of the substituent is R₁₆Same as
You.

The dye represented by the general formula (I) is represented by the general formula (IV)
-1) or (IV-2) is more preferable.
No. In the general formula (IV-1) or (IV-2), R₁₂,
R₁₃, R₁₄, R₁₅, R_{twenty one}, M, a, b, Y₁, Za is one
Synonymous with general formulas (II), (III-1) and (III-2)
You. Moreover, each preferable thing is also the same. Y₁Haichi
As in the general formula (III-1), preferably oxygen, sulfur, CR
₁₇R₁₈, NR ₁₉And more preferably sulfur, CR₁₇R
₁₈And most preferably CR₁₇R₁₈Represents R₁₇, R
₁₈, R₁₉Is more preferably an alkyl group. R₁₅
Is a preferred example of R_Two~ R_FourIs the same as the above, an alkyl group,
An aryl group is more preferable, and an alkyl group
More preferably, R_{twenty four}Is R₁₆The same thing is preferred
And more preferably a cyano group, an alkoxycarbonyl
Group, carboxyl group, acyloxy group, alkyl sulfo
Nyl group, arylsulfonyl group, sulfonic acid group, sulfo
Amido group, carbamoyl group, alkyl group, alkenyl
Group, alkoxy group, heterocyclic group, phosphonyl group, phospho
Ryl group, hydroxamic acid group, hydroxyl group, halogen
And more preferably a cyano group or an alkoxy group.
Rubonyl group, carboxyl group, acyloxy group, sulfo
Acid groups, alkyl groups, alkenyl groups, phosphonyl groups,
These are a sphoryl group, a hydroxyl group, and a halogen atom. a
Is preferably 1 or 2, and when a is 2, a benzene ring is formed.
It is also preferable to form it. m is preferably 0, 1 or 2
Yes, 0 or 1 is more preferred.

One of Y ₁₂ and Y ₁₃ represents NR ₂₁ and the other represents CR _23. Preferred examples are the same as Y ₂ and Y ₃ . R ₂₄ and R ₂₅ each independently represent a cyano group, an alkoxycarbonyl group, a carboxyl group, an acyl group, an acyloxy group, an alkylsulfonyl group, an arylsulfonyl group,
Sulfonic acid group, sulfonamide group, carbamoyl group, amino group, acylamino group, alkyl group, alkenyl group,
Aryl group, alkoxy group, alkylthio group, aryloxy group, heterocyclic group, phosphonyl group, phosphoryl group,
Represents a hydroxamic acid group, a hydroxyl group, an alkynyl group, a cyclohexyl group, or a halogen atom;
Same as ₁₆ . R ₂₃ has the same meaning as hydrogen or R ₂₄ and R ₂₅ , and preferred examples of the substituent are also the same. When a is 2 or more, R ₂₄ may be the same or different, and may combine with each other to form a ring. When b is 2 or more, R ₂₅ may be the same or different, and may combine with each other to form a ring. The ring formed is preferably a benzene ring.

In formulas (IV-1) and (IV-2), the ring forming Q ₂₁ is a pyrazolidinedione ring, a barbituric acid ring, a thiobarbituric acid ring, an isoxazolone ring, a pyrazolone ring, Represents a pyridone ring, rhodanine ring, pyrrolotriazole ring, pyrazolotriazole ring, indandione ring, hydantoin ring, thiohydantoin ring, thiazolidinedione ring, oxazolidinonethione ring, preferably
A pyrazolidinedione ring, a pyrazolone ring, a rhodanine ring, an indandione ring, a thiazolidinedione ring and an oxazolidinonethione ring are preferred, and a pyrazolidinedione ring, a pyrazolone ring and a rhodanine ring are particularly preferred.

The dye represented by the general formula (I) is represented by the general formula (IV)
It is particularly preferable to be represented by -1).

Specific examples of the compound represented by formula (I) of the present invention are shown below, but the present invention is not limited thereto. In addition, the structural formula of the dye described herein is only the ultimate structure of one of many possible resonance structures.

[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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The synthesis of the compound represented by the general formula (I) used in the present invention is carried out according to Ukrainskii Khimicheskii Zhurnal.
Reference can be made to Vol. 40, No. 3, pp. 253 to 258 and descriptions of documents cited in these documents.

The general method for synthesizing the dye of the present invention is shown below, but the present invention is not limited thereto.

[0051]

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When synthesizing the dye represented by the general formula (I) of the present invention, a method using a cyclic compound having a methylene moiety (—CH ₂ —) having a small acid dissociation constant (pKa) as a raw material is preferable. Is generally referred to as an active methylene compound, and is preferable because it has a wide variety of reaction raw materials. Furthermore, a so-called "4-equivalent coupler" which is known in silver halide photography
Is also preferred.

As shown in Scheme 1, the dye of the present invention has a terminal ethyl squarate 3 synthesized by reacting a quaternary salt 1 with diethyl squarate 2 in a solvent such as ethanol in the presence of a base such as triethylamine. Cyclic compound 4 having an active methylene moiety (... Q ₃₁ ... CH ₂
..) Is the equivalent of sodium methoxide or potassium t
-It can be easily obtained by reacting in a solvent such as butanol or ethanol in the presence of a base such as butoxide, triethylamine or potassium carbonate. X ₁ of the quaternary salt 1 represents a counter anion.

Next, the structure and material of the photoelectric conversion material and the photoelectric conversion element of the present invention will be described in detail. In the present invention, the photoelectric conversion material has a semiconductor and a dye sensitizing the semiconductor. The semiconductor used for photoelectric conversion is a so-called photoconductor,
It plays a role of absorbing light to separate charges and generate electrons and holes. In a dye-sensitized semiconductor, light absorption and the resulting generation of electrons and holes mainly occur in the dye, and the semiconductor is responsible for receiving and transmitting the electrons.

In the present invention, the dye-sensitized photoelectric conversion element comprises a conductive support, a semiconductor film (photosensitive layer) sensitized by a dye provided on the conductive support, a charge transfer layer, and a counter electrode. Here, the above photoelectric conversion material is used for a semiconductor film sensitized by a dye, that is, a photosensitive layer. A photocell that can use this photoelectric conversion element for a battery to work in an external circuit is a photocell. The photosensitive layer is designed according to the purpose, and may have a single-layer structure or a multilayer structure. Light incident on the photosensitive layer excites dyes and the like. The excited dye or the like has high-energy electrons, which are transferred from the dye or the like to the conduction band of the semiconductor fine particles and reach the conductive support by diffusion. At this time, molecules such as dyes are oxidized. In a photovoltaic cell, electrons on a conductive support return to an oxidized substance such as a dye through a counter electrode and a charge transfer layer while working in an external circuit, and the dye or the like is regenerated. The semiconductor film functions as a negative electrode of this battery. In the present invention, at the boundaries between the layers (for example, the boundary between the conductive layer and the photosensitive layer of the conductive support, the boundary between the photosensitive layer and the charge transfer layer, the boundary between the charge transfer layer and the counter electrode, etc.) They may be mutually diffused and mixed.

As the semiconductor, in addition to a simple semiconductor such as silicon and germanium, a III-V compound semiconductor, a metal chalcogenide (eg, oxide, sulfide, selenide, or the like), a compound having a perovskite structure, or the like is used. be able to. Preferably as a metal chalcogenide titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium or tantalum oxide, cadmium, zinc, lead, silver,
Examples include antimony, sulfide of bismuth, cadmium, selenide of lead, and telluride of cadmium. Examples of the compound semiconductor include phosphides such as zinc, gallium, indium, and cadmium, gallium arsenide, copper-indium-selenide, and copper-indium-sulfide. Further, as the compound having a perovskite structure, strontium titanate, calcium titanate, sodium titanate, barium titanate, and potassium niobate are preferably exemplified.

