JP2001237000A - Photoelectric transducer element and photocell as well as metal complex coloring matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal complex coloring matter having good light absorbing ability in a range from a visible light to an infrared ray as well as a photoelectric transducer element and a photocell each containing semiconductor particulates to which the coloring matter is adsorbed. SOLUTION: The photoelectric transducer element and the photocell each contains the semiconductor particulates made sensitive with the metal complex coloring matter represented by Formula 1, (LL1)m1(X1)m2M1(BL) M2(LL2)m3(X2)m4.CI, where M1 and M2 are metal atoms, BL is a ligand having two or more portions capable of two-seat coordination, represented by Formula 2 (where L is a coupling group, R1 is an acidic group such as a carboxyl group, R2 is a substitutional group, a1 and a2 are 0-4 integers, and n is a 0-2 integer), LL1 and LL2D are two- or three-seat ligands, represented by Formula 3, X1 and X2 are one- or two-seat ligands, m1 and m3 are 0-2 integers, m2 and m4 are 0-4 integers, and CI is a counter ion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal complex dye having high light absorption ability even in a long wavelength region, a photoelectric conversion element using semiconductor fine particles sensitized by the metal complex dye, and a photovoltaic cell comprising the same.

[0002]

2. Description of the Related Art As a solar cell used for photovoltaic power generation, a solar cell made of single-crystal silicon, polycrystalline silicon, amorphous silicon, or a compound such as cadmium telluride or indium copper selenide has been put into practical use or has been mainly used for research and development. Although it is a target, in order to spread it widely to household power sources, there are problems such as high production cost, difficulty in securing raw materials, long energy payback time, etc. There is a need. On the other hand, many solar cells using an organic material have been proposed for the purpose of increasing the area and reducing the cost, but generally have the problems of low conversion efficiency and poor durability.

[0003] Under such circumstances, Nature (Vol. 353,
737-740, 1991), and U.S. Pat.
O 94/04497, etc., have proposed a wet photoelectric conversion element and a solar cell using a titanium dioxide porous thin film spectrally sensitized with a ruthenium complex dye as a working electrode, and materials and manufacturing techniques for producing the same. . The first advantage of this wet photoelectric conversion element 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. Is that the absorption of the dye used is broad, so that light in almost all wavelength regions of visible light can be converted into electricity.

[0004] However, although known ruthenium complex dyes absorb visible light, they hardly absorb infrared light having a wavelength longer than 700 nm, and thus have a problem of low photoelectric conversion ability in the infrared region. Therefore, in order to further increase the conversion efficiency, it is desired to develop a dye having an absorptivity in a wide wavelength range from visible light to an infrared region and exhibiting a high photoelectric conversion ability.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a metal complex which has a high light absorption capacity not only in the visible light region but also in the infrared region and which can efficiently sensitize semiconductor fine particles to a long wavelength region. An object of the present invention is to provide a dye, a photoelectric conversion element having high photoelectric conversion efficiency by using such a metal complex dye, and a photovoltaic cell including the same.

[0006]

Means for Solving the Problems As a result of intensive studies in view of the above object, as a result, a ligand in which two or more sites capable of bidentate coordination to a metal atom are linked by a specific linking group, and 5
Or has the non-metallic atoms required to complete a six-membered ring,
A metal complex dye formed by coordination with a ligand capable of bidentate or tridentate coordination at a nitrogen atom, and, if necessary, a monodentate or bidentate coordinating with a thiocyanate group, 1,3-ketone, or the like. By coordinating the ligand, it is possible to obtain a metal complex dye having excellent light absorption ability even in a long wavelength region, and a semiconductor fine particle sensitized by such a metal complex dye has high photoelectricity suitable as a photoelectric conversion element. The present inventors have found that the photovoltaic cell exhibits good conversion efficiency and is a good photovoltaic cell, and has reached the present invention.

That is, the photoelectric conversion element of the present invention has the following general formula (I): (LL ₁ ) _m1 (X ₁ ) _m2 M ₁ (BL) M ₂ (LL ₂ ) _m3 (X ₂ ) _m4 · CI ·· (I) (where M ₁ and M ₂ each independently represent a metal atom, and BL represents the following general formula (II):

Embedded image (Where L represents a single bond, an oxygen atom, a sulfur atom, an alkenylene group, an alkynylene group, an arylene group or a heterorylene group, and R ₁ each independently represents a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group, a phosphoryl group. or an phosphonyl group, R ₂ each independently represents a substituent, a1 and a2 each independently represents an integer of 0 to 4, R ₁ when a1 is 2 or more may be the same or different, a2 Is 2 or more, R ₂ may be the same or different, and may be linked to each other to form a ring;
And R ₁ and R ₂ may be bonded to any position of the bipyridine ring), and represents a ligand having two or more bidentate coordination parts, LL ₁ and LL ₂ are each independently the following general formula (III):

Embedded image (However, Za, Zb and Zc are each independently 5 or 6
Represents a group of non-metallic atoms capable of forming a membered ring, and c is 0 or 1
Represents a bidentate or tridentate ligand represented by X ₁ and X ₂ each independently represents an acyloxy group, an acylthio group, a thioacyloxy group, a thioacylthio group, an acylaminooxy group, a thiocarbamate group, Dithiocarbamate group, thiocarbonate group, dithiocarbonate group,
Trithiocarbonate group, acyl group, thiocyanate group, isothiocyanate group, cyanate group, isocyanate group, cyano group, alkylthio group, arylthio group,
A monodentate or bidentate ligand coordinated with a group selected from the group consisting of an alkoxy group and an aryloxy group, or a halogen atom, a carbonyl, a dialkyl ketone, a 1,3-diketone, a carbonamide, a thiocarbonamide, a thiocarbonamide Represents a monodentate or bidentate ligand consisting of urea, m1 and m3
Are each independently an integer of 0 to 2, m2 and m4 each independently represent an integer of 0 to 4, and when m2 or m4 is 2 or more, X ₁ or X ₂ may be the same or different , Or X ₁ or X ₂ may be connected,
CI represents a counter ion when a counter ion is required to neutralize the charge), and is characterized by containing semiconductor fine particles sensitized by a metal complex dye represented by the following formula:

A photovoltaic cell according to the present invention is characterized by using the above-mentioned photoelectric conversion element.

According to the present invention, when the following conditions are satisfied, a photoelectric conversion element and a photovoltaic cell having more excellent light absorbing ability in a long wavelength region can be obtained.

(1) M ₁ and M ₂ in the general formula (I) are Ru, Fe,
Os, Cu, W, Cr, Mo, Ni, Pd, Pt, Co, Ir, Rh, Re, Mn
Alternatively, it is preferably Zn, more preferably Ru, Fe, Os or Cu, and particularly preferably Ru.

(2) L in the general formula (II) is preferably a single bond, an alkenylene group, an alkynylene group or a heterorylene group, particularly preferably an ethenylene group, an ethynylene group, a butadiynylene group or a 2,5-thienylene group. Or any of the groups

(3) a1 in the general formula (II) is preferably an integer of 0 to 2.

(4) R ₁ in the general formula (II) is preferably each independently a carboxyl group or a phosphonyl group.

(5) a2 in the general formula (II) is preferably an integer of 0 to 2.

(6) R ₂ in the general formula (II) independently represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group. , Amino group,
An acyl group, a sulfonamide group, an acyloxy group, a carbamoyl group, an acylamino group, a cyano group, or a halogen atom is preferable, and an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkoxy group,
More preferably, they are an aryloxy group, an amino group or an acylamino group.

(7) The 5- or 6-membered ring formed by Za, Zb and Zc in the general formula (III) is preferably each independently a pyridine ring or an imidazole ring. These rings may be monocyclic or condensed.

(8) c in the general formula (III) is preferably 0. That is, LL ₂ is preferably a bidentate ligand.

(9) BL in the general formula (I) is the following general formula (IV-1) or (IV-2):

Embedded image (However, L, R ₁ , R ₂ , a1 and a2 have the same meanings as in the general formula (II)).

(10) LL ₁ and LL ₂ in the general formula (I) are represented by the following general formulas (V-1) to (V-8):

Embedded image (However, R _{11 to} R ₁₈ each independently represent a carboxyl group,
Represents a sulfonic acid group, a hydroxyl group, a hydroxamic acid group, a phosphoryl group or a phosphonyl group, R _{19 to} R ₂₆ each independently represent a substituent, and R _{27 to} R ₃₁ each independently represent a hydrogen, an alkyl group, an alkenyl group or Represents an aryl group, R _{11 to} R ₂₆ may be bonded to any position on the ring,
d1 to d8, d13, d14 and d16 each independently represent an integer of 0 to 4, and d9 to d12 and d15 each independently represent 0 to 6
R ₁₉ when an integer, d1 to d8 is 2 or more when R ₁₁ to R ₁₈ may be the same or different, D9～d16 is 2 or more to R
₂₆ may be the same or different, and may be linked to each other to form a ring).

(11) R _{11 to} R in the general formulas (V-1) to (V-8)
Preferably, ₁₈ is each independently a carboxyl group or a phosphonyl group.

(12) R _{19 to} R in the general formulas (V-1) to (V-8)
₂₆ is each independently an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an amino group, an acyl group, a sulfonamide group, an acyloxy group, It is preferably a carbamoyl group, an acylamino group, a cyano group, or a halogen atom.

(13) In the general formulas (V-1) to (V-8), the general formulas (V-1), (V-2), (V-4) and (V-6) are preferable.
General formula (V-1) or (V-2) is more preferred.

(14) In formula (I), m1 and m3 are preferably 1, and m2 and m4 are preferably independently 1 or 2.

(15) The semiconductor fine particles are preferably titanium oxide fine particles.

In a more preferred metal complex dye,
m1 and m3 are 1, and m2 and m4 are independently 1 or 2.

[0026]

DETAILED DESCRIPTION OF THE INVENTION [1] Metal Complex Dye The metal complex dye used in the photoelectric conversion device of the present invention has the following general formula (I): (LL ₁ ) _m1 (X ₁ ) _m2 M ₁ (BL) M ₂ (LL ₂ ) _m3 (X ₂ ) _m4 · CI (I) Hereinafter, each component will be described in detail.

(A) Metal atoms M ₁ , M ₂ M ₁ and M ₂ each independently represent a metal atom. M ₁ and M ₂ are preferably metals capable of 4 or 6 coordination, more preferably Ru, Fe, Os, Cu, W, Cr, Mo, Ni, Pd, Pt, C
o, Ir, Rh, Re, Mn or Zn, particularly preferably R
u, Fe, Os or Cu, most preferably Ru. M
₁ and M ₂ are equal or different, preferably the same.

(B) Ligand BL The ligand BL is represented by the following general formula (II):

Embedded image Is represented by

In the general formula (II), L is a single bond, an oxygen atom,
Sulfur atom, alkenylene group (preferably having 2 to 2 carbon atoms)
20, for example, an ethenylene group, a butadienylene group), an alkynylene group (preferably having 2 to 20 carbon atoms, for example, an ethynylene group, butadiynylene group), an arylene group (preferably having 6 to 26 carbon atoms, for example, a 1,4-phenylene group, 1,2-phenylene group, 1,3-phenylene group, 1,4-naphthylene group, 2,
5-dimethoxy-1,4-phenylene group, 4,4'-biphenylene group), heterorylene group (preferably having 1 to 26 carbon atoms,
For example, a 2,5-pyridylene group, a 2,5-thienylene group, a 2,5-furanylene group, a 2,5-pyrrolylene group, a 2,5-benzothienylene group), more preferably a single bond, an alkenylene group, or an alkynylene A heteroarylene group, more preferably an ethenylene group, an ethinylene group, a butadiynylene group, or a 2,5-thienylene group.

R ₁ in the general formula (II) is independently a carboxyl group, a sulfonic acid group, a hydroxyl group, or a hydroxamic acid group (preferably having 1 to 20 carbon atoms, for example, -CONHO
H, -CONCH ₃ OH, etc.), a phosphoryl group (for example, -OP (O) (OH)
₂ ) and a phosphonyl group (e.g., -P (O) (OH) ₂ etc.), preferably a carboxyl group, a phosphoryl group or a phosphonyl group, more preferably a carboxyl group or a phosphonyl group, Preferably it is a carboxyl group. R ₁ may be the same or different, but is preferably the same.

