JP2001035550A - Electrolyte composition, photoelectric conversion element and photo-electrochemical battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide superior durability and charge transport performance by including a cross-linked polymer obtained by reacting a nitrogen-containing polymer compound with a compound having a specified structure. SOLUTION: This electrolyte composition comprises a cross-linked polymer obtained by the reaction of an electrophilic agent represented by formula I (X represents a desorption group, Q represents an allylene group or the like, Y represents an s-valent connecting group, and (s) represents an integer of 2 to 4) with a nitrogen-containing polymer compound. In the electrophilic agent, Y is preferably a phenylene group, when X is a halogen atom or the like, and Q is an arylene group, preferably, in the electrophilic agent, and an alkylene group when (s) is 2. The nitrogen-containing polymer compound preferably has a repeat unit represented by formula II. In the formula, R1 represents H or the like, L represents a 2-valent connecting group, Z represents a nitrogenous heterocyclic group, E represents a repeat unit derived from a compound having an ethylenic unsaturated group, (t) represents 0-1, (x) represents 5-100 wt.%, and (y) represents 0-95 wt.%. The electrophilic agent is desirably set to 5-200 mol% with respect to the reactive nitrogen atom of the nitrogen-containing polymer compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolyte composition having excellent durability and charge transport ability, a photoelectric conversion element exhibiting excellent durability and photoelectric conversion characteristics due to the use of the electrolyte composition, and a photoelectric conversion element having the same. The present invention relates to a photoelectrochemical cell including a conversion element.

[0002]

2. Description of the Related Art Conventionally, liquid electrolytes have been used as electrolytes for electrochemical devices such as batteries, capacitors, sensors, display devices, and recording devices. However, an electrochemical device using a liquid electrolyte is unreliable because a liquid leak may occur during long-term use or storage.

For example, Nature, Vol. 353, pp. 737-740, 1
In 991, U.S. Pat.No. 4,492,721 and the like disclose a photoelectric conversion element using semiconductor fine particles sensitized by a dye and a photoelectrochemical cell using the same, but also use a liquid electrolyte for the charge transfer layer in these. Therefore, there is a concern that the electrolyte solution may leak or be depleted during long-term use or storage, resulting in a significant decrease in photoelectric conversion efficiency or a failure to function as an element.

[0004] Under such circumstances, International Publication No. 93/20565 proposed a photoelectric conversion element using a solid electrolyte. Also, The Chemical Society of Japan, 7, 484 pages (1997), JP-A-7-2881142
No., Solid State Ionics, 89, 263 (1986) and Japanese Patent Application Laid-Open No. 9-27352 have proposed a photoelectric conversion device solidified using a crosslinked polyethylene oxide-based polymer solid electrolyte. However, photoelectric conversion elements using these solid electrolytes have insufficient photoelectric conversion characteristics, particularly short-circuit current density, and also have insufficient durability and large deterioration in characteristics over time.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an electrolyte composition having excellent durability and charge transport ability, and a photoelectric conversion exhibiting excellent durability and photoelectric conversion characteristics due to the use of this electrolyte composition. It is an object of the present invention to provide an element and a photoelectrochemical cell comprising such a photoelectric conversion element.

[0006]

Means for Solving the Problems As a result of intensive studies in view of the above object, the present inventor has found that the following general formula (1):

Embedded image (Where X represents a leaving group, Q represents an arylene group or a divalent linking group having a hetero atom, Y represents a s-valent linking group, and s represents an integer of 2 to 4). The present inventors have discovered that an electrolyte composition containing a crosslinked polymer obtained by reacting a nitrogen-containing polymer compound with a compound represented by the formula exhibits excellent durability and charge transport ability, and have reached the present invention.

That is, the electrolyte composition of the present invention contains a crosslinked polymer obtained under mild conditions by reacting a nitrogen-containing polymer compound with a highly reactive electrophile having a specific structure. Features. By using this electrolyte composition, it is possible to obtain a photoelectric conversion element and a photoelectrochemical cell which are excellent in photoelectric conversion characteristics and have little deterioration in characteristics with time.

The photoelectric conversion device of the present invention has a conductive layer, a photosensitive layer, a charge transfer layer and a counter electrode, wherein the charge transfer layer contains the above-mentioned electrolyte composition.

Further, a photoelectrochemical cell of the present invention is characterized by comprising the above-mentioned photoelectric conversion element.