It is more preferable that the semiconductor used in the present invention be used.
Specifically, specifically, Si, TiO_Two, SnO_Two, Fe_TwoO_Three, WO_Three, Zn
O, Nb_TwoO_Five, CdS, ZnS, PbS, Bi_TwoS_Three, CdSe, CdTe,
GaP, InP, GaAs, CuInS_Two, CuInSe_TwoIs mentioned. Sa
More preferably TiO_Two, ZnO, SnO_Two, Fe_TwoO_Three, WO_Three, Nb_TwoO
_Five, CdS, PbS, CdSe, InP, GaAs, CuInS_Two, CuInSe _Two
And particularly preferably, TiO_TwoOr Nb_TwoO_FiveAnd the most
Also preferably TiO_TwoIt is.

The semiconductor used in the present invention may be single crystal or polycrystal. Although a single crystal is preferable as the conversion efficiency, a polycrystal is preferable in terms of manufacturing cost, securing of raw materials, energy payback time, and the like, and a fine particle semiconductor having a nanometer to micrometer size is particularly preferable.

The particle diameter of these semiconductor fine particles is preferably 5 to 200 nm as a primary particle as an average particle diameter using a diameter when the projected area is converted into a circle, and particularly preferably 8 to 1 nm.
Preferably it is 00 nm. The average particle size of the semiconductor fine particles (secondary particles) in the dispersion is 0.01 to 10
It is preferably 0 μm.

Further, two or more kinds of fine particles having different particle size distributions may be mixed and used. In this case, the average size of the small particles is preferably 5 nm or less. Also, in order to improve the light capture rate by scattering incident light,
Semiconductor particles having a large particle size, for example, about 300 nm may be mixed.

The method for producing the semiconductor fine particles is described in Sol-gel described in "Sol-gel method science" by Agaku Shofusha (1988) by Sakubana Suzuka and "Thin-film coating technology by the sol-gel method" (1995) by Technical Information Association. Tadao Sugimoto, "Synthesis of Monodisperse Particles by New Synthetic Gel-Sol Method and Size Morphology Control" Materia, Vol. 35, No. 9, 1012
The gel-sol method described on pages 10 to 1018 (1996) is preferred.

A method of producing an oxide by hydrolyzing a chloride in an oxyhydrogen flame at a high temperature, which is developed by Degussa, is also preferable.

In the case of titanium oxide, any of the above sol-gel method, gel-sol method, and high-temperature hydrolysis method of chloride in an oxyhydrogen flame is preferred. Further, Manabu Kiyono's “Titanium oxide physical properties and applied technology” Gihodo Shuppan ( 1997) can also be used.

In the case of titanium oxide, among the sol-gel methods described above, in particular, “Journal of American
Ceramic Society Vol. 80, No. 12, 31
Pages 57 to 3171 (1997) "and Burnside et al.," Chemical Materials Vol. 10, No. 9, pages 2419 to 2425 "
The described method is preferred.

As the conductive support, use is made of a support such as metal, which has conductivity itself, or a glass or plastic support having a conductive layer containing a conductive agent (conductive agent layer) on the surface. Can be. In the latter case, a preferable conductive agent is a metal (for example, platinum, gold, silver, copper, aluminum, rhodium, indium, etc.), carbon, or a conductive metal oxide (indium-tin composite oxide, tin oxide doped with fluorine). And the like). The conductive agent layer preferably has a thickness of about 0.02 to 10 μm.

The lower the surface resistance of the conductive support, the better. The preferable range of the surface resistance is 100 Ω / □ or less, more preferably 40 Ω / □ or less. The lower limit is not particularly limited, but is usually about 0.1 Ω / □.

Preferably, the conductive support is substantially transparent. Substantially transparent means that light transmittance is 10%
The above means that it is preferably at least 50%, particularly preferably at least 70%. As the transparent conductive support, glass or plastic coated with a conductive metal oxide is preferable. Of these, conductive glass in which a conductive layer made of tin dioxide doped with fluorine is deposited on a transparent substrate made of low-cost soda-lime float glass is particularly preferable. In addition, for a low-cost and flexible photoelectric conversion element or solar cell, a transparent polymer film provided with the above conductive layer is preferably used.
Transparent polymer films include tetraacetyl cellulose (TAC), polyethylene terephthalate (PET),
Polyethylene naphthalate (PEN), syndioctatic polysterene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate (PAr), polysulfone (PSF), polyester sulfone (PES), polyetherimide (PE
I), cyclic polyolefins, brominated phenoxy and the like. When a transparent conductive support is used, it is preferable that light is incident from the support side. In this case, the coating amount of the conductive metal oxide is preferably 0.01 to 100 g per 1 m ² of a glass or plastic support.

It is preferable to use a metal lead for the purpose of lowering the resistance of the transparent conductive substrate. The material of the metal lead is preferably a metal such as aluminum, copper, silver, gold, platinum and nickel, and particularly preferably aluminum and silver. It is preferable that the metal lead is provided on a transparent substrate by vapor deposition, sputtering, or the like, and a transparent conductive layer made of tin oxide doped with fluorine or an ITO film is provided thereon. It is also preferable to provide a metal lead on the transparent conductive layer after providing the transparent conductive layer on a transparent substrate. The decrease in the amount of incident light due to the installation of metal leads is 1 to 10%, more preferably 1 to 5%.
It is.

Examples of the method of applying semiconductor fine particles on a conductive support include a method of applying a dispersion or colloid solution of semiconductor fine particles on a conductive support, and the above-described sol-gel method. In consideration of mass production of photoelectric conversion elements, liquid physical properties, and flexibility of a support, a wet film forming method is relatively advantageous. As a wet type film applying method, a coating method and a printing method are typical.

As a method of preparing a dispersion of semiconductor fine particles, in addition to the above-mentioned sol-gel method, a method of grinding in a mortar, a method of dispersing while pulverizing using a mill, or a method of synthesizing a semiconductor in a solvent when synthesizing. A method of precipitating it as fine particles and using it as it is may be mentioned. Examples of the dispersion medium include water and various organic solvents (eg, methanol, ethanol, isopropyl alcohol, dichloromethane, acetone, acetonitrile, ethyl acetate, etc.). When dispersing,
If necessary, a polymer, a surfactant, an acid, a chelating agent or the like may be used as a dispersing aid.

As a coating method, a roller method, a dipping method as an application system, an air knife method, a blade method and the like as a metering system.
No. 4,589,294, U.S. Pat. No. 2,761,419, and U.S. Pat.
A slide hopper method, an extrusion method, a curtain method and the like described in US Pat. As a general-purpose machine, a spin method or a spray method is also preferably used.

As the wet printing method, three printing methods including letterpress, offset, and gravure, intaglio, rubber plate, screen printing, and the like have been conventionally preferred.

From the above methods, a preferable film forming method is selected according to the liquid viscosity and the wet thickness.

The liquid viscosity greatly depends on the type and dispersibility of the semiconductor fine particles, the type of solvent used, and additives such as a surfactant and a binder. High viscosity liquid (for example, 0.01 to 500 Po
In ise), an extrusion method or a casting method is preferable, and in a low-viscosity liquid (for example, 0.1 Poise or less), a slide hopper method, a wire bar method, or a spin method is preferable, and a uniform film can be formed.

It should be noted that even in the case of applying a low-viscosity liquid by the extrusion method, the application is possible if the applied amount is a certain amount.