R ₂ in the general formula (II) independently represents a substituent, preferably an alkyl group (preferably having 1 to 20 carbon atoms, for example, a methyl group, an ethyl group, an isopropyl group,
t-butyl group, pentyl group, heptyl group, 1-ethylpentyl group, benzyl group, 2-ethoxyethyl group, 1-carboxymethyl group, etc., alkenyl group (preferably having 2 carbon atoms)
-20, such as a vinyl group, an allyl group, an oleyl group, etc., an alkynyl group (preferably having 2 to 20 carbon atoms, such as an ethynyl group, a butadiynyl group, a phenylethynyl group, etc.), and a cycloalkyl group (preferably having 3 carbon atoms). -20, for example, cyclopropyl group, cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, etc.), aryl group (preferably having 6 to 26 carbon atoms, for example, phenyl group, 1-naphthyl group, 4-methoxyphenyl group, 2 -Chlorophenyl group, 3-
A heterocyclic group (preferably having 2 to 20 carbon atoms, for example, a 4-pyridyl group, a 1-imidazolyl group,
2-benzimidazolyl group, 2-thiazolyl group, 2-oxazolyl group, etc.), alkoxy group (preferably having 1 carbon atom)
20, for example, methoxy group, ethoxy group, isopropyloxy group, benzyloxy group, etc., aryloxy group (preferably having 6 to 26 carbon atoms, for example, phenoxy group, 1-naphthyloxy group, 3-methylphenoxy group, 4- A methoxyphenoxy group or the like), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms such as an ethoxycarbonyl group, a 2-ethylhexyloxycarbonyl group or the like), an amino group (preferably having 0 to 20 carbon atoms such as an amino group, N , N-dimethylamino group, N, N-diethylamino group, N-ethylamino group, anilino group, etc.), acyl group (preferably having 1 to 20 carbon atoms such as acetyl group, benzoyl group, etc.), sulfonamide group ( Preferably 0 to 20 carbon atoms, for example, N, N-
Dimethylsulfonamide group, N-phenylsulfonamide group, etc.), acyloxy group (preferably having 1 to 2 carbon atoms)
0, for example, acetyloxy group, benzoyloxy group, etc.), carbamoyl group (preferably having 1 to 20 carbon atoms,
For example, N, N-dimethylcarbamoyl group, N-phenylcarbamoyl group, etc., acylamino group (preferably having 1 to 20 carbon atoms, such as acetylamino group, benzoylamino group, etc.), cyano group, or halogen atom (eg, fluorine atom , Chlorine atom, bromine atom, iodine atom, etc.).

R ₂ is more preferably an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an amino group or an acylamino group, and further preferably an alkyl group, an alkenyl group, an alkoxy group, an amino group, an acylamino group. And particularly preferably an alkyl group, an alkoxy group, or an amino group.

When BL contains an alkyl group, an alkenyl group or the like, they may be linear or branched, and may be substituted or unsubstituted. When BL contains an aryl group, a heterocyclic group, or the like, they may be monocyclic or condensed, and may be substituted or unsubstituted.

A1 representing the number of R _{1 in} the general formula (II) independently represents an integer of 0 to 4. When a1 is 2 or more, R ₁ may be the same or different. R ₁ may be substituted on any carbon atom on the bipyridine ring. Preferably, a1 is an integer of 0 to 2, and more preferably 0 or 1.

A2, which represents the number of R _{2 in} the general formula (II), each independently represents an integer of 0 to 4. When a2 is 2 or more, R ₂ may be the same or different. A ring may be formed. The ring to be formed is preferably a benzene ring,
Examples include a pyridine ring, a cyclohexane ring, and a cyclopentane ring. R ₂ may be substituted on any carbon atom on the bipyridine ring. Preferably, a2 represents an integer of 0 to 2, more preferably 0 or 1.

In the general formula (II), n represents an integer of 0 to 2, and n is preferably 0 or 1, and more preferably 0. That is, the ligand BL preferably has two sites capable of bidentate coordination.

The ligand BL has the general formula (IV-1) or (IV-
More preferably, it is represented by 2).

Embedded image In the general formula (IV-1) or (IV-2), L, R ₁ , R ₂ , a1 and a2 have the same meaning as in the general formula (II).

Specific examples of BL in the general formula (I) of the present invention are shown below, but the present invention is not limited to these.

[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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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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(C) Ligands LL ₁ , LL ₂ LL ₁ and LL ₂ each independently represent a bidentate or tridentate ligand. M1 and m3 representing the numbers of LL ₁ and LL ₂ are each independently 0
An integer of 2 to 2, preferably 0 or 1,
Is more preferable.

The ligands LL ₁ and LL ₂ are each independently represented by the following general formula (III):

Embedded image Is represented by

In the general formula (III), Za, Zb and Zc each independently represent a group of non-metallic atoms capable of forming a 5- or 6-membered ring. It may be substituted, and may be monocyclic or condensed. Za, Zb and Zc are preferably composed of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom and / or a halogen atom, and preferably form an aromatic ring.
In the case of a 5-membered ring, it is preferable to form an imidazole ring, an oxazole ring, a thiazole ring or a triazole ring, and in the case of a 6-membered ring, it is preferable to form a pyridine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring. Among them, an imidazole ring or a pyridine ring is more preferable.

In the general formula (III), c represents 0 or 1. c
Is preferably 0, ie LL ₁ and LL ₂ are preferably bidentate ligands.

The ligands LL ₁ and LL ₂ are each independently represented by the following general formulas (V-1) to (V-8):

Embedded image Preferably, it is represented by any of

R _{11 to} R ₁₈ in formulas (V-1) to (V-8) each independently represent a carboxyl group, a sulfonic group, a hydroxyl group or a hydroxamic group (preferably having 1 to 2 carbon atoms).
0, for example -CONHOH, -CONCH ₃ OH, etc.), represents one of a phosphoryl group (e.g., -OP (O) (OH) _2, etc.) and a phosphonyl group (e.g., -P (O) (OH) _2, etc.), It is preferably a carboxyl group, a phosphoryl group or a phosphonyl group, more preferably a carboxyl group or a phosphonyl group, and most preferably a carboxyl group.

R _{19 to} R ₂₆ in formulas (V-1) to (V-8) each independently represent a substituent, preferably an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group. , an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an amino group, an acyl group, a sulfonamido group, an acyloxy group, a carbamoyl group, an acylamino group, a cyano group or a halogen atom (or, preferred examples are the same as R ₂₎ represents, More preferably an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group or a halogen atom, particularly preferably an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, An amino group and an acylamino group.

R _{27 to} R ₃₁ in formulas (V-1) to (V-8) each independently represent hydrogen, an alkyl group, an alkenyl group or an aryl group (the preferred examples are the same as R ₂ ). , An alkyl group, or an alkyl group substituted by a carboxyl group is preferred. When LL ₁ and LL ₂ each include an alkyl group, an alkenyl group, or the like, they may be linear or branched, and may be substituted or unsubstituted. When LL ₁ and LL ₂ each include an aryl group, a heterocyclic group, or the like, they may be monocyclic or condensed, and may be substituted or unsubstituted.

R _{11 to} R ₂₆ in formulas (V-1) to (V-8) may be bonded to any position on the ring, and d1 to d6 each independently represent an integer of 0 to 4. And preferably represents an integer of 0 to 2, d7 and d8 each independently represent an integer of 0 to 4,
Preferably, it represents an integer of 0 to 3. d9 to d12 and d15 each independently represent an integer of 0 to 6, d13, d14 and d16
Each independently represents an integer of 0 to 4, and d9 to d16 preferably represent an integer of 0 to 3.

[0063] d1~d8 two or more when R ₁₁ to R ₁₈ may be the same or different, R ₁₉ to R ₂₆ when d9~d16 is 2 or more
May be the same or different, and may be connected to each other to form a ring. The ring to be formed is preferably a benzene ring, a pyridine ring, a cyclohexane ring, a cyclopentane ring or the like. Particularly d10 it is preferable to form a further pyridine ring R ₂₀ together are connected on the pyridine ring of 2 or more time.

The ligands LL ₁ and LL ₂ are represented by the general formulas (V-1) and (V-
It is more preferably represented by 2), (V-4) or (V-6), and more preferably represented by the general formula (V-1) or (V-2). LL ₁ and LL ₂ may be the same or different,
Preferably they are the same.

Specific examples of LL ₁ and LL ₂ in the general formula (I) of the present invention are shown below, but the present invention is not limited to these.

[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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(D) Ligands X ₁ and X _{2 In the} general formula (I), X ₁ and X ₂ each independently represent a monodentate or bidentate ligand, and the ligands X ₁ and X ₂ M3 and m4 independently represent an integer of 0 to 4, preferably 1 or 2,
When X ₁ and X ₂ are monodentate ligands, 2 is preferable, and when X ₁ and X ₂ are bidentate ligands, 1 is preferable. When m3 and m4 are 2 or more, X ₁ and X ₂ may be the same or different, and X ₁ and X ₂ may be connected to each other.

X ₁ and X _{2 each} represent an acyloxy group (preferably having 1 to 20 carbon atoms, for example, an acetyloxy group, a benzoyloxy group, a salicylic acid group, a glycyloxy group, an N, N-dimethylglycyloxy group, an oxalylene group ( −OC (O) C (O) O
-) Etc.), an acylthio group (preferably having 1 to 2 carbon atoms)
0, for example, acetylthio group, benzoylthio group, etc.), thioacyloxy group (preferably having 1 to 20 carbon atoms, for example, thioacetyloxy group (CH ₃ C (S) O—), etc.), thioacylthio group (preferably carbon atom 1-20, for example thio acetyl thio group _{(CH 3 C (S) S-} ), or the like thio benzoyl thio group (PhC (S) S-)) , acylamino group (preferably having 1 to 20 carbon atoms, such as N- methyl-benzoylamino group (PhC (O) N (CH 3) O-), an acetylamino group _{(CH 3 C (O) NHO-} )), thiocarbamate group (preferably 1 to carbon atoms 20, e.g., N, N-diethylthiocarbamate group, etc., dithiocarbamate group (preferably having 1 to 20 carbon atoms, e.g., N-phenyldithiocarbamate group, N, N-dimethyldithiocarbamate group, N, N-diethyldithio group) Carbamate group, N, N-dibenzyldi Oh carbamate group), thiocarbonate group (preferably having 1 to 20 carbon atoms, for example ethyl thiocarbonate group),
Dithiocarbonate group (preferably having 1 to 20 carbon atoms,
Such as ethyl dithiocarbonate group _{(C 2 H 5 OC (S} ) S-)
Etc.), trithiocarbonate group (preferably having 1 to 20 carbon atoms, for example ethyl trithiocarbonate group (C ₂ H ₅ SC
(S) S-) etc.), an acyl group (preferably having 1 to 2 carbon atoms)
0, for example, acetyl group, benzoyl group, etc.), thiocyanate group, isothiocyanate group, cyanate group, isocyanate group, cyano group, alkylthio group (preferably having 1 to 20 carbon atoms, for example, methanethio group, ethylenedithio group, etc.), arylthio group Group (preferably having 6 to 2 carbon atoms)
0, for example, a benzenethio group, 1,2-phenylenedithio group, etc.), an alkoxy group (preferably having 1 to 20 carbon atoms, such as a methoxy group) and an aryloxy group (preferably having 6 to 20 carbon atoms, such as a phenoxy group) , Quinoline-8
-Hydroxyl group), a monodentate or bidentate ligand coordinated by a group selected from the group consisting of: a halogen atom (preferably a chlorine atom, a bromine atom or an iodine atom);
Carbonyl (... CO), dialkyl ketones (preferably 3 to 20 carbon atoms, such as acetone _{((CH 3) 2 CO ...} ) (...
Represents a coordinate bond), 1,3-diketone (preferably 3 to 20 carbon atoms, such as acetylacetone _{(CH 3 C (O-) CH} = C
(O…) CH ₃ ), trifluoroacetylacetone (CF ₃ C (O
−) CH = C (O…) CH ₃ ), dipivaloylmethane (tC ₄ H ₉ C (O
−) CH = C (O…) C ₄ H ₉ -t), dibenzoylmethane (phC (O
−) CH = C (O…) ph), 3-chloroacetylacetone (CH ₃ C
(O-) CCl = C (O ...) CH 3) , etc.), carbonamido (preferably having 1 to 20 carbon atoms, for example, _{CH 3 N = C (CH 3} ) O -, - OC (=
NH) -C (= NH) O-like), thio carbonamido (preferably having 1 to 20 carbon atoms, such as _{CH 3 N = C (CH 3} ) S- , etc.), thiourea (preferably 1 to carbon atoms 20, for example, NH (...) = C (S
-) NH ₂ , CH ₃ NH (…) = C (S-) NHCH ₃ , (CH ₃ ) ₂ NH-C (S…) N (C
H ₃ ) represents a ligand consisting of ₂ ).