According to the present invention, when the following conditions are satisfied, an electrolyte composition, a photoelectric conversion element and a photoelectrochemical cell having more excellent photoelectric conversion characteristics and durability can be obtained. (1) The nitrogen-containing polymer compound has the following general formula (2):

Embedded image (However, R ₁ represents a hydrogen atom or an alkyl group, L represents a divalent linking group, Z represents a nitrogen-containing heterocyclic group, and E is a repeating unit derived from a compound having an ethylenically unsaturated group. And t is 0 or 1, x and y represent the weight composition ratio of the repeating unit, x is 5 to 100% by weight, and y is 0
~ 95% by weight. )). (2) The conjugate acid of the anion formed by elimination of X has a pKa of 10
It is preferred that: (3) X is preferably a halogen atom, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkylsulfonyloxy group or an arylsulfonyloxy group. (4) Q is -CO -, - COO -, - SO -, - SO 2 - or is preferably a phenylene group. (5) Z is preferably a pyridyl group or an imidazolyl group. (6) The photosensitive layer preferably contains a fine particle semiconductor sensitized by a dye. (7) The fine particle semiconductor is preferably a titanium dioxide fine particle semiconductor.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The photoelectric conversion element and the photoelectrochemical cell of the present invention provide a crosslinked polymer obtained by reacting an electrophile with a pendant nitrogen-containing polymer having a nitrogen-containing heterocyclic group in a side chain. It is characterized by using an electrolyte composition containing a coalescence. As a result, a photoelectric conversion element and a photoelectrochemical cell having excellent photoelectric conversion characteristics and preventing deterioration of the characteristics over time can be obtained.

[1] Electrolyte Composition The electrolyte composition of the present invention contains a crosslinked polymer obtained by reacting (A) an electrophile with (B) a nitrogen-containing polymer compound. Hereinafter, these compounds and reaction conditions will be described in detail.

(A) Electrophile The electrophile in the present invention is a compound having a leaving group capable of electrophilic reaction with a nitrogen atom of a nitrogen-containing polymer compound, and particularly having the following general formula (1):

Embedded image Is a compound having high activity represented by

In the general formula (1), X represents a leaving group. The conjugate acid of the anion formed by leaving the leaving group has a pKa of 10
It is preferably at most 5, more preferably at most 5. Preferred X includes a halogen atom, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, and the like. As the halogen atom, an iodine atom, a bromine atom and a chlorine atom are preferable, and an iodine atom and a bromine atom are more preferable. As the alkylcarbonyloxy group, an acetoxy group, a chloroacetyloxy group, a trichloroacetyloxy group, and a perfluoroacyloxy group (such as a trifluoroacetyloxy group) are preferable.
As the arylcarbonyloxy group, a benzoyloxy group, a chlorobenzoyloxy group, a fluorobenzoyloxy group and a p-nitrobenzoyloxy group are preferable. As the alkylsulfonyloxy group, a methylsulfonyloxy group, a chloromethylsulfonyloxy group, and a perfluoroalkylsulfonyloxy group (such as a trifluoromethylsulfonyloxy group) are preferable. As the arylsulfonyloxy group, a benzenesulfonyloxy group, a p-toluenesulfonyloxy group, a p-chlorobenzenesulfonyloxy group and a p-nitrobenzenesulfonyloxy group are preferable.

Q represents an arylene group or a divalent linking group having a hetero atom. These groups may have a substituent. Examples of the substituent include an alkyl group (eg, a methyl group and an ethyl group), a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), and a carboxy group. , A sulfo group, an alkoxycarbonyl group, an acyl group, a nitro group, a formyl group, an alkylsulfonyl group, an arylsulfonyl group, and the like.

When Q is an arylene group, the arylene group is preferably unsubstituted, and is preferably a phenylene group or a naphthylene group. When Q is a divalent linking group having a hetero atom, it is preferably an electron-withdrawing linking group, -CO -, - COO -, - SO- or -SO ₂ - and more preferably.

Y represents an s-valent linking group, and s represents an integer of 2 to 4. When s is 2, Y is an alkylene group, an arylene group, or these with -CO, -, - SO -, - SO 2 -, - O -, - NR- (R
Is a hydrogen atom or an alkyl group) and at least one linking group selected from the group consisting of -S-. In particular,-(CH ₂ ) _k- (k
Represents an integer of _{2~10), - CH 2 OCH 2} -, - (CH 2 CH 2 O) m CH 2 C
H ₂ -,-(C ₃ H ₆ O) _m C ₃ H _6- (m represents an integer of 1 to 30),

Embedded image

Embedded image Is more preferable. These linking groups may have a substituent, and preferably have 1 to 16 carbon atoms.