Screen printing is often used for applying a high-viscosity paste of semiconductor fine particles, and this method can also be used.

As described above, the method of applying the wet film may be appropriately selected according to the parameters such as the liquid viscosity of the coating liquid, the coating amount, the support, and the coating speed.

Further, the layer containing semiconductor fine particles need not be limited to a single layer. It is also possible to apply a multi-layered dispersion liquid having different particle diameters, and different types of semiconductors.
Alternatively, multi-layer coating of coating layers having different compositions of binders and additives can be performed, and multi-layer coating is effective even when the film thickness is insufficient by one-time coating. The extrusion method or slide hopper method is suitable for multi-layer coating. In the case of multi-layer coating, multi-layer coating may be performed at the same time, or several to dozens of times may be sequentially applied. Furthermore, a screen printing method can also be preferably used in the case of successive coating.

In general, as the thickness of the layer containing semiconductor fine particles increases, the amount of dye carried per unit projected area increases, so that the light capture rate increases. However, the diffusion distance of generated electrons increases, so that the loss due to charge recombination also increases. growing. Therefore, the semiconductor fine particle-containing layer has a preferable thickness, but is typically 0.1 to 100 μm. When used as a photovoltaic cell, the thickness is preferably 1 to 30 μm,
It is more preferable that the thickness be 25 μm. The coating amount of the semiconductor fine particles per 1 m ² of the support is preferably 0.5 to 400 g, more preferably 5 to 100 g.

The semiconductor fine particles are preferably subjected to a heat treatment in order to bring the particles into electronic contact with each other after being applied to the conductive support, and to improve the strength of the coating film and the adhesion to the support. A preferred range of the heat treatment temperature is 40 ° C. or more and less than 700 ° C.,
It is not less than 00 ° C and not more than 600 ° C. The heat treatment time is 1
It is about 0 minutes to 10 hours. When a support having a low melting point or softening point, such as a polymer film, is used, high-temperature treatment is not preferable because it causes deterioration of the support. Further, it is preferable that the temperature is as low as possible from the viewpoint of cost. The lowering of the temperature can be achieved by the above-mentioned combination of small semiconductor particles of 5 nm or less, heat treatment in the presence of a mineral acid, and the like.

After the heat treatment, chemical plating using, for example, an aqueous solution of titanium tetrachloride for the purpose of increasing the surface area of the semiconductor particles, increasing the purity in the vicinity of the semiconductor particles, and increasing the efficiency of electron injection from the dye into the semiconductor particles. Alternatively, electrochemical plating using an aqueous solution of titanium trichloride may be performed.

The semiconductor fine particles preferably have a large surface area so that many dyes can be adsorbed. For this reason, the surface area in the state where the semiconductor fine particle layer is coated on the support is preferably at least 10 times, more preferably at least 100 times the projected area. The upper limit is not particularly limited, but is usually about 1000 times.

As a method of adsorbing the dye on the semiconductor fine particles, a method of immersing the working electrode containing the semiconductor particles which are well dried in the dye solution, or a method of applying the dye solution to the semiconductor fine particle layer and adsorbing it can be used. . In the former case, a dipping method, a dipping method, a roller method, an air knife method, or the like can be used. The latter coating method includes a wire bar method, a slide hopper method, an extrusion method, a curtain method, a spin method, and a spray method, and the printing method includes letterpress, offset, gravure, screen printing, and the like. The solvent can be appropriately selected according to the solubility of the dye. For example, alcohols (methanol, ethanol, t-butanol, benzyl alcohol, etc.), nitriles (acetonitrile, propionitrile, 3-methoxypropionitrile, etc.), nitromethane, halogenated hydrocarbons (dichloromethane, dichloroethane, chloroform, chlorobenzene) ), Ethers (eg, diethyl ether, tetrahydrofuran), dimethyl sulfoxide, amides (eg, N, N-dimethylformamide, N, N-dimethylacetamide), N-methylpyrrolidone, 1,3-dimethylimidazolidinone , 3-methyloxazolidinone, esters (ethyl acetate, butyl acetate, etc.), carbonates (diethyl carbonate, ethylene carbonate, propylene carbonate, etc.), ketones (acetone, 2-butanone, cyclohexanone, etc.), hydrocarbons Hexane, petroleum ether, benzene, toluene, etc.) or mixed solvents thereof.

As in the case of the formation of the semiconductor fine particle layer, the liquid viscosity is not limited to the extrusion method for a high-viscosity liquid (for example, 0.01 to 500 Poise), and various printing methods are used for the low-viscosity liquid (for example, 0.1 Poise or less). A slide hopper method, a wire bar method, or a spin method is suitable, and a uniform film can be obtained.

As described above, the viscosity of the dye coating solution, the coating amount,
An application method may be appropriately selected according to parameters such as a support and a coating speed. The time required for dye adsorption after coating should be as short as possible in consideration of mass production.

Since the presence of unadsorbed dye causes disturbance of device performance, it is preferable to remove the dye by washing immediately after adsorption. It is preferable to perform cleaning with a polar solvent such as acetonitrile and an organic solvent such as an alcohol solvent using a wet cleaning tank. In order to increase the amount of the adsorbed dye, it is preferable to perform the heat treatment before the adsorption. After the heat treatment, in order to avoid adsorption of water on the surface of the semiconductor fine particles, it is also preferable to quickly adsorb the dye at 40 to 80 ° C. without returning to normal temperature.

The amount of the dye used is preferably from 0.01 to 100 mmol per 1 m ² of the support. The amount of the dye adsorbed on the semiconductor fine particles is preferably 0.01 to 1 mmol per 1 g of the semiconductor fine particles. With such an amount of the dye, a sensitizing effect in the semiconductor can be sufficiently obtained. On the other hand, if the amount of the dye is small, the sensitizing effect becomes insufficient, and if the amount of the dye is too large, the dye not adhering to the semiconductor floats and causes a reduction in the sensitizing effect. In addition,
In the present invention, the dye of the present invention and a known dye, in order to widen the wavelength range of photoelectric conversion as much as possible and to increase the conversion efficiency,
For example, a ruthenium complex dye, an organic dye (for example, polymethine dye) and the like can be used in combination. Dyes to be mixed and their proportions can be selected so as to match the intended wavelength range and intensity distribution of the light source.

A colorless compound may be co-adsorbed for the purpose of reducing the interaction between dyes such as association. Examples of the hydrophobic compound to be co-adsorbed include steroid compounds having a carboxy group (for example, chenodeoxycholic acid). Further, an ultraviolet absorber can be used in combination.

For the purpose of accelerating the removal of excess dye, the surface of the semiconductor fine particles may be treated with an amine after adsorbing the dye. Preferred amines include pyridine, 4-tert-butylpyridine, polyvinylpyridine and the like. When these are liquids, they may be used as they are or may be used by dissolving them in an organic solvent.

Hereinafter, the charge transfer layer and the counter electrode will be described in detail. The charge transfer layer is a layer having a function of replenishing the oxidized dye with electrons. Examples of typical charge transfer layers that can be used in the present invention include a liquid (electrolytic solution) in which a redox couple is dissolved in an organic solvent, and a so-called gel in which a liquid in which a redox couple is dissolved in an organic solvent is impregnated in a polymer matrix. Examples include an electrolyte and a molten salt containing a redox couple.
Further, a solid electrolyte or a hole transporting material can be used.