The ligands X ₁ and X ₂ are preferably an acyloxy group, thioacylthio group, acylaminooxy group, dithiocarbamate group, dithiocarbonate group, trithiocarbonate group, thiocyanate group, isothiocyanate group, cyanate group , A ligand coordinated with a group selected from the group consisting of an isocyanate group, a cyano group, an alkylthio group, an arylthio group, an alkoxy group and an aryloxy group, or a halogen atom, carbonyl, 1,3-diketone, thiourea And more preferably a group selected from the group consisting of an acyloxy group, an acylaminooxy group, a dithiocarbamate group, a thiocyanate group, an isothiocyanate group, a cyanate group, an isocyanate group, a cyano group and an arylthio group. Ligand,
Or a halogen atom or a ligand comprising 1,3-diketone and thiourea, more preferably a dithiocarbamate group, a thiocyanate group, an isothiocyanate group, a cyanate group, an isocyanate group, a halogen atom, and a 1,3-diketone. Particularly preferred are a dithiocarbamate group, a thiocyanate group, an isothiocyanate group, and a 1,3-diketone.

When the ligands X ₁ and X ₂ include 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 an aryl group, a heterocyclic group, a cycloalkyl group and the like are contained, they may be substituted or unsubstituted, and may be monocyclic or condensed.

When X ₁ and X ₂ are bidentate ligands, X ₁ and X ₂ are
Acyloxy group, acylthio group, thioacyloxy group,
Thioacylthio, acylaminooxy, thiocarbamate, dithiocarbamate, thiocarbonate, dithiocarbonate, trithiocarbonate,
A ligand coordinated with a group selected from the group consisting of an acyl group, an alkylthio group, an arylthio group, an alkoxy group and an aryloxy group, or a ligand composed of 1,3-diketone, carbonamide, thiocarbonamide, or thiourea It is preferably a ligand. When X ₁ and X ₂ are monodentate ligands,
X ₁ and X ₂ are a ligand coordinated with a group selected from the group consisting of a thiocyanate group, an isothiocyanate group, a cyanate group, an isocyanate group, a cyano group, an alkylthio group and an arylthio group, or a halogen atom, a carbonyl, a dialkyl It is preferably a ligand composed of ketone and thiourea.

The specific examples of the ligands X ₁ and X ₂ of the present invention are shown below, but the present invention is not limited to these. It should be noted that the structural formula shown here is only one of the limit structures among a number of possible resonance structures, and the distinction between a covalent bond (represented by-) and a coordination bond (represented by ...) is formal. It does not represent a distinction.

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In the general formula (I), M ₁ and M ₂ represent Cu, Pd, Pt, etc.
In the case of a metal that prefers coordination, m1 and m3 are preferably 0 or 1. m1, m3 is 0, when X _1, X ₂ are bidentate m @ 2, m4 it is preferred when the 1,1 bidentate ligand is 2. When m1 and m3 are 1, m2 and m4 are preferably 0.

[0096] When metal prefer six-coordinate, when m1, m3 is 0, when X _1, X ₂ are bidentate at 4 when the m @ 2, m4 is 2,1 bidentate ligand Preferably, there is. When m1 and m3 are 1
m2 and m4 are preferably integers of 1 to 3, and X ₁ and X ₂ are
1 or 2 for bidentate ligand, 2 for monodentate ligand
Or it is preferably 3. When m1 and m3 are 2, m
2, m4 is preferably 0. In the case of a metal that prefers hexacoordination, m1 and m3 are preferably 0 or 1, and 1
Is more preferable.

(E) Counter ion CI CI in the general formula (I) represents a counter ion when a counter ion is required to neutralize the electric charge. Whether a dye is a cation or anion, or has a net ionic charge, depends on the metal, ligand, and substituents in the dye. When the substituent has a dissociable group, it may dissociate and have a negative charge, and in this case also, the charge of the entire molecule is neutralized by CI.

Typical positive counterions are inorganic or organic ammonium ions (eg, tetraalkylammonium ions, pyridinium ions, etc.), alkali metal ions and protons. On the other hand, the negative counter ion may be either an inorganic or organic anion, for example, a halogen anion (for example, a fluoride ion, a chloride ion, a bromide ion, an iodide ion), or a substituted arylsulfonate ion (for example, p-ion). -Toluenesulfonate ion, p-chlorobenzenesulfonate ion, etc.), aryldisulfonate ion (for example, 1,3-benzenedisulfonate ion,
1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion, etc.), alkyl sulfate ion (eg, methyl sulfate ion), sulfate ion, nitrate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate Ion, hexafluorophosphate ion, picrate ion, acetate ion, trifluoromethanesulfonic acid ion and the like. Further, as the charge-balancing counterion, an ionic polymer or another dye having a charge opposite to that of the dye may be used, or a metal complex ion (for example, bisbenzene-1,2-dithiolatonickel (III), etc.) may be used. It is.

(F) Linking Group The dye represented by the general formula (I) has an appropriate interlocking group for the surface of the semiconductor fine particles of from 1 to 6.
And preferably 1 to 4. Preferred linking groups are carboxyl, sulfonic, hydroxyl, hydroxamic (eg, -CO
Acidic groups (substituents having dissociable protons) such as NHOH, phosphoryl groups (eg, -OP (O) (OH) _2, etc.), and phosphonyl groups (eg, -P (O) (OH) _2, etc.) is there.

The above acidic groups are represented by BL and L in the general formula (I).
It is preferable to have a total of 1 to 12 in any of L ₁ and LL ₂ , more preferably 2 to 8 in total, and still more preferably 2 to 6 in total.

(G) Specific Examples of Metal Complex Dyes Among the above metal complex dyes, particularly preferable ones are those represented by the following general formula (I): (LL ₁ ) _m1 (X ₁ ) _m2 M ₁ (BL) M ₂ (LL ₂ ) _m3 (X ₂ ) _m4 · CI (I) (where M ₁ and M ₂ represent Ru, and BL represents the above general formula (IV-
1) or a ligand having two or more bidentate coordination units represented by (IV-2), and LL ₁ and LL ₂ are each independently the above-mentioned general formulas (V-1) to (V-1) -8) 2
X ₁ and X ₂ each independently represent an acyloxy group, an acylthio group, a thioacyloxy group,
Thioacylthio, acylaminooxy, acetylaminooxy, thiocarbamate, dithiocarbamate, thiocarbonate, dithiocarbonate, trithiocarbonate, acyl, thiocyanate,
Monodentate or bidentate ligand coordinated by a group selected from the group consisting of isothiocyanate group, cyanate group, isocyanate group, cyano group, alkylthio group, arylthio group, alkoxy group and aryloxy group, or halogen atom , Carbonyl, dialkyl ketone, 1,3-diketone, carbonamide, thiocarbonamide, thiourea, represents a monodentate or bidentate ligand, m1 and m3 are each independently an integer of 0 to 1, m2 and m4 each independently represent a 1-4 integer, when m2 or m4 is 2 or more, X ₁ or X ₂ is not may be the same or different, respectively, also has X ₁ or between X ₂ together linked May be, CI
Represents a counter ion when a counter ion is required to neutralize the charge).

Specific examples of the metal complex dye of the present invention are shown below, but the present invention is not limited thereto.

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In the synthesis of the metal complex dye represented by the general formula (I) of the present invention, the synthesis of the ligand is performed according to the method described in J. Org. Chem., 62,
1491, (1997), Chem. Commun., 1996, 1707, etc., and the method cited in the literature. The complexation synthesis can be carried out with reference to literatures such as J. Am. Chem. Soc., 115, 6382, (1993) and the methods cited in the literatures.

[2] Photoelectric Conversion Element The photoelectric conversion element of the present invention has semiconductor fine particles sensitized by the metal complex dye in the photosensitive layer. Preferably, as shown in FIG. 1, the conductive layer 10, the photosensitive layer 20, the charge transfer layer 30, and the counter electrode conductive layer 40 are laminated in this order, and the photosensitive layer 20 is sensitized by the metal complex dye 22 of the present invention. 21 and a charge transporting material 23 filled in a space between the semiconductor fine particles 21. The charge transport material 23 is composed of the same components as the materials used for the charge transfer layer 30. Further, a substrate 50 may be provided on the conductive layer 10 side and / or the counter electrode conductive layer 40 side in order to impart strength to the photoelectric conversion element. Hereinafter, in the present invention, a layer composed of the conductive layer 10 and the optional substrate 50 is referred to as a “conductive support”, and a layer composed of the counter electrode conductive layer 40 and the optional substrate 50 is referred to as a “counter electrode”. The photovoltaic cell connects the photoelectric conversion element to an external circuit to perform work. The conductive layer 10, the counter electrode conductive layer 40, and the substrate 50 in FIG. 1 are respectively a transparent conductive layer 10a, a transparent counter electrode conductive layer 40a,
The transparent substrate 50a may be used.

In the photoelectric conversion device of the present invention shown in FIG. 1, the light incident on the photosensitive layer 20 containing the semiconductor fine particles 21 sensitized by the metal complex dye 22 excites the dye 22, etc., and the excited dye 22, etc. High-energy electrons inside are semiconductor fine particles 21
And reaches the conductive layer 10 by diffusion. At this time, molecules such as the dye 22 are oxidized. In the photovoltaic cell, while the electrons in the conductive layer 10 work in an external circuit, the dye 22 passes through the counter electrode conductive layer 40 and the charge transfer layer 30.
And the dye 22 is regenerated. The photosensitive layer 20 functions as a negative electrode. At the boundary of each layer (for example, the boundary between the conductive layer 10 and the photosensitive layer 20, the boundary between the photosensitive layer 20 and the charge transfer layer 30, the boundary between the charge transfer layer 30 and the counter electrode conductive layer 40, etc.), They may be mutually diffused and mixed. Hereinafter, each layer will be described in detail.

(A) Conductive Support The conductive support comprises (1) a single layer of a conductive layer, or (2) two layers of a conductive layer and a substrate. A substrate is not necessarily required if a conductive layer that maintains sufficient strength and sealing properties is used.

In the case of (1), a conductive layer having sufficient strength and having conductivity, such as metal, is used as the conductive layer.

In the case of (2), a conductive agent is contained on the photosensitive layer side.
A substrate having a conductive layer can be used. Preferred conductive agents are metals (for example, platinum, gold, silver, copper, aluminum, rhodium, indium, etc.), carbon, or conductive metal oxides (indium-tin composite oxide, tin oxide doped with fluorine, etc.). Is mentioned. The thickness of the conductive layer is preferably about 0.02 to 10 μm.

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

When light is irradiated from the conductive support side, the conductive support is preferably substantially transparent.
Substantially transparent means that the light transmittance is 10% or more, preferably 50% or more, and particularly preferably 70% or more.

The transparent conductive support is preferably formed by forming a transparent conductive layer made of a conductive metal oxide on the surface of a transparent substrate such as glass or plastic by coating or vapor deposition. 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 preferable. For a low-cost and flexible photoelectric conversion element or solar cell, a transparent polymer film provided with a conductive layer is preferably used. Transparent polymer film materials include tetraacetyl cellulose (TAC),
Polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate (PAr), polysulfone (PSF), polyester sulfone (PES), Examples include polyetherimide (PEI), cyclic polyolefin, and brominated phenoxy. To ensure sufficient transparency,
The coating amount of the conductive metal oxide is preferably a support 1 m ² per 0.01~100g of glass or plastic.

It is preferable to use a metal lead for the purpose of lowering the resistance of the transparent conductive support. 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. The metal lead is preferably 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 preferably provided thereon. It is also preferable to provide a metal lead on the transparent conductive layer after providing the transparent conductive layer on the transparent substrate. The decrease in the amount of incident light due to the installation of the metal leads is preferably within 10%, more preferably 1 to 5%.

(B) Photosensitive Layer In the photosensitive layer containing semiconductor fine particles sensitized by the metal complex dye of the present invention, the semiconductor fine particles act as a so-called photoreceptor, absorb light to separate electric charges, and form electrons and positive electrons. Creates a hole. In the dye-sensitized semiconductor fine particles, light absorption and the resulting generation of electrons and holes mainly occur in the dye, and the semiconductor fine particles have a role of receiving and transmitting the electrons.