Examples of the substituents on the linking group Y include an alkyl group (methyl group, ethyl group, etc.), an aryl group (phenyl group, naphthyl group, etc.), a halogen atom (fluorine atom,
Chlorine, bromine, iodine, etc., hydroxyl, carboxy, sulfo, acylamino (acetamido,
Benzamide group), sulfonamide group, carbamoyl group, acyloxy group, alkoxycarbonyl group, acyl group, alkoxy group (methoxy group, ethoxy group, methoxyethoxy group, etc.), aryloxy group (phenoxy group, etc.), nitro group, formyl Group, alkylsulfonyl group,
An arylsulfonyl group, an amino group, an aryl group and the like can be mentioned.

When s is 3, Y is the following general formula (3):

Embedded image Is preferably represented by

In the general formula (3), B ₁ is

Embedded image (Wherein, R ₅ represents. A hydrogen atom or an alkyl group or an alkoxy group having 1 to 8 carbon atoms,) represents either.

In the general formula (3), L ₁ , L ₂ and L ₃ each independently represent a divalent linking group, and a preferred embodiment is the same as the linking group Y when s is 2. It may be different. a, b and c are each independently 0 or 1.

When s is 3, Y is

[Formula 10] Alternatively, these and the preferred divalent linking group Y when s is 2
And more preferably a trivalent linking group formed by combining These linking groups may have a substituent, and examples of the substituent include the substituents that Y described above when s is 2 may have.

When s is 4, Y is the following general formula (4):

[Formula 11] Is preferably represented by

In the general formula (4), B ₂ is

Embedded image L ₄ , L ₅ , L ₆ and L ₇ each independently represent a divalent linking group, and a preferred embodiment is the same as the linking group Y when s is 2, and is the same or different May be. e, f, g and h are each independently 0 or 1.

When s is 4, Y is

Embedded image Alternatively, these and the preferred divalent linking group Y when s is 2
And more preferably a tetravalent linking group formed by combining These linking groups may have a substituent, and examples of the substituent include the substituents that Y described above when s is 2 may have.

-CH ₂ sandwiched between X and Q in the general formula (1)
-The group may have a substituent. Examples of the substituent include the substituents that Y described above when s is 2 may have.

The electrophile is preferably used in an amount of 5 to 200 mol%, more preferably 5 to 150 mol%, particularly preferably 10 to 100 mol%, based on the reactive nitrogen atom in the nitrogen-containing polymer. preferable.

Hereinafter, specific examples 1-1 to 1-36 of the compound represented by the general formula (1) will be shown, but the present invention is not limited thereto.

[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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(B) Nitrogen-Containing Polymer Compound The nitrogen-containing polymer compound used in the present invention is a pendant polymer compound having a nitrogen-containing heterocyclic group in a side chain and represented by the following general formula (2):

Embedded image (However, R ₁ represents a hydrogen atom or an alkyl group, L represents a divalent linking group, Z represents a nitrogen-containing heterocyclic group, and E is a repeating unit derived from a compound having an ethylenically unsaturated group. And t is 0 or 1, x and y represent the weight composition ratio of the repeating unit, x is 5 to 100% by weight, and y is 0
~ 95% by weight. )). The nitrogen atom of the nitrogen-containing heterocyclic group Z is alkylated or quaternized by an electrophile to form a crosslinked polymer.

R ₁ represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom or a methyl group.

The linking group L may be any divalent linking group having at least one atom selected from the group consisting of a carbon atom, an oxygen atom, a nitrogen atom and a sulfur atom.
OO-, -OCO-, -CONR- or -NRCO- (R represents a hydrogen atom or a lower alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), or 1 selected from these. The linking group is preferably a linking group formed by combining one or more groups with one or more groups selected from an alkylene group, an arylene group, and —O—. Here, the alkylene group or the arylene group includes a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like), a hydroxyl group, an amino group, a nitro group, a carboxy group, a carbamoyl group, a sulfonic acid group, a sulfonamide group, and an acyl group. Group (formyl group, acetyl group, etc.), acyloxy group, acylamino group (acetamide group, benzamide group, etc.), alkyl group, alkoxy group (methoxy group, ethoxy group, methoxyethoxy group, etc.), akoxycarbonyl group, alkylsulfonyl group ,
It may have a substituent such as an aryl group, an aryloxy group (such as a phenoxy group), or an arylsulfonyl group.