The electrolytic solution used in the present invention comprises an electrolyte, a solvent,
And additives. The electrolyte of the present invention is LiI as a combination (iodides I ₂ and an iodide, NaI, KI, CsI, metal iodide such as CaI ₂ or tetraalkylammonium iodide, pyridinium iodide, imidazolium iodide, etc. 4 Iodine salts of quaternary ammonium compounds), Br
Combination of ₂ and bromide (bromide is LiBr, N
ABR, KBr, CsBr, metal bromide such as CaBr ₂ or tetraalkylammonium bromide,
Bromide salts of quaternary ammonium compounds such as pyridinium bromide), metal complexes such as ferrocyanate-ferricyanate and ferrocene-ferricinium ions, sulfur compounds such as sodium polysulfide and alkylthiol-alkyldisulfide, and viologen Dyes, hydroquinone-quinone and the like can be used. I ₂ and LiI or pyridinium iodide Among these, an electrolyte that combines iodine salt of imidazolium iodide and quaternary ammonium compounds are preferred in the present invention. The above-mentioned electrolytes may be used as a mixture. The electrolyte is EP-718
No.288, WO95 / 18456, J. Electrochem.Soc., Vol.14
3, No. 10, 3099 (1996), Inorg. Chem. 1996, 35, 1168-1178
The salt in a molten state at room temperature (molten salt) described in (1) can also be used. When a molten salt is used as an electrolyte, a solvent need not be used.

The preferred electrolyte concentration is 0.1M or more and 15M.
Or less, more preferably 0.2M or more and 10M or less. When iodine is added to the electrolyte, a preferable concentration of iodine is 0.01 M or more and 0.5 M or less.

The solvent used for the electrolyte in the present invention is a compound capable of exhibiting excellent ionic conductivity by decreasing the viscosity and improving the ionic mobility or increasing the dielectric constant and improving the effective carrier concentration. Desirably. Examples of such a solvent include carbonate compounds such as ethylene carbonate and propylene carbonate, 3-methyl-
Heterocyclic compounds such as 2-oxazolidinone, dioxane, ether compounds such as diethyl ether, ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, chain ethers such as polypropylene glycol dialkyl ether, methanol, ethanol,
Alcohols such as ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, and polypropylene glycol monoalkyl ether; polyhydric alcohols such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, and glycerin; acetonitrile; Nitrile compounds such as glutaronitrile, methoxyacetonitrile, propionitrile, and benzonitrile; aprotic polar substances such as dimethyl sulfoxide (DMSO) and sulfolane; and water can be used.

Further, according to the present invention, J. Am. Ceram. Soc.,
80 (12) 3157-3171 (1997), ter-butylpyridine, and basic compounds such as 2-picoline and 2,6-lutidine can also be added. A preferred concentration range when adding a basic compound is 0.05 M or more and 2 M or less.

In the present invention, the electrolyte may be gelled (solidified) by a technique such as addition of a polymer, addition of an oil gelling agent, polymerization containing a polyfunctional monomer, or crosslinking reaction of the polymer. When gelling by adding a polymer, use the Polymer Electrolyte Review-1 and 2
(Co-edited by JR MacCallum and CA Vincent, ELSEVIER APPLI
Compounds described in (ED SCIENCE) can be used, and particularly, polyacrylonitrile and polyvinylidene fluoride can be preferably used. When gelling by adding an oil gelling agent, use J. Chem Soc. Japan, Ind.
Chem.Sec., 46, 779 (1943), J. Am. Chem. Soc., 111,
5542 (1989), J. Chem. Soc., Chem. Commun., 1993, 3
90, Angew. Chem. Int. Ed. Engl., 35, 1949 (1996), Ch.
em. Lett., 1996, 885, J. Chm. Soc., Chem. Commun.,
Although the compounds described in 1997,545 can be used, preferred compounds are compounds having an amide structure in the molecular structure.

When the gel electrolyte is formed by polymerization of polyfunctional monomers, a solution is prepared from the polyfunctional monomers, polymerization initiator, electrolyte, and solvent, and the solution is prepared by a method such as a casting method, a coating method, a dipping method, or an impregnation method. A method in which a sol-like electrolyte layer is formed on an electrode supporting a dye and then gelled by radical polymerization is preferable. The polyfunctional monomer is preferably a compound having two or more ethylenically unsaturated groups, for example, divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate. Ethylene glycol diacrylate, triethylene glycol dimethacrylate,
Preferred examples include pentaerythritol triacrylate and trimethylolpropane triacrylate. The monomers constituting the gel electrolyte may contain a monofunctional monomer in addition thereto, and may include acrylic acid or α-
Esters or amides derived from alkylacrylic acids (such as methacrylic acid) (such as Nis
o-propylacrylamide, acrylamide, 2-acrylamide-2-methylpropanesulfonic acid, acrylamidopropyltrimethylammonium chloride,
Methyl acrylate, hydroxyethyl acrylate,
n-propyl acrylate, n-butyl acrylate,
2-methoxyethyl acrylate, cyclohexyl acrylate, etc.), vinyl esters (eg, vinyl acetate), esters derived from maleic acid or fumaric acid (eg, dimethyl maleate, dibutyl maleate, diethyl fumarate, etc.), maleic acid, Fumaric acid,
p-styrenesulfonic acid sodium salt, acrylonitrile, methacrylonitrile, dienes (eg, butadiene, cyclopentadiene, isoprene), aromatic vinyl compound (eg, styrene, p-chlorostyrene, sodium styrenesulfonate), nitrogen-containing heterocycle A vinyl compound having a quaternary ammonium salt,
N-vinylformamide, N-vinyl-N-methylformamide, vinyl sulfonic acid, sodium vinyl sulfonate, vinylidene fluoride, vinylidene chloride, vinyl alkyl ethers (eg, methyl vinyl ether), ethylene, propylene, 1-butene, isobutene, N-phenylmaleimide and the like can be preferably used. The preferred weight composition range of the polyfunctional monomer in the total amount of the monomers is preferably 0.5% by weight or more and 70% by weight or less, more preferably 1.0% by weight or more and 5% by weight or more.
0% by weight or less.

The above-mentioned monomers are generally described in Takatsu Otsu and Masayoshi Kinoshita: Experimental Method for Polymer Synthesis (Chemical Doujin) and Takatsu Otsu: Lecture Polymerization Reaction Theory 1 Radical Polymerization (I) (Chemical Doujin) It can be polymerized by radical polymerization, which is a simple polymer synthesis method. The monomer for gel electrolyte that can be used in the present invention can be radically polymerized by heating, light, electron beam, or electrochemically, but it is particularly preferable to radically polymerize by heating. The polymerization initiator preferably used when the crosslinked polymer is formed by heating,
For example, 2,2'-azobisisobutyronitrile, 2,2
2'-azobis (2,4-dimethylvaleronitrile),
Azo initiators such as dimethyl 2,2'-azobis (2-methylpropionate) (dimethyl 2,2'-azobisisobutyrate); and peroxide initiators such as benzoyl peroxide. The preferable addition amount of the polymerization initiator is 0.01% by weight or more and 20% by weight or less, more preferably 0.1% by weight or more and 10% by weight based on the total amount of the monomers.
It is as follows.

The weight composition range of the monomers in the gel electrolyte is preferably 0.5% by weight or more and 70% by weight or less, more preferably 1.0% by weight or more and 50% by weight or less.

When the electrolyte is gelled by a crosslinking reaction of the polymer, it is desirable to use a polymer containing a crosslinkable reactive group and a crosslinking agent together. In this case, a preferable crosslinkable reactive group is a nitrogen-containing heterocyclic ring (for example, a pyridine ring, an imidazole ring, a thiazole ring, an oxazole ring, a triazole ring, a morpholine ring, a piperidine ring, a piperazine ring, etc.), and a preferable crosslinking agent. Is a bifunctional or higher functional reagent capable of electrophilic reaction with a nitrogen atom (for example, alkyl halide, aralkyl halide, sulfonic acid ester, acid anhydride, acid chloride, isocyanate, etc.).