(1) Semiconductor Fine Particles Semiconductor fine particles include a simple semiconductor such as silicon or germanium, a III-V compound semiconductor, a metal chalcogenide (eg, oxide, sulfide, selenide, etc.), or a perovskite structure. Compounds (for example, strontium titanate, calcium titanate, sodium titanate, barium titanate, potassium niobate, etc.) can be used.

Preferred metal chalcogenides are titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, oxides of niobium or tantalum, cadmium, zinc, lead, silver, Examples include antimony or bismuth sulfide, cadmium or lead selenide, and cadmium telluride. Other compound semiconductors include phosphides such as zinc, gallium, indium and cadmium, selenides of gallium-arsenic or copper-indium, and sulfides of copper-indium.

Preferred specific examples of the semiconductor used in the present invention are Si, TiO ₂ , SnO ₂ , Fe ₂ O ₃ , WO ₃ , ZnO, Nb ₂ O ₅ , CdS, Zd
nS, PbS, Bi ₂ S ₃ , CdSe, CdTe, GaP, InP, GaAs, CuIn
S ₂ , CuInSe ₂ or the like, more preferably TiO ₂ , ZnO, Sn
O ₂ , Fe ₂ O ₃ , WO ₃ , Nb ₂ O ₅ , CdS, PbS, CdSe, InP, GaAs,
CuInS ₂ or CuInSe ₂ , particularly preferably TiO ₂ or Nb ₂ O ₅ , most preferably TiO ₂ .

The semiconductor used in the present invention may be single crystal or polycrystal. From the viewpoint of conversion efficiency, a single crystal is preferable,
Polycrystal is preferred from the viewpoints of production cost, securing of raw materials, energy payback time and the like.

The particle size of the semiconductor fine particles is generally on the order of nm to μm, but the average particle size of the primary particles obtained from the diameter when the projected area is converted into a circle is preferably from 5 to 200 nm, and from 8 to 200 nm. 100 nm is more preferred. The average particle size of the semiconductor fine particles (secondary particles) in the dispersion is preferably 0.01 to 100 μm.

Two or more types of fine particles having different particle size distributions may be mixed. In this case, the average size of the small particles is 5 nm.
It is preferred that: For the purpose of improving the light capture rate by scattering incident light, semiconductor particles having a large particle size, for example, about 300 nm may be mixed.

As methods for producing semiconductor fine particles, Sakuhana Sao's "Sol-Gel Method Science" Agne Shofusha (1998) and Technical Information Association "Sol-Gel Method for Thin Film Coating" (1995 ), Tadao Sugimoto, "Synthesis of Monodisperse Particles and Size Morphology Control by New Synthetic Gel-Sol Method", Materia, Vol. 35, No. 9, 1012-1018.
The gel-sol method described on page (1996) is preferred. Also
A method developed by Degussa to produce an oxide by high-temperature hydrolysis of a chloride in an oxyhydrogen salt is also preferable.

When the semiconductor fine particles are titanium oxide, any of the above-mentioned sol-gel method, gel-sol method, and high-temperature hydrolysis method in chloride oxyhydrogen salt are preferred. Applied Technology "Gihodo Publishing (1997)
The sulfuric acid method and the chlorine method described in (1) can also be used. Further, the sol-gel method is described in Barb et al., Journal of American Ceramic Society, Vol. 80, Vol.
No. 12, pages 3157-3171 (1997), and Burnside et al., Chemical Materials, Vol. 10, No. 9,
The method described on pages 2419 to 2425 is also preferred.

(2) Semiconductor fine particle layer In order to coat the semiconductor fine particles on the conductive support, in addition to the method of applying a dispersion or colloid solution of the semiconductor fine particles on the conductive support, the above-mentioned sol-gel is used. A method can also be used. In consideration of mass production of photoelectric conversion elements, physical properties of semiconductor fine particle liquid, flexibility of a conductive support, and the like, a wet film forming method is relatively advantageous. As a wet film forming method, a coating method and a printing method are typical.

As a method for preparing a dispersion of semiconductor fine particles, in addition to the above-described sol-gel method, a method of grinding in a mortar, a method of dispersing while pulverizing using a mill, or a method of preparing a solvent when synthesizing a semiconductor. A method of precipitating fine particles in the solution 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.). At the time of dispersion, a polymer, a surfactant, an acid, a chelating agent, or the like may be used as a dispersing aid, if necessary.

As a coating method, a roller method, a dip method as an application system, an air knife method, a blade method, etc. as a metering system.
No. 589, the wire bar method disclosed in U.S. Pat.
The slide hopper method, extrusion method, curtain method and the like described in JP-A Nos. 94, 2761419, 2761791 and the like are preferable. As a general-purpose machine, a spin method or a spray method is also preferable. As the wet printing method, intaglio printing, rubber printing, screen printing, and the like are preferable, including three major printing methods of letterpress, offset and gravure. From these, a preferable film forming method is selected according to the liquid viscosity and the wet thickness.

The viscosity of the dispersion liquid of the semiconductor fine particles greatly depends on the type and dispersibility of the semiconductor fine particles, the kind of the solvent used, and additives such as a surfactant and a binder. For a high viscosity liquid (for example, 0.01 to 500 Poise), an extrusion method, a casting method, a screen printing method, or the like is preferable. For 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. If a certain amount of coating is used, application by the extrusion method is possible even in the case of a low-viscosity liquid. As described above, a wet film forming method may be appropriately selected according to the viscosity of the coating solution, the coating amount, the support, the coating speed, and the like.

The layer of semiconductor fine particles is not limited to a single layer, but a multi-layer coating of a dispersion of semiconductor fine particles having different particle diameters or a coating layer containing semiconductor fine particles of different types (or different binders and additives) may be applied in multiple layers. It can also be applied. Multilayer coating is effective even when the film thickness is insufficient by one coating. The extrusion method or the slide hopper method is suitable for multilayer 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 semiconductor fine particle layer (same as the thickness of the photosensitive layer) becomes larger, the amount of dye carried per unit projected area increases, so that the light capture rate increases, but the diffusion distance of generated electrons increases. Therefore, the loss due to charge recombination also increases. Therefore, the preferred thickness of the semiconductor fine particle layer is
It is 0.1-100 μm. When used in a photovoltaic cell, the thickness of the semiconductor fine particle layer is preferably 1 to 30 μm,
More preferably, it is μm. 1m support for semiconductor fine particles
^The coating amount per ² is preferably 0.5 to 400 g, more preferably 5 to 100 g.

After coating the semiconductor fine particles on the conductive support, the semiconductor fine particles are brought into electronic contact with each other,
Heat treatment is preferably performed to improve the strength of the coating film and the adhesion to the support. A preferred heating temperature range is from 40 ° C to less than 700 ° C, more preferably from 100 ° C to 600 ° C. The heating time is about 10 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. It is preferable that the temperature be as low as possible from the viewpoint of cost. The lowering of the temperature can be attained by the above-mentioned combined use of small semiconductor particles of 5 nm or less, heat treatment in the presence of a mineral acid, and the like.

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

The semiconductor fine particles preferably have a large surface area so that many dyes can be adsorbed. Therefore, the surface area in a state where the layer of semiconductor fine particles is coated on the support is preferably 10 times or more the projected area,
Further, it is preferably 100 times or more. The upper limit is not particularly limited, but is usually about 1000 times.

(3) Adsorption of Metal Complex Dye on Semiconductor Fine Particles The metal complex dye is adsorbed on the semiconductor fine particles by dipping a conductive support having a well-dried semiconductor fine particle layer in a solution of the metal complex dye. Alternatively, a method of applying a solution of a metal complex dye to the semiconductor fine particle layer 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. In the case of the immersion method, the adsorption of the metal complex dye may be performed at room temperature, or may be performed by heating and refluxing as described in JP-A-7-249790. The latter coating method includes a wire bar method, a slide hopper method, an extrusion method, a curtain method, a spin method, a spray method, and the like, and a printing method includes letterpress, offset, gravure, screen printing, and the like. The solvent can be appropriately selected according to the solubility of the metal complex 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 (diethyl ether, tetrahydrofuran, etc.), dimethyl sulfoxide, amides (N, N-
Dimethylformamide, N, N-dimethylacetamide, etc.)
N-methylpyrrolidone, 1,3-dimethylimidazolidinone,
3-methyloxazolidinone, esters (ethyl acetate,
Butyl acetate, etc.), carbonates (diethyl carbonate, ethylene carbonate, propylene carbonate, etc.), ketones (acetone,
Examples thereof include 2-butanone, cyclohexanone, etc.), hydrocarbons (hexane, petroleum ether, benzene, toluene, etc.), water, and a mixed solvent thereof.

As for the viscosity of the solution of the metal complex dye, similarly to the formation of the semiconductor fine particle layer, a high viscosity liquid (for example, 0.01
~ 500 Poise), various printing methods other than the extrusion method are suitable, and low viscosity liquids (for example, 0.1 Poise or less)
In this case, a slide hopper method, a wire bar method or a spin method is suitable, and any of them can form a uniform film.

Thus, the viscosity of the coating solution of the metal complex dye,
The dye adsorption method may be appropriately selected according to the amount of application, the conductive support, the application speed, and the like. The time required for dye adsorption after coating should be as short as possible in consideration of mass production.

Since the presence of the metal complex dye which has not been adsorbed disturbs the performance of the device, it is preferable to remove the dye by washing immediately after the adsorption. It is preferable to perform washing with a polar solvent such as acetonitrile and an organic solvent such as an alcohol solvent using a wet washing tank. In order to increase the amount of dye adsorbed,
It is preferable to perform a heat treatment before the adsorption. After the heat treatment, it is preferable that the dye be quickly adsorbed at a temperature of 40 to 80 ° C. without returning to room temperature in order to avoid the adsorption of water on the surface of the semiconductor fine particles.

The total amount of the metal complex dye used is preferably 0.01 to 100 mmol per unit surface area (1 m ² ) of the conductive 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. By setting the adsorption amount of the metal complex dye as described above, a sufficient sensitizing effect in the semiconductor can be obtained. On the other hand, if the amount of the dye is too 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 order to widen the wavelength range of photoelectric conversion as much as possible and to increase the conversion efficiency, two or more dyes may be mixed. In this case, it is preferable to select the dyes to be mixed and the ratio thereof so as to match the wavelength range and the intensity distribution of the light source. Specifically, the metal complex dye of the present invention is
It is possible to use more than one kind in combination, or to use the metal complex dye of the present invention in combination with a conventional metal complex dye and / or polymethine dye.

For the purpose of reducing the interaction between metal complex dyes such as association, a colorless compound may be co-adsorbed on the semiconductor fine particles. Examples of the hydrophobic compound to be co-adsorbed include a steroid compound having a carboxyl group (for example, chenodeoxycholic acid). Further, an ultraviolet absorber can be used in combination.

For the purpose of promoting the removal of excess metal complex dye, the surface of the semiconductor fine particles may be treated with amines after adsorbing the metal complex dye. Preferred amines include pyridine, 4-t-butylpyridine, polyvinylpyridine and the like. When these are liquids, they may be used as they are, or may be used after being dissolved in an organic solvent.

(C) Charge Transfer Layer The charge transfer layer is a layer having a function of replenishing the oxidized metal complex dye with electrons. Typical materials that can be used for the charge transfer layer include a liquid (electrolytic solution) in which a redox couple is dissolved in an organic solvent, a so-called gel electrolyte in which a liquid in which a redox couple is dissolved in an organic solvent is impregnated in a polymer matrix,
Molten salts containing a redox couple may be mentioned. Further, a solid electrolyte or a hole transporting material can be used.

The electrolytic solution used in the present invention preferably comprises an electrolyte, a solvent and an additive. As the electrolyte,
(A) I ₂ and an iodide (a metal iodide such as LiI, NaI, KI, CsI, and CaI ₂ , or an iodide salt of a quaternary ammonium compound such as a tetraalkylammonium iodide, a pyridinium iodide, an imidazolium iodide, and the like) ), And (b) Br ₂ and bromide (LiBr, NaBr, KBr, CsBr, C
a bromide such as aBr ₂ or a bromide salt of a quaternary ammonium compound such as tetraalkylammonium bromide and pyridinium bromide); Metal complexes, (d) sodium polysulfide, sulfur compounds such as alkylthiol-alkyldisulfide, (e) viologen dyes, hydroquinone-quinone and the like can be used. Among them, I ₂ and LiI or pyridinium iodide, electrolyte obtained by combining the iodine salt of imidazolium iodide quaternary ammonium compounds such as id are preferred. The above electrolytes may be used as a mixture. The electrolyte is EP718288, WO95 / 18456, J. Electrochem. So
c., Vol. 143, No. 10, 3099 (1996), Inorg. Chem., 35,
1168-1178 (1996) and the like, salts in a molten state at room temperature (molten salts) can also be used. When a molten salt is used as an electrolyte, a solvent need not be used.