Among these, the linking group L is -COO-, -COO-
_{(CH 2 CH 2 O) n} - (n is from 1 to 30 _{integer), - COO- (C 3 H} 6 O) n - (n
Is an integer of _{1~30), - COO- (CH 2} ) n - (n is an integer of from 1 to _{10), - COO- (CH 2)} n -OCO- (n is an integer of from 1 to 10), - COO -
(CH ₂ ) _m -OCO- (CH ₂ ) _n- (m and n are integers from 1 to 10), -CO
O- (CH ₂ CH ₂ O) _n -CO- (n is an integer of 1 to 30), -COO- (CH ₂ CH
_{2 O) m -CO- (CH 2} ) n - (m is 1-30 of integral, n represents an integer of 1 to _{10), - COO- (C 3 H} 6 O) n -CO- (n is 1 to 30 integer), -COO-
_{(C 3 H 6 O) m} -CO- (CH 2) n - (m is 1-30 of integral, n represents an integer of 1 to 10), - CONH -, - CON (CH 3) -, - CONH- (CH ₂ ) _n- (n is 1 to
10), -CONH- (CH ₂ ) ₃ -O- (CH ₂ CH ₂ O) _n- (CH ₂ ) ₃ -NHCO-
(N is 1 to 30 _{integer), - CONH-C 3 H} 6 -O- (CH 2 CH 2 O) n -C 3 H 6 -
NHCO- (n 1 to 30 _{integer), - CONH-C 3 H} 6 -O- (C 3 H 6 O) n -C 3
H ₆ -NHCO- (n is an integer of 1 to 30), -COO- (CH ₂ ) _n -O-COO- (n
_{COO- (CH 2) n -NHCO- (} n is an integer of from 1 to 10), - - an integer of 1 to 10), is _{OCO -, - OCO- (CH 2} ) n - (n is an integer of from 1 to 10 ), -OC
_{OO- (CH 2) n - (} n is an integer of from 1 to _{10), - NHCO- (CH 2)} n - (n is an integer of from 1 to _{10), - NHCO- (CH 2)} n -CONH- (n is an integer of from 1 to _{10), - NHCO- (CH 2)} m -CONH- (CH 2) n - (m and n are 1 to 10
Is particularly preferable, or —NHCO—O— (CH ₂ ) _n —OCO— (n is an integer of 1 to 10).

The nitrogen-containing heterocyclic ring constituting the nitrogen-containing heterocyclic group Z may be an unsaturated ring or a saturated ring, and may have an atom other than a nitrogen atom. Examples of the unsaturated ring include a pyridine ring, an imidazole ring, a thiazole ring, an oxazole ring,
And a triazole ring. As a saturated ring,
Examples include a morpholine ring, a piperidine ring, and a piperazine ring. The nitrogen-containing heterocyclic ring is preferably an unsaturated ring, and more preferably a pyridine ring or an imidazole ring. These are preferably unsubstituted, but may be substituted with an alkyl group (such as a methyl group).