In the present invention, an organic or inorganic hole transporting material or a combination thereof can be used in place of the electrolyte. Organic hole transporting materials applicable to the present invention include N, N'-diphenyl-N, N'-bis (4-
Methoxyphenyl)-(1,1'-biphenyl) -4,4'-
Diamine (J. Hagen et al., Synthetic Metal 89 (1997) 21
5-220), 2,2 ', 7,7'-tetrakis (N, N-di-p-methoxyphenylamine) 9,9'-spirobifluorene (Nature, V
ol. 395, 8 Oct. 1998, p583-585 and WO97 / 10617), 1,
Aromatic diamine compounds in which tertiary aromatic amine units of 1-bis {4- (di-p-tolylamino) phenyl} cyclohexane are linked (JP-A-59-194393);
Aromatic amines containing two or more tertiary amines represented by -bis [(N-1-naphthyl) -N-phenylamino] biphenyl and having two or more condensed aromatic rings substituted with nitrogen atoms (Japanese Patent Application Laid-Open No. 5-234681), an aromatic triamine having a starburst structure as a derivative of triphenylbenzene (U.S. Pat. No. 4,923,774, JP-A-4-308688), N
, N'-Diphenyl-N, N'-bis (3-methylphenyl)
Aromatic diamines such as-(1,1'-biphenyl) -4,4'-diamine (U.S. Pat. No. 4,764,625), α, α, α ′
, Α'-Tetramethyl-α, α'-bis (4-di-p-tolylaminophenyl) -p-xylene (JP-A-3-269084), p-phenylenediamine derivative Asymmetric triphenylamine derivatives (Japanese Unexamined Patent Publication
JP-A-129271), a compound in which a pyrenyl group is substituted with a plurality of aromatic diamino groups (JP-A-4-175395), and an aromatic diamine in which a tertiary aromatic amine unit is linked by an ethylene group (JP-A-4-264189) JP-A-5-25473), an aromatic diamine having a styryl structure (JP-A-4-290851), a benzylphenyl compound (JP-A-4-364153), and a tertiary amine linked by a fluorene group (JP-A-5-25473).
JP-A-5-239455), triamine compounds (JP-A-5-239455), and pisdipyridylaminobiphenyl (JP-A-5-32455).
0634), N, N, N-triphenylamine derivatives (JP-A-6-1972), aromatic diamines having a phenoxazine structure (JP-A-7-138562), and diaminophenylphenanthridine derivatives (JP-A-7-138562). Kaihei 7-252474)
And the like, α-octylthiophene and α, ω-dihexyl-α-octylthiophene (Adv. Mater. 1997, 9, N0.7, p557), hexadodecyldodecithiophene (Angew. Chem. Int. Ed. Engl. 1995, 3
4, No.3, p303-307), 2,8-dihexylanthra [2,3-b:
6,7-b '] dithiophene (JACS, Vol120, N0.4,1998, p664-67
2) Oligothiophene compounds such as polypyrrole (K. Mu
rakoshi et al.,; Chem. Lett. 1997, p471), ¨ Hand
book of Organic Conductive Molecules and Polymers
Vol.1,2,3,4¨ (by NALWA, published by WILEY) Polyacetylene and its derivatives, poly (p-phenylene) and its derivatives, poly (p-phenylenevinylene) and its derivatives, and polythienyl Conductive polymers such as lenvinylene and its derivatives, polythiophene and its derivatives, polyaniline and its derivatives, polytoluidine and its derivatives can be preferably used. In addition, Nature, Vo
l. 395, 8 Oct. 1998, p583-585, to control the dopant level.
Li [(CF ₃ SO ₂ ) ₂ N to add a compound containing a cation radical such as bromophenyl) aminium hexachloroantimonate or to control the potential of the oxide semiconductor surface (compensate for the space charge layer). ] May be added.

The organic hole transporting material can be introduced into the inside of the electrode by a method such as a vacuum evaporation method, a casting method, a coating method, a spin coating method, an immersion method, an electrolytic polymerization method, and a photoelectrolytic polymerization method. When a hole transport material is used instead of an electrolyte, Electorochim. Acta 40, 643-652
(1995), it is preferable to apply a thin layer of titanium dioxide as an undercoat layer using a technique such as spray pyrolysis.

When an inorganic solid compound is used instead of the electrolyte, copper iodide (p-CuI) (J. Phys. D: Appl. Phys. 31
(1998) 1492-1496), copper thiocyanate (Thin Solid Film)
s 261 (1995) 307-310, J. Appl. Phys. 80 (8), 15 Octobe
r 1996, p4749-4754, Chem. Mater. 1998, 10, 1501-150.
9, Semicond. Sci. Technol. 10, 1689-1693) can be introduced into the inside of the electrode by a method such as a casting method, a coating method, a spin coating method, a dipping method, and an electrolytic plating method.

There are two methods for forming the charge transfer layer. One is a method in which a counter electrode is first adhered to a semiconductor fine particle-containing layer carrying a sensitizing dye, and a liquid charge transfer layer is sandwiched between the counter electrodes. Another one
The first is a method in which the charge transfer layer is directly provided on the semiconductor fine particle-containing layer, and the counter electrode is subsequently provided.

As the method of sandwiching the charge transfer layer in the former case, a normal pressure process utilizing a capillary phenomenon by immersion or the like and a vacuum process of replacing the gas phase with a liquid phase at a pressure lower than normal pressure can be used.

In the latter case, the wet charge transfer layer is provided with a counter electrode in an undried state, and measures are taken to prevent liquid leakage at the edge. In the case of a gel electrolyte, there is also a method of applying it by a wet method and solidifying it by a method such as polymerization. In this case, a counter electrode can be provided after drying and fixing. As a method for applying a wet organic hole transport material or a gel electrolyte in addition to the electrolytic solution, the immersion method, the roller method, the dipping method, the air knife method, the extrusion method, and the slide method are the same as the method for applying the semiconductor fine particle-containing layer and the dye. A hopper method, a wire bar method, a spin method, a spray method, a casting method, various printing methods and the like can be considered. In the case of a solid electrolyte or a solid hole (hole) transport material, the charge transfer layer can be formed by a dry film forming process such as a vacuum evaporation method or a CVD method, and then a counter electrode can be provided.

In consideration of mass production, in the case of an electrolyte which cannot be solidified or a wet hole transport material, it is possible to cope by sealing the edge portion immediately after coating, but it is possible to solidify. In the case of a hole transport material, it is more preferable to solidify the film by, for example, photopolymerization or thermal radical polymerization after forming the hole transport layer by wet application. As described above, the film application method may be appropriately selected depending on the physical properties of the liquid and the process conditions.

Incidentally, the water content in the charge transfer layer was 10,
2,000 ppm or less, more preferably 2,0 ppm.
It is at most 00 ppm, particularly preferably at most 100 ppm.

The counter electrode functions as a positive electrode of the photovoltaic cell when the photoelectric conversion element is a photovoltaic cell. As the counter electrode, a support having a conductive layer can be used as in the case of the above-described conductive support. However, the support is not necessarily required in a configuration in which the strength and the sealing property are sufficiently maintained. Specifically, the conductive material used for the counter electrode is a metal (for example, platinum,
Gold, silver, copper, aluminum, rhodium, indium, etc., carbon, or conductive metal oxide (indium-
Tin composite oxide, tin oxide doped with fluorine, etc.). The thickness of the counter electrode is not particularly limited,
It is preferably 3 nm or more and 10 μm or less. In the case of a metal material, the film thickness is preferably 5 μm or less, more preferably 5 nm or more and 3 μm or less.