The preferred electrolyte concentration is 0.1 to 15M, more preferably 0.2 to 10M. The preferred concentration of iodine when adding iodine to the electrolyte is 0.01 to 0.5 M.
It is.

As the solvent for the electrolyte, a compound which can exhibit excellent ionic conductivity because it has a low viscosity and a high ion mobility, a high dielectric constant and a high effective carrier concentration, or both is used. It is desirable. Examples of such solvents include, for example, the following.

(A) Carbonates Esters such as ethylene carbonate, propylene carbonate, vinylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and dipropyl carbonate are preferred.

(B) Lactones For example, γ-butyrolactone, γ-valerolactone, γ-caprolactone, clotlactone, γ-caprolactone, δ-valerolactone and the like are preferable.

(C) Ethers Preferred are, for example, ethyl ether, 1,2-dimethoxyethane, diethoxyethane, trimethoxymethane, ethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, 1,3-dioxolan, 1,4-dioxane and the like.

(D) Alcohols Preferred are, for example, methanol, ethanol, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether and the like.

(E) Glycols For example, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin and the like are preferable.

(F) Glycol ethers Preferred are, for example, ethylene glycol dialkyl ether, propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether and the like.

(G) Tetrahydrofurans For example, tetrahydrofuran, 2-methyltetrahydrofuran and the like are preferable.

(H) Nitriles For example, acetonitrile, glutarodinitrile, propionitrile, methoxyacetonitrile, benzonitrile and the like are preferable.

(I) Carboxylic esters Esters such as methyl formate, methyl acetate, ethyl acetate and methyl propionate are preferred.

(J) Phosphoric acid triesters For example, trimethyl phosphate, triethyl phosphate and the like are preferable.

(K) Heterocyclic compounds For example, N-methylpyrrolidone, 4-methyl-1,3-dioxane, 2-methyl-1,3-dioxolan, 3-methyl-2-oxazolidinone, 1,3-propanesal Ton, sulfolane and the like are preferred.

(L) Other aprotic organic solvents such as dimethyl sulfoxide, formamide, N, N-dimethylformamide, nitromethane, etc.
Water and the like are preferred.

Of these, carbonate-based, nitrile-based and heterocyclic compound-based solvents are preferred. These solvents may be used as a mixture of two or more as necessary.

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

The electrolyte can be gelled (solidified) by a method such as addition of a polymer or an oil gelling agent, polymerization of coexisting polyfunctional monomers, and crosslinking reaction with the polymer. When gelling by adding a polymer, use "Polymer Electrolyte Reviews-1,2" (JR Mac
ELSEIVER APPLIED SCIE co-edited by CaLLum and CA Vincent
NCE) can be used,
In particular, it is preferable to use polyacrylonitrile and polyvinylidene fluoride. When gelation is performed by adding an oil gelling agent, use J. Chem. Soc. Japan, Ind. Chem. Se.
c., 46, 779 (1943), J. Am. Chem. Soc., 111, 5542.
(1989), J. Chem. Soc., Chem. Commun., 1993, 390, A
ngew. Chem. Int. Ed. Engl., 35, 1949 (1996), Chem.
Lett., 1996, 885; J. Chem. Soc., Chem. Commun., 5
45 (1997) and the like can be used. Among these, preferred are compounds having an amide structure in the molecular structure.

When a gel electrolyte is formed by polymerization of polyfunctional monomers coexisting in the electrolyte, a solution is prepared from the polyfunctional monomers, a polymerization initiator, an electrolyte and a solvent,
Coating is performed on the dye-sensitized semiconductor fine particle layer (photosensitive layer 20) by a method such as a casting method, a coating method, a dipping method, and an impregnation method. FIG.
As shown in (2), it is preferable to fill the voids between the dye-sensitized semiconductor fine particles 21 with a sol-like electrolyte, form a sol-like electrolyte layer on the photosensitive layer 20, and then gel it by radical polymerization.

The polyfunctional monomer is preferably a compound having two or more ethylenically unsaturated groups, for example, divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol. Diacrylate, triethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate and the like are preferred.

The gel electrolyte may contain a monofunctional monomer in addition to the above polyfunctional monomer. Examples of the monofunctional monomer include esters or amides derived from acrylic acid or α-alkylacrylic acid (eg, methacrylic acid) (eg, N-isopropylacrylamide, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, Derived from acrylamidopropyltrimethylammonium chloride, methyl acrylate, hydroxyethyl acrylate, N-propyl acrylate, N-butyl acrylate, 2-methoxyethyl acrylate, cyclohexyl acrylate, etc., vinyl esters (eg vinyl acetate), maleic acid or fumaric acid Esters (eg, dimethyl maleate, dibutyl maleate, diethyl fumarate, etc.) and organic acid salts (eg, sodium salt of maleic acid, fumaric acid or p-styrenesulfonic acid) ), A nitrile (acrylonitrile,
Methacrylonitrile, etc.), dienes (eg, butadiene, cyclopentadiene, isoprene, etc.), aromatic vinyl compounds (eg, styrene, p-chlorostyrene, sodium styrenesulfonate, etc.), vinyl compounds having a nitrogen-containing heterocyclic ring, Vinyl compounds having a quaternary ammonium salt, N-vinylformamide, N-vinyl-N-methylformamide, vinylsulfonic acid, sodium vinylsulfonate, vinylidene fluoride, vinylidene chloride, vinyl alkyl ethers (eg, methyl vinyl ether) , Olefins (ethylene, propylene, 1-
Butene, isobutene, etc.), N-phenylmaleimide and the like. The ratio of the polyfunctional monomer to the total amount of the monomers is preferably 0.5 to 70% by weight, more preferably
1.0 to 50% by weight.

The above-mentioned monomers for gel electrolytes are described in Takatsu Otsu,
Masayoshi Kinoshita, "Experimental Methods for Polymer Synthesis" (Chemical Doujin)
Alternatively, the polymerization can be carried out by a radical polymerization method which is a general polymer synthesis method described in “Lecture Polymerization Theory 1 Radical Polymerization (I)” by Takayuki Otsu (Chemical Doujinshi). Radical polymerization of monomers for gel electrolyte is performed by heating, light,
It can be carried out by ultraviolet rays, electron beams or the like or electrochemically, but it is particularly preferable to carry out radical polymerization by heating.

When a crosslinked polymer is formed by heating, preferred polymerization initiators are, for example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (dimethylvaleronitrile), dimethyl 2,2 ′ Azo initiators such as azobis (2-methylpropionate) and peroxide initiators such as benzoyl peroxide. The preferable addition amount of the polymerization initiator is 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, based on the total amount of the monomers.

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

When the electrolyte is gelled by the crosslinking reaction of the polymer, it is desirable to use a polymer having a crosslinking reactive group and a crosslinking agent together. Preferred crosslinkable reactive groups are
It 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 capable of electrophilic reaction with a nitrogen atom. Reagents having two or more functionalities (eg, alkyl halides, aralkyl halides, sulfonic acid esters, acid anhydrides, acid chlorides, isocyanates, etc.).

Organic and / or inorganic hole transport materials can be used in place of the electrolyte. Examples of the organic hole transporting material that can be preferably used in the present invention include the following.

(A) Aromatic amines N, N'-diphenyl-N, N'-bis (4-methoxyphenyl)-(1,
1'-biphenyl) -4,4'-diamine (J. Hagen et al., Syn
thetic Metal, 89, 215-220 (1997)), 2,2 ', 7,7'-tetrakis (N, N-di-p-methoxyphenylamine) -9,9'-spirobifluorene (Nature, Vol. .395, 8 Oct. 1998, p
p.583-585 and WO97 / 10617), aromatic diamine compounds in which tertiary aromatic amine units of 1,1-bis [4- (di-p-tolylamino) phenyl] cyclohexane are linked (Japanese Unexamined Patent Publication No. 59-1)
No. 94393) and 4,4′-bis [(N-1-naphthyl) -N-phenylamino] biphenyl containing two or more tertiary amines and two or more fused aromatic rings having a nitrogen atom , An aromatic triamine having a starburst structure with a derivative of triphenylbenzene (US Pat. No. 4,923,774, JP-A-4-308688), N, N'-
Aromatic diamines such as diphenyl-N, N′-bis (3-methylphenyl)-(1,1′-biphenyl) -4,4′-diamine (US Pat. No. 4,764,625), α, α, α ′, α'-tetramethyl-α, α'-
Bis [4- (di-p-tolylamino) phenyl] -p-xylene (JP-A-3-269084), a p-phenylenediamine derivative, and a triphenylamine derivative whose whole molecule is sterically asymmetric (JP-A-4-129271) ), A compound in which a pyrenyl group is substituted with a plurality of aromatic diamino groups (JP-A-4-175395), an aromatic diamine in which a tertiary aromatic amine unit is linked by an ethylene group (JP-A-4-264189), styryl Aromatic diamines having a structure (Japanese Patent Application Laid-Open No. 4-290851), benzylphenyl compounds (Japanese Patent Application Laid-Open No. 4-364153), tertiary amines linked by a fluorene group (Japanese Patent Application Laid-Open No. 5-25473), and triamine compounds (JP-A-5-25473) Kaihei 5-239455), bis (dipyridylamino) biphenyl (JP-A-5-320634), N, N, N-triphenylamine derivatives (JP-A-6-1972), and aromatic diamines having a phenoxazine structure Kaihei 7-138562), diaminophenylfe Ntorijin derivatives (JP-A-7-252474) and the like.

(B) Oligothiophene compounds α-octylthiophene and α, ω-dihexyl-α-octylthiophene (Adv. Mater., Vol. 9, No. 7, 5578)
(1997)), hexadodecyldodecithiophene (Angew. C
hem. Int. Ed. Engl., 34, No. 3, 303-307 (1995)),
2,8-dihexyl anthra [2,3-b: 6,7-b '] dithiophene (JACS, Vol. 120, No. 4, 664-672 (1998)) and the like.

(C) Conductive Polymer Polypyrrole (K. Murakoshi et al., Chem. Lett., 19
97, p.471), polyacetylene and its derivatives, poly
(p-phenylene) and its derivatives, poly (p-phenylenevinylene) and its derivatives, polythienylenevinylene and its derivatives, polythiophene and its derivatives,
Polyaniline and its derivatives, polytoluidine and its derivatives ("Handbook of Organic Conduc
tive Molecules and Polymers ", Vol. 1-4 (NALWA
Author, WILEY publication)).

Organic, hole-transporting materials include Nature,
As described in Vol. 395, 8 Oct. 583-585 (1998), a compound containing a cation radical such as tris (4-bromophenyl) aminium hexachloroantimonate is used to control the dopant level. Alternatively, a salt such as Li [(CF ₃ SO ₂ ) ₂ N] may be added in order to control the potential of the oxide semiconductor surface (compensate for the space charge layer).

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, use Electorochim. Acta, 40, 643-6 to prevent short circuits.
It is preferable to apply a thin layer of titanium dioxide as an undercoat layer by using a technique such as spray pyrolysis described in JP 52 (1995).

When an inorganic solid compound is used in place of the electrolyte, copper iodide (p-CuI) (J. Phys. D: Appl. Phys.,
31, 1492-1496 (1998)), copper thiocyanate (Thin Sol
id Films, 261, 307-310 (1995), J. Appl. Phys., 80
(8), 15 October 1996, 4749-4754, Chem. Mater., 1
0, 1501-1509, (1998), SemiCond. Sci. Technol., 1
0, 1689 to 1693) can be introduced into 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.

To form the charge transfer layer, the following two methods can be used. One is to attach a counter electrode via a spacer on the dye-sensitized semiconductor fine particle layer,
This is a method in which the open ends of both are immersed in an electrolyte solution to allow the electrolyte solution to penetrate into the semiconductor fine particle layer and the gap between the semiconductor fine particle layer and the counter electrode. The other is a method in which an electrolyte solution is applied to the semiconductor fine particle layer so that the electrolyte solution penetrates into the semiconductor fine particle layer, a charge transfer layer is formed on the semiconductor fine particle layer, and finally a counter electrode is provided.