E represents a repeating unit derived from a compound having an ethylenically unsaturated group. Preferred examples of the compound having an ethylenically unsaturated group include acrylic acid and α-alkylacrylic acid (such as methacrylic acid). Or amides (N-isopropylacrylamide, Nn-butylacrylamide, Nt-
Butylacrylamide, N, N-dimethylacrylamide,
N-methylmethacrylamide, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, acrylamidopropyltrimethylammonium chloride, methacrylamide, diacetone acrylamide, N-methylolacrylamide, N-methylolmethacrylamide, methyl acrylate, ethyl acrylate, hydroxy Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, 2-hydroxypropyl acrylate,
2-methyl-2-nitropropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, t-pentyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-methoxyethoxyethyl acrylate, 2,2 , 2-trifluoroethyl acrylate, 2,2-dimethylbutyl acrylate,
3-methoxybutyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, n-pentyl acrylate, 3-pentyl acrylate, octafluoropentyl acrylate, n-hexyl acrylate,
Cyclohexyl acrylate, cyclopentyl acrylate, cetyl acrylate, benzyl acrylate, n-
Octyl acrylate, 2-ethylhexyl acrylate, 4-methyl-2-propylpentyl acrylate, heptadecafluorodecyl acrylate, n-octadecyl acrylate, methyl methacrylate, 2-methoxyethoxyethyl methacrylate, ethylene glycol ethyl carbonate methacrylate, 2,2,2 -Trifluoroethyl methacrylate, tetragluoropropyl methacrylate, hexafluoropropyl methacrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, t-pentyl methacrylate, 2-methoxyethyl methacrylate , 2-ethoxyethyl methacrylate, benzyl methacrylate, heptadecafluorodecyl methacrylate Rate, n- octadecyl methacrylate, 2-isobornyl methacrylate, 2-
Norbornyl methyl methacrylate, 5-norbornene-2
-Ylmethyl methacrylate, 3-methyl-2-norbornylmethyl methacrylate, dimethylaminoethyl methacrylate, etc.), vinyl esters (vinyl acetate, etc.), esters derived from maleic acid or fumaric acid (dimethyl maleate, maleic acid) Dibutyl, diethyl fumarate, etc.), maleic acid, fumaric acid, sodium salt of p-styrenesulfonic acid, acrylonitrile, methacrylonitrile, dienes (butadiene, cyclopentadiene, isoprene, etc.), aromatic vinyl compounds (styrene, p- Chlorostyrene, t-butylstyrene, α-methylstyrene, sodium styrenesulfonate), N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, vinylsulfone Acid, vinyl sulfonic acid Beam, sodium allyl sulfonate, sodium methallyl sulfonate, vinylidene fluoride, vinylidene chloride, vinyl alkyl ethers (methyl vinyl ether), ethylene, propylene, 1-butene, isobutene, N- phenylmaleimide, and the like.

In the present invention, other than the above, compounds having an ethylenically unsaturated group described in Research Disclosure, No. 1995 (July 1980) can be used.

X and y are each independently a nitrogen-containing heterocyclic group
It represents the weight composition ratio of the repeating unit containing Z and the repeating unit E derived from the compound having an ethylenically unsaturated group, wherein x is preferably 5 to 100% by weight, and y is preferably 0 to 95% by weight. More preferably, x is 10 to 95% by weight and y is 5% by weight.
~ 90% by weight. The repeating unit containing Z and the repeating unit E may be used in combination of two or more.

The weight average molecular weight of the nitrogen-containing polymer compound is preferably 1,000 to 100,000. More preferably, it is 2000 to 100,000.

Preferred specific examples 2-1 to 2-52 of the nitrogen-containing polymer compound represented by the general formula (2) are shown below, but the invention is not limited thereto.

[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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The nitrogen-containing polymer compound of the present invention is disclosed in "Experimental Method for Polymer Synthesis" by Takayuki Otsu and Masayoshi Kinoshita (Chemical Doujin)
Takayuki Yasu "Course polymerization reaction theory 1 radical polymerization (1)"
It can be synthesized by radical polymerization which is a general polymer synthesis method described in (Chemical Doujin). The nitrogen-containing polymer compound can be subjected to radical polymerization by heating, light or electron beam, or electrochemically, but it is particularly preferable to perform radical polymerization by heating, and in this case, a polymerization initiator preferably used is 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2-azobis (2-methylpropionate), dimethyl 2,2-azobisisobuty Azo initiators such as acrylates, peroxide initiators such as lauryl peroxide, benzoyl peroxide, and t-butyl peroctoate.

(C) Crosslinking Reaction The crosslinked polymer used in the electrolyte composition of the present invention is obtained by a crosslinking reaction between a nitrogen atom of a nitrogen-containing polymer compound and an electrophile. The cross-linking reaction is preferably performed in a state where a salt coexists in addition to the nitrogen-containing polymer compound and the electrophile. In the electrolyte composition of the present invention, a salt is essential as an electrolyte. A salt can be added after crosslinking, but this is not preferred because it becomes difficult to uniformly disperse the salt in the crosslinked polymer.

As the reaction solution, (i) a solution containing a nitrogen-containing polymer compound, an electrophile and a salt dissolved in a solvent, or (ii) monomers constituting the nitrogen-containing polymer compound,
A solution in which a polymerization initiator, an electrophile, and a salt are dissolved in a solvent can be used, but (i) is preferably used.

The salts include (a) I ₂ and iodide (LiI, Na
A metal iodide such as I, KI, CsI, CaI ₂ or an iodine salt of a quaternary ammonium compound such as tetraalkylammonium iodide, pyridinium iodide, imidazolium iodide, etc.), and (b) Br ₂ Bromides (metal bromides such as LiBr, NaBr, KBr, CsBr, and CaBr ₂ or bromide salts of quaternary ammonium compounds such as tetraalkylammonium bromide and pyridinium bromide)
(C) metal complexes such as ferrocyanate-ferricyanate and ferrocene-ferricinium ions; (d) sulfur compounds such as sodium polysulfide and alkylthiol-alkyl disulfide; (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 salts may be used as a mixture.