In order for light to reach the photosensitive layer, at least one of the conductive support and the counter electrode must be substantially transparent. In the photovoltaic cell of the present invention, it is preferable that the conductive support is transparent and sunlight is incident from the support side. In this case, it is more preferable that the counter electrode has a property of reflecting light. In the present invention, as the counter electrode, glass or plastic on which a metal or a conductive oxide is deposited, or a metal thin film can be used.

As described in the description of the application of the charge transfer layer, there are two types of application of the counter electrode: the application on the charge transfer layer and the application on the layer containing the semiconductor fine particles first. In either case, depending on the type of counter electrode material and the type of charge transfer layer,
The counter electrode material can be appropriately formed on the charge transfer layer or the semiconductor fine particle-containing layer by a method such as coating, laminating, vapor deposition, or bonding. For example, in the case of attaching a counter electrode, a substrate provided as a conductive layer can be attached by a method such as application, evaporation, or CVD of the above conductive material. When the charge transfer layer is solid, the above-mentioned conductive material is directly applied thereon, plated, PVD, CV
The counter electrode can be formed by a technique such as D.

Further, it is also possible to provide a layer having other necessary functions such as a protective layer and an antireflection film on the conductive support or the counter electrode of the working electrode. When such layers are separated in function by multiple layers, simultaneous multilayer coating and sequential coating can be performed, but simultaneous multilayer coating is more preferable in terms of productivity. In the simultaneous multi-layer coating, the slide hopper method and the extrusion method are suitable in consideration of productivity and uniformity of film formation. In addition, these functional layers can be provided by a technique such as vapor deposition or pasting depending on the material.

In the photovoltaic cell of the present invention, it is preferable to seal the side surface of the cell with a polymer, an adhesive or the like in order to prevent deterioration of components and volatilization of contents.

Next, a cell structure and a module structure when the photoelectric conversion element of the present invention is applied to a so-called solar cell will be described.

The structure inside the cell of the dye-sensitized solar cell is as follows:
Basically, it is the same as the above-described photoelectric conversion element or photovoltaic cell, but various forms are possible according to the purpose as shown in FIG. 2 or FIG. When roughly divided into two, a structure that allows light to enter from both sides [FIGS. 2 (a), (d) and 3 (g)]
And types [FIGS. 2 (b) (c) and 3 (e) (f) (h)] that are possible only from one side.

FIG. 2A shows a dye-adsorbed TiO ₂ layer 10 which is a layer containing dye-adsorbed semiconductor fine particles between transparent conductive layers 12.
And the charge transfer layer 11. FIG.
(B), a metal lead 9 is partially provided on a transparent substrate 13;
Further, a transparent conductive layer 12 is provided, an undercoat layer 14, a dye-adsorbed TiO ₂ layer 10, a charge transfer layer 11 and a metal layer 8 are provided in this order, and a support substrate 15 is further provided.
FIG. 2 (c) shows that a metal layer 8 is further provided on a support substrate 15, a dye-adsorbed TiO ₂ layer 10 is provided via an undercoat layer 14, and a charge transfer layer 11 and a transparent conductive layer 12 are further provided.
This is a structure in which a transparent substrate 13 partially provided with a metal lead 9 is arranged with the metal lead 9 side inside. FIG. 2 (d)
Has a structure in which a metal lead 9 is partially provided on a transparent substrate 13, and an undercoat layer 14, a dye-adsorbed TiO ₂ layer 10, and a charge transfer layer 11 are interposed between a transparent conductive layer 12 and a transparent conductive layer 12. FIG. 3 (e) has a transparent conductive layer 12 on a transparent substrate 13, a dye-adsorbed TiO ₂ layer 10 is provided via an undercoat layer 14, and a charge transfer layer 11 and a metal layer 8 are further provided thereon. This is a structure in which a support substrate 15 is arranged. FIG.
(F) has a metal layer 8 on a support substrate 15, a dye-adsorbed TiO ₂ layer 10 is provided via an undercoat layer 14, a charge transfer layer 11 and a transparent conductive layer 12 are further provided, and a transparent substrate 13 is arranged. FIG. 3 (g) shows a transparent conductive layer 1 between transparent substrates 13 having a transparent conductive layer 12.
2 on the inside, the undercoat layer 14, the dye-adsorbed TiO ₂ layer 1
0 and the charge transfer layer 11 are interposed. FIG.
(H), a metal layer 8 is provided on a support substrate 15, a dye-adsorbed TiO ₂ layer 10 is provided via an undercoat layer 14, a solid charge transfer layer 16 is further provided, and a part of the metal layer 8 or This is a structure having metal leads 9.

The module structure of the dye-sensitized solar cell of the present invention can have basically the same structure as a conventional solar cell module. In general, a cell is formed on a supporting substrate such as a metal or ceramic, and the cell is covered with a filling resin or a protective glass, etc., so that light can be taken in from the opposite side of the supporting substrate. It is also possible to use a transparent material such as tempered glass for the substrate, form a cell thereon, and take in light from the transparent support substrate side. Specifically, a module structure called a superstrate type, a substrate type, or a potting type, or a module structure such as a substrate integrated type used in an amorphous silicon solar cell or the like is possible. These module structures can be appropriately selected depending on the purpose of use and the place of use (environment). FIG. 4 shows an example in which the element of the present invention is formed into a module with an integrated substrate.

The structure shown in FIG. 4 has a transparent conductive layer 12 on one surface of a transparent substrate 13, on which a dye-adsorbed Ti
A cell provided with an O ₂ layer 10, a solid charge transfer layer 16 and a metal layer 8 is modularized and comprises a transparent substrate 13.
An anti-reflection layer 17 is provided on the other surface. In this case, in order to increase the utilization efficiency of incident light, it is preferable to increase the area ratio of the dye-adsorbed TiO ₂ layer 10 as the photosensitive portion (the area ratio when viewed from the transparent substrate 13 side which is the light incident surface). preferable.

A typical structure of a superstrate type or a substrate type is that cells are arranged at regular intervals between supporting substrates which are transparent on one or both sides and have been subjected to antireflection treatment, and metal leads or adjacent cells are provided between adjacent cells. They are connected by a flexible wiring or the like, and have a structure in which current collecting electrodes are arranged on the outer edge to take out generated power to the outside. Various types of plastic materials such as ethylene vinyl acetate (EVA) can be used between the substrate and the cell in the form of a film or a filling resin, depending on the purpose, in order to protect the cell and increase current collection efficiency. When using in places where it is not necessary to cover the surface with a hard material, such as places where there is little external impact, make the surface protective layer of a transparent plastic film or cure the above-mentioned filling and sealing material. It is also possible to provide a protection function and eliminate the support substrate on one side. The periphery of the support substrate is fixed in a sandwich shape with a metal frame in order to seal the inside and ensure the rigidity of the module, and the space between the support substrate and the frame is hermetically sealed with a sealing material.

When a flexible material is used for the cell itself, the supporting substrate, the filler and the sealing member, a solar cell can be formed on a curved surface. In this way, solar cells having various shapes and functions according to the purpose of use and environment of use can be manufactured.

[0120] In a super straight type solar cell module, for example, while a front substrate sent from a substrate supply device is conveyed by a belt conveyor or the like, a cell is placed thereon with a sealing material, an inter-cell connection lead wire, and a back surface sealing. After laminating sequentially with materials and the like, a back substrate or a back cover can be placed, and a frame can be set on the outer edge to make it.