In the former case, as a method for infiltrating the electrolyte solution into the gap between the semiconductor fine particle layer and the counter electrode, a normal pressure method utilizing a capillary phenomenon, and an upper open end of the semiconductor fine particle layer and the counter electrode (dipping in the electrolyte solution). There is a decompression method that sucks from the open end that does not exist.

In the latter case, in the case of a wet type charge transfer layer, a counter electrode is provided in an undried state to take measures to prevent liquid leakage at the edge portion. In the case of a gel electrolyte, a counter electrode may be provided after being wet-coated and solidified by a method such as polymerization, or a solid may be provided after the counter electrode is provided. As a method of forming a layer of a wet organic hole transport material or a gel electrolyte in addition to the electrolytic solution, as in the case of forming a semiconductor fine particle layer and dye adsorption, a dipping method, a roller method, a dipping method, an air knife method, An extrusion method, a slide hopper method, a wire bar method, a spin method, a spray method, a casting method, various printing methods and the like can be used. In the case of a solid electrolyte or a solid hole (hole) transport material, the charge transfer layer may be formed by a dry film forming process such as a vacuum evaporation method or a CVD method, and then a counter electrode may be provided.

In the case of an electrolyte which cannot be solidified or a wet hole transport material, it is preferable to seal the edge portion immediately after application, and in the case of a hole transport material which can be solidified, it is preferable to provide a positive hole by wet application. After forming the hole transport layer, it is preferable to solidify the film by a method such as photopolymerization or thermal radical polymerization. As described above, the film application method may be appropriately selected depending on the physical properties of the electrolyte and the process conditions.

The amount of water in the charge transfer layer was 10,000 ppm.
The following is preferred, more preferably 2,000 ppm or less, and particularly preferably 100 ppm or less.

(D) Counter electrode The counter electrode functions as a positive electrode of a photovoltaic cell when the photoelectric conversion element is a photovoltaic cell. The counter electrode may have a single-layer structure of a counter electrode conductive layer made of a conductive material, or may be composed of a counter electrode conductive layer and a support substrate, similarly to the above-described conductive support. Examples of the conductive material used for the counter electrode conductive layer include metals (for example, platinum, gold, silver, copper, aluminum, rhodium, indium, etc.), carbon, and conductive metal oxides (indium-tin composite oxide, tin oxide doped with fluorine). Etc.)
And the like. Preferred examples of the supporting substrate for the counter electrode are glass and plastic, to which the above-described conductive material is applied or vapor-deposited. The thickness of the counter electrode conductive layer is not particularly limited, but is preferably 3 nm to 10 μm. When the counter electrode conductive layer is made of metal, its thickness is preferably 5 μm or less, more preferably in the range of 5 nm to 3 μm.

Since light may be irradiated from one or both of the conductive support and the counter electrode, at least one of the conductive support and the counter electrode must be substantially transparent in order for light to reach the photosensitive layer. I just need. From the viewpoint of improving power generation efficiency,
It is preferable that the conductive support is made transparent and light is incident from the conductive support side. In this case, the counter electrode preferably has a property of reflecting light. As such a counter electrode, glass or plastic on which a metal or a conductive oxide is deposited, or a metal thin film can be used.

The procedure for providing the counter electrode support is as follows:
Providing a charge transfer layer after forming it,
(B) There are two cases in which a counter electrode is disposed on a layer of dye-sensitized semiconductor fine particles via a spacer, and then the space is filled with an electrolyte solution. In the case of (a), a conductive material is applied directly on the charge transfer layer, plated or vapor-deposited (PVD, CVD), or the conductive layer side of the substrate having the conductive layer is attached. In the case of (b), a counter electrode is assembled and fixed on the dye-sensitized semiconductor fine particle layer via a spacer, and the open end of the obtained assembly is immersed in an electrolyte solution, and utilizing capillary action or decompression. An electrolyte solution is made to penetrate into the gap between the dye-sensitized semiconductor fine particle layer and the counter electrode. In this case, if the electrolyte is a polymer electrolyte or the like, crosslinking is performed by heating or the like as necessary.
Further, similarly to the case of the conductive support, it is preferable to use a metal lead for the purpose of reducing the resistance of the counter electrode, particularly when the counter electrode is transparent. Note that the preferable material and the installation method of the metal lead, the decrease in the amount of incident light due to the installation of the metal lead, and the like are the same as those of the conductive support.

(E) Other Layers A functional layer such as a protective layer or an antireflection layer may be provided on one or both of the conductive support serving as an electrode and the counter electrode. When such a functional layer is formed in multiple layers, a simultaneous multilayer coating method or a sequential coating method can be used, but from the viewpoint of productivity, the simultaneous multilayer coating method is preferable. In the simultaneous multi-layer coating method, a slide hopper method or an extrusion method is suitable in consideration of productivity and uniformity of a coating film. In forming these functional layers, an evaporation method, a sticking method, or the like can be used depending on the material.

(F) Specific Example of Internal Structure of Photoelectric Conversion Element As described above, the internal structure of the photoelectric conversion element can take various forms according to the purpose. When roughly divided into two, a structure in which light can enter from both sides and a structure in which light can be entered only from one side are possible. 2 to 9 exemplify an internal structure of a photoelectric conversion element which can be preferably applied to the present invention.

FIG. 2 shows the transparent conductive layer 10a and the transparent counter electrode conductive layer 4.
The photosensitive layer 20 and the charge transfer layer 30 are interposed between the photosensitive layer 20a and the light transfer layer 0a, and have a structure in which light enters from both sides.
FIG. 3 shows that a metal lead 11 is partially provided on a transparent substrate 50a, a transparent conductive layer 10a is further provided, an undercoat layer 60, a photosensitive layer 20, a charge transfer layer 30, and a counter electrode conductive layer 40 are provided in this order. The substrate 50 is arranged, and has a structure in which light is incident from the conductive layer side. FIG. 4 shows that the conductive layer 10 is provided on the support substrate 50, the photosensitive layer 20 is provided via the undercoat layer 60, the charge transfer layer 30 and the transparent counter electrode conductive layer 40a are provided, and the metal leads 11 are partially provided. The provided transparent substrate 50a is arranged with the metal lead 11 side inside, and has a structure in which light enters from the counter electrode side. FIG. 5 shows that the undercoat layer 60, the photosensitive layer 20, the charge transfer layer 30 and the undercoat layer 60 are provided between the two transparent substrates 50a, each of which is provided with the metal lead 11 partially and the transparent conductive layer 10a or the transparent counter electrode conductive layer 40a. And light enters from both sides. FIG. 6 shows a transparent substrate 50a.
A transparent conductive layer 10a is provided thereon, and the photosensitive layer 2
0, the charge transfer layer 30 and the counter electrode conductive layer 40 are further provided, and the support substrate 50 is disposed thereon. In this structure, light enters from the conductive layer side. FIG. 7 has a conductive layer 10 on a support substrate 50, and a photosensitive layer 20 provided with an undercoat layer 60 interposed therebetween.
Further provided a charge transfer layer 30 and a transparent counter electrode conductive layer 40a,
The transparent substrate 50a is disposed thereon, and has a structure in which light enters from the counter electrode side. FIG. 8 has a transparent conductive layer 10a on a transparent substrate 50a, a photosensitive layer 20 is provided via an undercoat layer 60, a charge transfer layer 30 and a transparent counter electrode conductive layer 40a are further provided, and the transparent substrate 50a is provided thereon. They are arranged so that light enters from both sides. FIG. 9 shows that the conductive layer 10 is provided on the supporting substrate 50, and the photosensitive layer 20 is provided via the undercoat layer 60.
And a solid charge transfer layer 30 is further provided thereon, and a counter electrode conductive layer 40 or a metal lead 11 is partially provided on the solid charge transfer layer 30, so that light enters from the counter electrode side.

[3] Photocell The photocell of the present invention is one in which the above-mentioned photoelectric conversion element is made to work in an external circuit. When the charge transfer layer is an ion conductive electrolyte, a photoelectrochemicell (photoelectrochemi
cal cell). It is preferable that the side surface of the photovoltaic cell is sealed with a polymer, an adhesive, or the like in order to prevent deterioration of components and volatilization of the contents. The external circuit itself connected to the conductive support and the counter electrode via the lead may be a known one.

[4] Dye-Sensitized Solar Cell When the photoelectric conversion element of the present invention is applied to a so-called solar cell, the structure inside the cell is basically the same as the above-described structure of the photoelectric conversion element. Hereinafter, a module structure of a solar cell using the photoelectric conversion element of the present invention will be described.

The dye-sensitized solar cell of the present invention can have a module structure basically similar to a conventional solar cell module. The solar cell module generally has a structure in which cells are formed on a supporting substrate such as a metal and a ceramic, and the cells are covered with a filling resin or a protective glass or the like, and light is taken in from the opposite side of the supporting substrate. It is also possible to adopt a structure in which a transparent material such as tempered glass is used for the support substrate, a cell is formed thereon, and light is taken in from the transparent support substrate side. Specifically, a module structure called a superstrate type, a substrate type, or a potting type, a substrate-integrated module structure used in an amorphous silicon solar cell, and the like are known. The module structure of the dye-sensitized solar cell of the present invention can be appropriately selected depending on the purpose of use, the place of use, and the environment.

In a typical superstrate type or substrate type module, cells are arranged at fixed intervals between supporting substrates which are transparent on one or both sides and have been subjected to anti-reflection treatment, and adjacent cells are made of metal leads or flexible. It is connected by wiring and the like, and a current collecting electrode is arranged on the outer edge, so that generated power can be taken out. Between the substrate and the cell, various kinds of plastic materials such as ethylene vinyl acetate (EVA) may be used in the form of a film or a filling resin, depending on the purpose, in order to protect the cell and improve current collection efficiency. Also, when used in places where it is not necessary to cover the surface with a hard material, such as places where there is little external impact, the surface protective layer is made of a transparent plastic film, or the above resin is cured to cure the protective function. It is possible to 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 secure the inside sealing and 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 filling material, and the sealing material, a solar cell can be formed on a curved surface.

[0205] In a super straight type solar cell module, for example, while a front substrate sent out from a substrate supply device is conveyed by a belt conveyor or the like, a cell is formed thereon with a sealing material-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 produce.

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 wire, the sealing material, and the like. It can be manufactured by placing a front cover and setting a frame on the periphery.

FIG. 10 shows an example of a structure in which the photoelectric conversion element of the present invention is formed into a substrate-integrated module. 10 has one face transparent conductive layer 10a on the transparent substrate 50a, further photosensitive layer 20 containing a dye-adsorbed TiO ₂ thereon, the solid charge transfer layer 30 and the metal counter electrically conductive layer 40 Is provided as a module, and an antireflection layer 70 is provided on the other surface of the substrate 50a.
Represents a structure provided with. In the case of such a structure, it is preferable to increase the area ratio of the photosensitive layer 20 (the area ratio when viewed from the substrate 50a which is the light incident surface) in order to increase the utilization efficiency of incident light.

In the case of the module having the structure shown in FIG. 10, selective plating, selective etching, and CVD are performed so that the transparent conductive layer, the photosensitive layer, the charge transfer layer, the counter electrode, and the like are three-dimensionally arranged at regular intervals on the substrate. , PVD and other semiconductor process technologies, laser scribing after pattern coating or wide coating, plasma CVM (Solar Energy Materials and Sola)
r Cells, 48, pp. 373-381), and a desired module structure can be obtained by patterning with a mechanical method such as grinding.

[0209] Other members and steps will be described below in detail.

Examples of the sealing material include liquid EVA (ethylene vinyl acetate), depending on the purpose of imparting weather resistance, imparting electrical insulation, improving light-collecting efficiency, and improving cell protection (impact resistance).
Various materials such as a film-like EVA and a mixture of a vinylidene fluoride copolymer and an acrylic resin can be used. It is preferable to use a sealing material having high weather resistance and moisture resistance between the outer edge of the module and the frame surrounding the periphery. In addition, the strength and light transmittance can be increased by mixing a transparent filler into the sealing material.

When the sealing material is fixed on the cell, a method suitable for the physical properties of the material is used. In the case of film-like materials, various methods such as roll pressing, bar coating, spray coating, screen printing, etc. are possible. is there.

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 a sealing layer is continuously laminated by the above method. Can be highly productive.

In order to increase the power generation efficiency, the surface of the substrate (generally tempered glass) on the light intake side of the module may be subjected to an anti-reflection treatment. Examples of the antireflection treatment method include 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 taken into the module without any loss. However, the light transmitted through the photoelectric conversion layer and reaching the inside thereof is reflected and the efficiency is reduced toward the photoelectric conversion layer. It is also important to return well. As a method of increasing the light reflectance, after mirror polishing the surface of the supporting substrate, a method of depositing or plating Ag or Al, etc., an alloy layer such as Al-Mg, Al-Ti at the bottom layer of the cell as a reflective layer. There are a method of providing a texture structure and a method of forming a texture structure in the lowermost layer by annealing.

Further, in order to increase the power generation efficiency, it is important to reduce the connection resistance between cells in order to suppress the internal voltage drop. As a method of connecting the cells, wire bonding and connection using a conductive flexible sheet are generally used.However, a method of fixing the cells using a conductive adhesive tape or a conductive adhesive and simultaneously electrically connecting the cells, There is also a method of pattern-coating a conductive hot melt at a desired position.

In the case of a solar cell using a flexible support such as a polymer film, the cells are sequentially formed by the above-described method while the roll-shaped support is being sent out, cut into a desired size, and the peripheral portion is made flexible and moisture-proof. The battery body can be manufactured by sealing with a material having a property.
Also, Solar Energy Materials and Solar Cells, 48,
A module structure called “SCAF” described in p383-391 can also be used. Further, a solar cell using a flexible support can be used by being adhered and fixed to a curved glass or the like.

As described in detail above, solar cells having various shapes and functions can be manufactured according to the purpose of use and environment of use.

[0219]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

(A) Synthesis of Metal Complex Dye The synthesis method of the metal complex dye D-98 is as follows.

[0221]

Embedded image

1. Synthesis of D-98 Ruthenium (III) chloride trihydrate: 10.44 g (40 mmol)
Was dissolved in 50 ml of dimethyl sulfoxide (DMSO) and refluxed for 5 minutes. After concentrating to 25 ml, 200 ml of acetone was added. After cooling to room temperature, the crystals were separated by filtration and washed with acetone and ether to obtain 13.9 g (yield: 72%) of Ru complex 2 as yellow crystals.

0.87 g (1.8 mmol) of Ru complex 2 and 0.54
g (1.8 mmol) of diethyl bipyridinedicarboxylate 3 was dissolved in 5 ml of chloroform and refluxed for 4 hours in a nitrogen atmosphere. After concentration, a small amount of acetone was added to dissolve, and then ether was added to precipitate crystals. After filtration, the crystals were washed with ether to obtain 0.85 g (yield: 75%) of yellow crystals of Ru complex 4.

0.126 g (0.2 mol) of Ru complex 4 and 0.032
4 g (0.4 mmol) of sodium thiocyanate in 30 ml of DMF
And 10 ml of water, and the mixture was refluxed for 2 hours in a nitrogen atmosphere. Further, J. Org. Chem., 62,1491, (199
7) Ligand 5 synthesized by the method described in 0.0334 g (0.1 mm
ol) and refluxed for 10 hours. 10 ml of triethylamine was added, and the mixture was refluxed for further 6 hours and concentrated. Purified by Sephadex column LH-20 (developing solvent: methanol)
After dissolving in water, dilute nitric acid was added to obtain 0.10 g of D-98 crystals. The structure was confirmed by NMR spectrum and elemental analysis.

2. Synthesis of Other Dyes Other metal complex dyes used in the following Examples were synthesized in the same manner as the above Synthesis Examples by appropriately combining the specific examples of each ligand. Each ligand is described in J. Org. Chem., 62, 1
491, (1997), Chem. Commun., 1996, 1707 and the like or the references cited therein.

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

(C) Preparation of TiO ₂ Electrode Adsorbing Dye Conductive glass having tin oxide layer doped with fluorine (TCO glass-U manufactured by Asahi Glass Co., Ltd. cut into a size of 20 mm × 20 mm, The above dispersion was applied to the conductive surface side having a surface resistance of about 30 Ω / □ using a glass rod (application amount of semiconductor fine particles: 20 g / m ² ). At this time, a part of the conductive surface side (3 from the end)
mm) to form a spacer, and glass was arranged side by side so that the adhesive tape was positioned at both ends, and applied eight at a time. After application, the adhesive tape was peeled off and air-dried at room temperature for one day. Next, the glass was placed in an electric furnace (muffle furnace FP-32 type, manufactured by Yamato Scientific Co., Ltd.), and baked at 450 ° C. for 30 minutes.
To give an O ₂ electrode. After the electrode was taken out and cooled, it was immersed in a methanol solution (2 × 10 ⁻⁴ mol / l each) of the metal complex dye of the present invention and Comparative Dye 1 for 15 hours. The dyed TiO ₂ electrode was immersed in 4-t-butylpyridine for 15 minutes, washed with ethanol, and air-dried. The thickness of the obtained photosensitive layer was 10 μm.

[0228]

Embedded image

(D) Fabrication of Photovoltaic Cell The dye-sensitized TiO ₂ electrode substrate (20 mm
× 20 mm) was overlaid with a platinum-deposited glass of the same size. Next, an electrolytic solution (3-methoxypropionitrile was used as an electrolyte to form a 1-
Iodine salt of methyl-3-hexylimidazolium (0.65mol
/ l) and iodine (0.05 mol / l) were impregnated and introduced into a TiO ₂ electrode to obtain a photovoltaic cell. According to the present embodiment, a conductive support layer made of a conductive glass (a conductive layer 10a provided on a glass transparent substrate 50a), a dye-sensitized TiO ₂ photosensitive layer 20 shown in FIG. A photovoltaic cell was prepared in which the charge transfer layer 30 made of the electrolytic solution, the counter electrode conductive layer 40 made of platinum, and the transparent substrate 50a made of glass were laminated in this order and sealed with an epoxy-based sealant.

(E) Measurement of Photoelectric Conversion Wavelength and Photoelectric Conversion Efficiency The photoelectric conversion efficiency of the obtained photoelectric conversion element at 800 nm was measured using an IPCE (Incident Photon to Current Con
version Efficiency). Table 1
Table 2 summarizes the photoelectric conversion efficiencies of photovoltaic cells using each metal complex dye.

[0231]

[Table 1]

From Table 1, it is found that Comparative Dye 1 for 800 nm light was used.
Shows no photoelectric conversion ability because of no absorption ability, whereas the metal complex dye of the present invention shows good photoelectric conversion ability. As described above, all of the dyes of the present invention have high photoelectric conversion ability not only in visible light but also in infrared region.

[0233]

As described in detail above, the metal complex dye of the present invention has good light absorption in a wide wavelength range from visible light to infrared light, and therefore contains semiconductor fine particles adsorbing such a metal complex dye. The photoelectric conversion element has high photoelectric conversion characteristics over a range from visible light to infrared light. A photovoltaic cell including such a photoelectric conversion element is extremely effective as a solar cell.

[Brief description of the drawings]

FIG. 1 is a partial sectional view showing the structure of a preferred photoelectric conversion element of the present invention.

FIG. 2 is a partial sectional view showing the structure of a preferred photoelectric conversion element of the present invention.

FIG. 3 is a partial sectional view showing the structure of a preferred photoelectric conversion element of the present invention.

FIG. 4 is a partial sectional view showing the structure of a preferred photoelectric conversion element of the present invention.

FIG. 5 is a partial sectional view showing the structure of a preferred photoelectric conversion element of the present invention.

FIG. 6 is a partial sectional view showing the structure of a preferred photoelectric conversion element of the present invention.

FIG. 7 is a partial sectional view showing the structure of a preferred photoelectric conversion element of the present invention.

FIG. 8 is a partial sectional view showing the structure of a preferred photoelectric conversion element of the present invention.

FIG. 9 is a partial sectional view showing the structure of a preferred photoelectric conversion element of the present invention.

FIG. 10 is a partial cross-sectional view illustrating an example of the structure of a substrate-integrated solar cell module using the metal complex dye of the present invention.

[Explanation of symbols]

 10 conductive layer 10a transparent conductive layer 11 metal lead 20 photosensitive layer 21 semiconductor fine particles 22 metal complex dye 23 charge transport material 30 charge Moving layer 40: Counter conductive layer 40a: Transparent counter conductive layer 50: Substrate 50a: Transparent substrate 60: Undercoat layer 70: Anti-reflection layer

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[Procedure amendment]

[Submission date] May 26, 2000 (2005.2.
6)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 1

[Correction method] Change

[Correction contents]

Embedded image (However, L is a single bond, an oxygen atom, a sulfur atom, an alkenylene group, an alkynylene group, an arylene group or a divalent compound.
It represents a heterocyclic group, each R ₁ is independently a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group, represents a phosphoryl group or a phosphonyl group, R ₂ each independently represents a substituent, a1 and a2 respectively Each independently represents an integer of 0 to 4; when a1 is 2 or more, R ₁ may be the same or different; when a2 is 2 or more, R ₂ may be the same or different; And n represents an integer of 0 to 2, and R ₁ and R ₂ may be bonded to any position of the bipyridine ring. LL ₁ and LL ₂ each independently represent the following general formula (III):

Embedded image (However, Za, Zb and Zc are each independently 5 or 6
Represents a group of non-metallic atoms capable of forming a membered ring, and c is 0 or 1
Represents bidentate or tridentate ligand represented by the representative), X _1, X ₂ each independently an acyloxy group, an acylthio group, thio acyl group, Chioashiruchio group, acylamino group, thiocarbamate group, Dithiocarbamate group, thiocarbonate group, dithiocarbonate group, trithiocarbonate group, acyl group, thiocyanate group,
Monodentate or bidentate ligand coordinated by a group selected from the group consisting of isothiocyanate group, cyanate group, isocyanate group, cyano group, alkylthio group, arylthio group, alkoxy group and aryloxy group, or halogen atom , Carbonyl, dialkyl ketone, 1,3-diketone, carbonamide, thiocarbonamide, represents a monodentate or bidentate ligand consisting of thiourea, m1 and m3 are each independently an integer of 0 to 2, m2 and m4 each independently represents an integer of 0 to 4, when m2 or m4 is 2 or more, X ₁ or X ₂ is not may be the same or different, respectively, also has X ₁ or between X ₂ together linked CI refers to a counter ion when a counter ion is required to neutralize the charge.) And a photoelectric conversion element.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] Claim 10

[Correction method] Change

[Correction contents]

Embedded image (However, L is a single bond, an oxygen atom, a sulfur atom, an alkenylene group, an alkynylene group, an arylene group or a divalent compound.
It represents a heterocyclic group, each R ₁ is independently a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group, represents a phosphoryl group or a phosphonyl group, each R ₂ is independently an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl Alkyl group, aryl group, heterocyclic group,
An alkoxy group, an aryloxy group, an alkoxycarbonyl group, an amino group, an acyl group, a sulfonamide group, an acyloxy group, a carbamoyl group, an acylamino group, a cyano group, or a halogen atom; a1 and a2 each independently represent 0 to 4; Represents an integer, when a1 is 2 or more, R ₁ may be the same or different, and when a2 is 2 or more, R ₂ may be the same or different, or may be connected to each other to form a ring , R ₁ and R ₂ may be bonded to any position of the bipyridine ring), and LL ₁ and LL ₂ each represent a ligand having two or more bidentate coordination parts Independently, the following general formulas (V-1) to (V-
8):

Embedded image (However, R _{11 to} R ₁₈ each independently represent a carboxyl group,
Represents a sulfonic acid group, a hydroxyl group, a hydroxamic acid group, a phosphoryl group or a phosphonyl group, and R _{19 to} R ₂₆ each independently represent an alkyl group, an alkenyl group,
Alkynyl group, cycloalkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkoxycarbonyl group, amino group, acyl group, sulfonamide group, acyloxy group, carbamoyl group, acylamino group, cyano group, or halogen atom Wherein R _{27 to} R ₃₁ each independently represent hydrogen, an alkyl group, an alkenyl group or an aryl group; R _{11 to} R ₂₆ may be bonded at any position on the ring; d 1 to d 8, d 13, d14 and d16 each independently represent an integer of 0 to 4, it represents an integer of d9~d12 and d15 each independently 0-6, the R ₁₁ to R ₁₈ when d1~d8 is 2 or more the same or different from each other at best, D9～d16 is the R ₁₉ to R ₂₆ when two or more may be the same or different, linked to may form a ring) by coordination of bidentate or tridentate represented together X ₁ , X ₂ are each independently an acyloxy group, an acylthio group, a thioacyloxy group, a thioacylthio group, an acylaminooxy group, a thiocarbamate group, a dithiocarbamate group, a thiocarbonate group, a dithiocarbonate group, a trithiocarbonate group, an acyl group Group, thiocyanate group,
Monodentate or bidentate ligand coordinated by a group selected from the group consisting of isothiocyanate group, cyanate group, isocyanate group, cyano group, alkylthio group, arylthio group, alkoxy group and aryloxy group, or halogen atom , Carbonyl, dialkyl ketone, 1,3-diketone, carbonamide, thiocarbonamide, thiourea represents a monodentate or bidentate ligand, m1 and m3 are each independently an integer of 0 to 1, m2 and m4 each independently represent a 1-4 integer, when m2 or m4 is 2 or more, X ₁ or X ₂ is not may be the same or different, respectively, also has X ₁ or between X ₂ together linked CI represents a counter ion when a counter ion is required to neutralize the charge).