On the other hand, in the case of the substrate type, while the support substrate sent out from the substrate supply device is conveyed by a belt conveyor or the like, the cells are sequentially stacked thereon together with the inter-cell connection lead wires and the sealing material. It can be manufactured by placing a front cover and setting a frame on the periphery.

The module having the structure shown in FIG. 4 is formed by selective plating, selective etching, and CVD so that transparent electrodes, photosensitive layers, charge transfer layers, back electrodes, and the like are arranged three-dimensionally at regular intervals on a supporting substrate.・ Laser scribing or plasma CVM (Solar Ener) after semiconductor process technology such as PVD, or pattern application or wide application
gy Materials and Solar Cells, 48, p373-381) or a mechanical method such as grinding or the like, and a desired module structure can be obtained.

Hereinafter, other members and steps will be described in detail. Examples of the sealing material include liquid-state EVA (ethylene vinyl acetate) and EVA in the form of a film of a mixture of vinylidene fluoride copolymer and an acrylic resin. Various materials can be used according to the purpose of improving (impact).

These are fixed on the cell according to the physical properties of the sealing material. For a film-like material, heat adhesion after roll pressing or heat adhesion after vacuum pressing, and for a liquid or paste-like material, a roll adhesion. There are various methods such as coating, bar coating, spray coating, screen printing and the like.

Further, the strength and the light transmittance can be increased by mixing a transparent filler into the sealing material.

The space between the outer edge of the module and the frame surrounding the peripheral edge is preferably sealed with a resin having high weather resistance and moisture resistance.

When a flexible material such as PET or PEN is used as the support substrate, a roll-shaped support is drawn out to form a cell thereon, and then the sealing layer is continuously laminated by the above method. And a highly productive process can be made.

In order to increase the power generation efficiency, the surface of the substrate (generally tempered glass) on the light intake side of the module is subjected to an antireflection treatment. This includes a method of laminating an antireflection film and a method of coating an antireflection layer.

Further, by treating the surface of the cell by a method such as grooving or texturing, it is possible to increase the utilization efficiency of incident light.

In order to increase the power generation efficiency, it is most important that the light is introduced into the module without loss. However, the light that has passed through the photoelectric conversion layer and has reached the inside thereof is reflected and efficiently returned to the photoelectric conversion layer side. It is also important. For this purpose, a method of mirror-polishing the surface of the supporting substrate and then depositing or plating Ag or Al or the like, a method of providing an alloy layer such as Al-Mg or Al-Ti as a reflective layer on the lowermost layer of the cell,
Alternatively, there is a method in which a texture structure is formed in the lowermost layer by annealing to increase the reflectance.

To increase the power generation efficiency, it is important to reduce the connection resistance between cells in order to suppress the internal voltage drop.

Although connection is generally made by wire bonding or a conductive flexible sheet, a method of using a conductive pressure-sensitive adhesive tape or a conductive adhesive to have both a cell fixing function and an electrical connection function, a conductive hot melt Is applied to a desired position in a pattern.

In the case of a solar cell using a flexible support such as a polymer film, cells are sequentially formed and cut into a desired size by the method described in the description of semiconductor coating while feeding a roll-shaped support. In addition, the periphery can be sealed with a flexible and moisture-proof material to produce a battery body. Also, Solar Energy Materials andSo
LAR Cells, 48, p383-391, and a module structure called “SCAF” can also be used.

In the case of a solar cell having a flexible support, it can be further used by bonding it to a curved glass or the like.

[0135]

The present invention will be specifically described below with reference to examples. Example 1: Synthesis of D-31

[0136]

Embedded image

Indolenine quaternary salt 11, 7.92 g (2
0 mmol), 3.44 g of diethyl squarate 2
(20 mmol), 4.2 g of triethylamine (40 m
mol) was dissolved in 50 ml of ethanol and refluxed for 4 hours. After cooling, the crystals were separated by filtration and washed with ethanol, and 5.7 g of yellow crystals of terminal ethyl squarate 12 (yield: 82)
%).

Ethyl squarate terminal 12, 1.04 g
(3 mmol), pyrazolidinedione 13, 0.83 g
(3.3 mmol) and 0.69 g (3.6 mmol) of a 28% sodium methoxide / methanol solution were dissolved in 20 ml of butanol and refluxed for 2 hours. After cooling, hydrochloric acid was added to adjust the pH to 3. The crystals are filtered off and washed with ethanol,
1.36 g (82% yield) of orange crystals of D-31 were obtained. The structure was confirmed by NMR spectrum and MS spectrum. Example 2: Synthesis of D-35

[0139]

Embedded image

0.87 g (yield: 60%) of orange crystals of D-35 was obtained in exactly the same manner as in the synthesis of D-31 except that pyrazolone 14 was used in an equimolar amount instead of pyrazolidinedione 13. Was. The structure was confirmed by NMR spectrum and MS spectrum. Example 3: Synthesis of D-3

[0141]

Embedded image

In the synthesis of 12, instead of the quaternary salt 11, 4
Ethyl terminal squarate 16 was synthesized in exactly the same manner except that an equimolar amount of the grade salt 15 was used. In the synthesis of D-31,
0.90 g of red crystal of D-3 was obtained in exactly the same manner except that equimolar 16 was used instead of ethyl squarate 12 and rhodanine 17 was used instead of pyrazolidinedione 13. The structure was confirmed by NMR spectrum and MS spectrum.

[Measurement of absorption spectrum]

D-3, D-15, D-19, D-31,
The absorption spectra of D-35, D-36, D-37 and D-71 in methylene chloride were measured. Table 1 shows the absorption maximum wavelength.

[0145]

[Table 1]

It can be seen that the dye of the present invention has various maximum absorption wavelengths in the visible light region.

Example 4: (1) Preparation of Titanium Dioxide Dispersion Titanium dioxide (Nippon Aerosil Co., Ltd.) was placed in a 200 ml stainless steel vessel whose inside was coated with Teflon.
Degussa P-25) 15 g, water 45 g, dispersant (Triton X-100, manufactured by Aldrich) 1
g of zirconia beads having a diameter of 0.5 mm (manufactured by Nikkato Co., Ltd.), and dispersed for 2 hours at 1500 rpm using a sand grinder mill (manufactured by Imex). The zirconia beads were removed by filtration from the dispersion. In this case, the average particle size of the titanium dioxide was 2.5 μm. The particle size at this time was measured with a master sizer manufactured by MALVERN.

(2) Preparation of TiO ₂ Electrode Adsorbing Dye Conductive surface of conductive glass coated with fluorine-doped tin oxide (TCO glass-U manufactured by Asahi Glass cut into a size of 20 mm × 20 mm) The dispersion was applied to the side using a glass rod. At this time, adhesive tape is applied to a part (3 mm from the end) on the conductive surface side as a spacer,
Arrange the glass so that the adhesive tape is
It was applied one by one. After application, the adhesive tape was peeled off and air-dried at room temperature for one day. Next, this glass was placed in an electric furnace (muffle furnace FP-32 manufactured by Yamato Scientific Co., Ltd.) and heated at 450 ° C. for 3 hours.
After baking for 0 minutes, a TiO ₂ electrode was obtained. After the electrode was taken out and cooled, it was immersed in a methanol solution of the dye shown in Table 1 (each dye was 3 × 10 ⁻⁴ mol / l) for 15 hours. The TiO ₂ electrode on which the dye was dyed was immersed in 4-tert-butylpyridine for 15 minutes, washed with ethanol and dried naturally. The thickness of the photosensitive layer thus obtained was 10 μm, and the coating amount of the semiconductor fine particles was 20 g / m ² . The surface resistance of the conductive glass was about 30Ω / □.