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction contents]

That is, the photoelectric conversion element of the present invention has the following general formula (I): (LL ₁ ) _m1 (X ₁ ) _m2 M ₁ (BL) M ₂ (LL ₂ ) _m3 (X ₂ ) _m4 · CI ·· (I) (where M ₁ and M ₂ each independently represent a metal atom, and BL represents the following general formula (II):

Embedded image (However, L is a single bond, an oxygen atom, a sulfur atom, an alkenylene group, an alkynylene group, an arylene group or a divalent compound.
Represents a cyclic group , R ₁ each independently represents a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group, a phosphoryl group or a phosphonyl group, R ₂ each independently represents a substituent, a1 and a2 each represent independently represent an integer of 0 to 4, a1 is 2 or more when R ₁ may be the same or different, a2 is 2 or more when R ₂ may be the same or different and bonded to each other ring Where n is 0
And R ₁ and R ₂ may be bonded to any position of the bipyridine ring), and represents a ligand having two or more bidentate coordination parts, LL ₁ and LL ₂ are each independently the following general formula (III):

Embedded image (However, Za, Zb and Zc are each independently 5 or 6
Represents a group of non-metal atoms capable of forming a membered ring, c represents 0 or 1), represents a bidentate or tridentate ligand represented by X ₁ and X ₂ each independently represents an acyloxy group, Acylthio group, thioacyloxy group, thioacylthio group, acylaminooxy group, thiocarbamate group, dithiocarbamate group, thiocarbonate group, dithiocarbonate group, trithiocarbonate group, acyl group, thiocyanate group, isothiocyanate group, cyanate Group, isocyanate group, cyano group, alkylthio group, arylthio group, alkoxy group and aryloxy group, a monodentate or bidentate ligand coordinated with a group selected from the group consisting of a halogen atom, carbonyl, dialkyl ketone , 1,
Represents a monodentate or bidentate ligand consisting of 3-diketone, carbonamide, thiocarbonamide, and thiourea, m1 and m3 are each independently an integer of 0 to 2, m2 and m4
Each independently represents an integer of 0 to 4, and m2 or m4 is 2
When the above, X ₁ or X ₂ may be the same or different and each also may be linked is X ₁ or between X ₂ together, CI if necessary counterions to neutralize the charge Of the semiconductor complex sensitized by a metal complex dye represented by the following formula:

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction contents]

(1) L in the general formula (II) is preferably any one of a single bond, an alkenylene group, an alkynylene group and a divalent heterocyclic group. It is preferably any one of a, 5-thienylene group.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0029

[Correction method] Change

[Correction contents]

In the general formula (II), L is a single bond, an oxygen atom,
Sulfur atom, alkenylene group (preferably having 2 to 2 carbon atoms)
20, for example, an ethenylene group, a butadienylene group), an alkynylene group (preferably having 2 to 20 carbon atoms, for example, an ethynylene group, butadiynylene group), an arylene group (preferably having 6 to 26 carbon atoms, for example, a 1,4-phenylene group, 1,2-phenylene group, 1,3-phenylene group, 1,4-naphthylene group, 2,
5-dimethoxy-1,4-phenylene group, 4,4'-biphenylene group), divalent heterocyclic group (preferably having 1 to 26 carbon atoms,
For example, a 2,5-pyridylene group, a 2,5-thienylene group, a 2,5-furanylene group, a 2,5-pyrrolylene group, a 2,5-benzothienylene group), more preferably a single bond, an alkenylene group, or an alkynylene And a divalent heterocyclic group, more preferably an ethenylene group, an ethynylene group, a butadiynylene group, or a 2,5-thienylene group.

Claims (11)

[Claims] [Claim 1] the following general formula _{(I): (LL 1)} m1 (X 1) m2 M 1 (BL) M 2 (LL 2) m3 (X 2) m4 · CI ··· (I) ( However, M ₁ and M ₂ each independently represent a metal atom, and BL represents the following general formula (II): (Where L represents a single bond, an oxygen atom, a sulfur atom, an alkenylene group, an alkynylene group, an arylene group or a heterorylene group, and R ₁ each independently represents a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group, a phosphoryl group. or an phosphonyl group, R ₂ each independently represents a substituent, a1 and a2 each independently represents an integer of 0 to 4, R ₁ when a1 is 2 or more may be the same or different, a2 Is 2 or more, R ₂ may be the same or different, and may be linked to each other to form a ring;
Represents an integer of 2 to 2, and R ₁ and R ₂ may be bonded to any position of the bipyridine ring), and represents a ligand having two or more bidentate coordination parts; ₁ and LL ₂ are each independently represented by the following general formula (III): (However, Za, Zb and Zc are each independently 5 or 6
Represents a group of non-metallic atoms capable of forming a membered ring, and c is 0 or 1
Represents a bidentate or tridentate ligand represented by X ₁ and X ₂ each independently represents an acyloxy group, an acylthio group, a thioacyloxy group, a thioacylthio group, an acylaminooxy group, a thiocarbamate group, Dithiocarbamate group, thiocarbonate group, dithiocarbonate group,
Trithiocarbonate group, acyl group, thiocyanate group, isothiocyanate group, cyanate group, isocyanate group, cyano group, alkylthio group, arylthio group,
A monodentate or bidentate ligand coordinated with a group selected from the group consisting of an alkoxy group and an aryloxy group, or a halogen atom, a carbonyl, a dialkyl ketone, a 1,3-diketone, a carbonamide, a thiocarbonamide, a thiocarbonamide Represents a monodentate or bidentate ligand composed of urea, m1 and m3 each independently represent an integer of 0 to 2, m2 and m4 each independently represent an integer of 0 to 4, and m2 or m4 represents 2 In the above case, X ₁ or X ₂ may be the same or different, and X ₁ or X ₂ may be linked to each other.CI is a case where a counter ion is required to neutralize the charge. A photoelectric conversion element comprising semiconductor fine particles sensitized by a metal complex dye represented by the following formula: 2. The photoelectric conversion device according to claim 1, wherein R ₂ is independently an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, A photoelectric conversion element, which represents an alkoxycarbonyl group, an amino group, an acyl group, a sulfonamide group, an acyloxy group, a carbamoyl group, an acylamino group, a cyano group, or a halogen atom. 3. The photoelectric conversion device according to claim 1, wherein M ₁ and M ₂ in the general formula (I) each independently represent R
A photoelectric conversion element characterized by being u, Fe, Os or Cu. 4. The photoelectric conversion device according to claim 3, wherein M ₁ and M ₂ in the general formula (I) are Ru. 5. The photoelectric conversion device according to claim 1, wherein BL in the general formula (I) is the following general formula (IV-1) or (IV-2): (However, L, R ₁ , R ₂ , a1 and a2 have the same meanings as in the general formula (II)). 6. The photoelectric conversion device according to claim 1, wherein LL ₁ and LL ₂ in the general formula (I) are each independently represented by the following general formulas (V-1) to (V-8) ): (However, R _{11 to} R ₁₈ each independently represent a carboxyl group,
Represents a sulfonic acid group, a hydroxyl group, a hydroxamic acid group, a phosphoryl group or a phosphonyl group, R _{19 to} R ₂₆ each independently represent a substituent, and R _{27 to} R ₃₁ each independently represent a hydrogen, an alkyl group, an alkenyl group or Represents an aryl group, R _{11 to} R ₂₆ may be bonded to any position on the ring,
d1 to d8, d13, d14 and d16 each independently represent an integer of 0 to 4, and d9 to d12 and d15 each independently represent 0 to 6
R ₁₉ when an integer, d1 to d8 is 2 or more when R ₁₁ to R ₁₈ may be the same or different, D9～d16 is 2 or more to R
₂₆ may be the same or different, and may be connected to each other to form a ring). 7. The photoelectric conversion device according to claim 6, wherein R _{19 to} R ₂₆ are each independently an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group, and an aryl group. A photoelectric conversion element, which represents an oxy group, an alkoxycarbonyl group, an amino group, an acyl group, a sulfonamide group, an acyloxy group, a carbamoyl group, an acylamino group, a cyano group, or a halogen atom. 8. The photoelectric conversion device according to claim 1, wherein said semiconductor fine particles are titanium oxide fine particles. 9. A photovoltaic cell using the photoelectric conversion element according to claim 1. [Claim 10] the following general formula _{(I): (LL 1)} m1 (X 1) m2 M 1 (BL) M 2 (LL 2) m3 (X 2) m4 · CI ··· (I) ( However, M ₁ and M ₂ represent Ru, and BL represents the following general formula (IV-
1) or (IV-2): (Where L represents a single bond, an oxygen atom, a sulfur atom, an alkenylene group, an alkynylene group, an arylene group or a heterorylene group, and R ₁ each independently represents a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group, a phosphoryl group. Or represents a phosphonyl group, R ₂ each independently an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an amino group,
Acyl group, a sulfonamido group, an acyloxy group, a carbamoyl group, an acylamino group, a cyano group or a halogen atom,, a1 and a2 each independently represents an integer of 0 to 4, R ₁ when a1 is 2 or more identical When a2 is 2 or more, R ₂ may be the same or different, and may be linked to each other to form a ring; R ₁ and R ₂
May be bonded to any position of the bipyridine ring)
Represents a ligand having two or more bidentate coordination moieties, and LL ₁ and LL ₂ are each independently the following general formulas (V-1) to (V-
8): embedded image (However, R _{11 to} R ₁₈ each independently represent a carboxyl group,
Represents a sulfonic acid group, a hydroxyl group, a hydroxamic acid group, a phosphoryl group or a phosphonyl group, and R _{19 to} R ₂₆ each independently represent an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group , Aryloxy group, alkoxycarbonyl group, amino group, acyl group, sulfonamide group, acyloxy group, carbamoyl group, acylamino group, cyano group,
Or represents a halogen atom, R _{27 to} R ₃₁ each independently represent hydrogen, an alkyl group, an alkenyl group or an aryl group, R _{11 to} R ₂₆ may be bonded to any position on the ring,
d1 to d8, d13, d14 and d16 each independently represent an integer of 0 to 4, and d9 to d12 and d15 each independently represent 0 to 6
R ₁₉ when an integer, d1 to d8 is 2 or more when R ₁₁ to R ₁₈ may be the same or different, D9～d16 is 2 or more to R
₂₆ may be the same or different, and may be linked to each other to form a ring), and X ₁ and X ₂ each independently represent an acyloxy group An acylthio group, a thioacyloxy group, a thioacylthio group, an acylaminooxy group, a thiocarbamate group, a dithiocarbamate group, a thiocarbonate group, a dithiocarbonate group, a trithiocarbonate group, an acyl group, a thiocyanate group, an isothiocyanate group, Cyanate group,
A monodentate or bidentate ligand coordinated with a group selected from the group consisting of an isocyanate group, a cyano group, an alkylthio group, an arylthio group, an alkoxy group and an aryloxy group, or a halogen atom, carbonyl, dialkyl ketone, Represents a monodentate or bidentate ligand consisting of 1,3-diketone, carbonamide, thiocarbonamide, and thiourea, m1 and m3 are each independently an integer of 0 to 1, m2 and m4 are each independently 1 represents to 4 integer, when m2 or m4 is 2 or more, X ₁ or X ₂ may be the same or different and each also may be linked is X ₁ or between X ₂ together, CI charge Represents a counter ion when a counter ion is required to neutralize the compound. 11. The complex dye according to claim 10, wherein m1 and m3 are 1, and m2 and m4 are independently 1 or 2.
A metal complex dye characterized by the following.