(3) Fabrication of photoelectrochemical cell

The color-sensitized T prepared as described above
An iO ₂ electrode substrate (2 cm × 2 cm) was overlaid with platinum-evaporated glass of the same size. Next, 0.65 mol / liter of iodine salt of 1-methyl-3-hexylimidazolium and 0.05 iodine of iodine of 1-methyl-3-hexylimidazolium were used as an electrolyte in an electrolytic solution (3-methoxypropionitrile) using a capillary phenomenon in a gap between both glasses. (Mol / liter added)
It was introduced into a TiO ₂ electrode to obtain a photoelectrochemical cell. According to this embodiment, as shown in FIG. 1, conductive glass 1 (a conductive agent layer 2 is provided on glass), TiO ₂ layer 3, dye layer 4, electrolytic solution 5, platinum layer 6, and glass 7 were laminated in this order, and a photoelectrochemical cell sealed with an epoxy-based sealing agent was produced.

(4) Measurement of photoelectric conversion wavelength and photoelectric conversion efficiency

The photoelectric conversion capability of the photoelectric conversion element of the present invention was measured by using IPCE (Incident Photonto Current Conversi
on Efficiency). Table 2 summarizes the wavelength at which the photochemical cell using each dye exhibits the maximum conversion capability and the photoelectric conversion efficiency of the monochromatic light.

[0153]

[Table 2]

In any of the dyes of the present invention, highly efficient photoelectric conversion characteristics are observed in the visible light region.

[0155]

According to the present invention, there is provided a dye-sensitized photoelectric conversion element having high photoelectric conversion characteristics in the visible light region.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a configuration of a photoelectrochemical cell prepared in an example.

FIG. 2 is a cross-sectional view showing a basic configuration example of a photoelectrochemical cell.

FIG. 3 is a cross-sectional view illustrating a basic configuration example of a photoelectrochemical cell.

FIG. 4 is a cross-sectional view showing an example of a module configuration of a substrate integrated type.

[Explanation of symbols]

REFERENCE SIGNS LIST 1 conductive glass 2 conductive agent layer 3 TiO ₂ layer 4 dye layer 5 electrolytic solution 6 platinum layer 7 glass 8 metal layer 9 metal lead 10 dye-adsorbed TiO ₂ layer 11 charge transfer layer 12 transparent conductive layer 13 transparent substrate 14 undercoat layer 15 Support substrate 16 Solid charge transfer layer 17 Antireflection layer

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H056 CA01 CA02 CA05 CB01 CB06 CC02 CC08 CE01 CE03 CE06 DD03 DD04 DD06 DD19 DD23 DD30 FA05 5F051 AA14 5H032 AA06 AS16 BB05 EE02 EE16 EE18 EE20

Claims (7)

[Claims] 1. A dye represented by the following general formula (I):
Characterized by containing semiconductor particles sensitized by heat
Conversion material. Embedded imageIn the general formula (I), R₁Are OH, SH, SeH, TeH,
NR_FiveR₆R represents any of_Five, R₆Is German
Stands for hydrogen, an alkyl group, or an aryl group. R _Two~ R_Four
Each independently represents hydrogen or a substituent, and is linked to each other
To form a ring. m represents an integer of 0 to 2. P
₁Represents a cycloalkene ring group or a heterocyclic group,
Q₁, Q_TwoAre independently oxygen, sulfur, selenium, ter
NR₇Or cycloalkane ring group, cycloalkene
A ring group or a heterocyclic group;₇Represents a hydrogen, an alkyl group,
Represents a reel group,₁, Q_TwoAt least one of
Cycloalkane ring group, cycloalkene ring group, heterocyclic group
Represents any of 2. The photoelectric conversion material according to claim 1, wherein the dye represented by the general formula (I) is represented by the general formula (II). Embedded image In the general formula (II), P ₁ and m have the same meaning as in the general formula (I). R ₁₂ , R ₁₃ , and R ₁₄ each independently represent hydrogen, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and may be linked to each other to form a ring.
Q ₁₁ represents a 5- or 6-membered cycloalkane ring group, cycloalkene ring group or heterocyclic group. 3. The photoelectric conversion material according to claim 2, wherein the dye represented by the general formula (II) is represented by the general formula (III-1) or (III-2). Embedded image In the general formulas (III-1) and (III-2), R ₁₂ , R ₁₃ , R
₁₄ , m and Q ₁₁ have the same meanings as in formula (II). General formula (II
In I-1), Y ₁ is oxygen, sulfur, selenium, tellurium, CR
₁₇ represents R ₁₈ , NR ₁₉ , and R ₁₇ , R ₁₈ , and R ₁₉ each independently represent hydrogen, an alkyl group, an alkenyl group, or an aryl group. R ₁₅ represents hydrogen, an alkyl group, an alkenyl group, or an aryl group. R ₁₆ represents a substituent, and a represents an integer of 0 to 4. When a is 2 or more, R ₁₆ may be the same or different,
They may be connected to each other to form a ring. General formula (III-
In 2), one of Y ₂ and Y ₃ represents NR ₂₁ and the other represents CR ₂₂ ; R ₂₁ represents hydrogen, an alkyl group, an alkenyl group, or an aryl group; and R ₂₂ represents hydrogen or a substituent. .
Za represents one π bond for connecting a conjugate. R ₂₀ represents a substituent, and b represents an integer of 0 to 4. When b is 2 or more, R ₂₀ may be the same or different, and may combine with each other to form a ring. 4. In the general formula (III-1), Y ₁ is CR ₁₇ R
_The photoelectric conversion material according to claim 3, which is represented by ₁₈ . 5. The semiconductor fine particles sensitized by a dye are titanium oxide fine particles.
The photoelectric conversion material according to any one of the above. 6. A photoelectric conversion element comprising a conductive support coated with the photoelectric conversion material according to claim 1, a charge transfer layer, and a counter electrode. 7. The following general formula (IV-1) or (IV-2)
A polymethine dye represented by the formula: Embedded image In the general formula (IV-1) or (IV-2), R ₁₂ , R ₁₃ , R
₁₄ , R ₁₅ , R ₂₁ , m, a, b, Y ₁ and Za are represented by the general formula (I
It is synonymous with I), (III-1) and (III-2).
One of Y ₁₂ and Y ₁₃ represents NR ₂₁ and the other represents CR ₂₃ ; R ₂₄ and R ₂₅ each independently represent a cyano group, an alkoxycarbonyl group, a carboxyl group, an acyl group, an acyloxy group, an alkylsulfonyl group, Arylsulfonyl group, sulfonic acid group, sulfonamide group, carbamoyl group, amino group, acylamino group, alkyl group, alkenyl group, aryl group, alkoxy group, alkylthio group, aryloxy group, heterocyclic group, phosphonyl group, phosphoryl group, Represents a hydroxamic acid group, a hydroxyl group, an alkynyl group, a cycloalkyl group, and a halogen atom. R ₂₃ has the same meaning as hydrogen or R ₂₄ and R ₂₅ . When a is 2 or more, R ₂₄
May be the same or different, and may be connected to each other to form a ring. When b is 2 or more, R ₂₅ may be the same or different, and may combine with each other to form a ring. Q ₂₁ represents a pyrazolidinedione ring group, a barbituric acid ring group, a thiobarbituric acid ring group, an isoxazolone ring group, a pyrazolone ring group, a pyridone ring group, a rhodanin ring group, a pyrrolotriazole ring group, or a pyrazolotriazole ring. Group, indandione ring group, hydantoin ring group, thiohydantoin ring group, thiazolidinedione ring group, and oxazolidinonethione ring group.