EP 718288, WO 95/18456, J. Electroch
em. Soc., Vol. 143, No. 10, 3099 (1996), Inorg. Che
m., 35, 1168-1178 (1996), a salt in a molten state at room temperature (hereinafter, referred to as a room temperature molten salt) can also be used. When a room temperature molten salt is used as an electrolyte, a solvent may not be used. As the room temperature molten salt used in the electrolyte of the present invention, for example, WO95 / 18456, JP-A-8-259543
, Electrochemistry, Vol. 65, No. 11, p. 923 (1997) and the like can be used, such as pyridinium salts, imidazolium salts, and triazonium salts.

The room temperature molten salt used in the present invention includes the following general formulas (Ya), (Yb) and (Yc):

Embedded image And the like represented by any of the above are preferred.

In the general formula (Ya), Q _y1 represents an atomic group capable of forming a 5- or 6-membered aromatic cation together with a nitrogen atom, and R _y1 represents a substituted or unsubstituted alkyl group or alkenyl group.

The constituent atoms of the atomic group Q _y1 are preferably selected from a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom and a sulfur atom. The 6-membered ring formed by Q _y1 is preferably a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring or a triazine ring, and more preferably a pyridine ring. The 5-membered ring formed by Q _y1 is preferably an oxazole ring, a thiazole ring, an imidazole ring, a pyrazole ring, an isoxazole ring, a thiadiazole ring, an oxadiazole ring or a triazole ring,
It is more preferably an oxazole ring, a thiazole ring or an imidazole ring, and particularly preferably an oxazole ring or an imidazole ring.

In the general formula (Yb), A _y1 represents a nitrogen atom or a phosphorus atom, and R _y2 , R _y3 , R _y4 and R _y5 each independently represent a substituted or unsubstituted alkyl group or alkenyl group. However, three or more of R _y2 , R _y3 , R _y4 and R _y5 are not simultaneously aryl groups. Also, R _y2 ,
Two or more of R _y3 , R _y4 and R _y5 are connected to each other to form A _{y 1}
May form a non-aromatic ring containing

In the general formula (Yc), R _y6 , R _y7 , R _y8 , R _y9 , R
_y10 and _Ry11 each independently represent a substituted or unsubstituted alkyl group or alkenyl group, and two or more of them may be linked to each other to form a ring structure.

Formulas (Y-a), (Y-b) and (Y-c)
The compound represented by any of Q _y1Or R_y1~ R_y11
May form a multimer.

In the general formulas (Ya), (Yb) and (Yc), R _{y1 to} R _y11 represent a substituted or unsubstituted alkyl group (preferably having 1 to 24 carbon atoms and having a branched or branched chain structure). Or may be cyclic, such as a methyl group,
Ethyl, propyl, butyl, isopropyl, pentyl, hexyl, octyl, 2-ethylhexyl, t-octyl, decyl, dodecyl, tetradecyl, 2-hexyldecyl, octadecyl, cyclohexyl A cyclopentyl group) or a substituted or unsubstituted alkenyl group (preferably having 2 to 24 carbon atoms, which may be linear or branched, for example, a vinyl group or an allyl group). Represents an alkyl group having 3 to 18 carbon atoms or an alkenyl group having 2 to 18 carbon atoms, more preferably an alkyl group having 4 to 6 carbon atoms.

In formulas (Ya), (Yb) and (Yc), Q _y1 and R _{y1 to} R _y11 may have a substituent. Examples of a preferable substituent include a halogen atom (a fluorine atom , Chlorine, bromine, iodine, etc.), cyano,
Alkoxy group (methoxy group, ethoxy group, methoxyethoxy group, etc.), aryloxy group (phenoxy group, etc.), alkylthio group (methylthio group, ethylthio group, etc.), acyl group (acetyl group, propionyl group, benzoyl group, etc.),
Sulfonyl group (methanesulfonyl group, benzenesulfonyl group, etc.), acyloxy group (acetoxy group, benzoyloxy group, etc.), sulfonyloxy group (methanesulfonyloxy group, toluenesulfonyloxy group, etc.), phosphonyl group (diethylphosphonyl group, etc.) ), Amide group (acetylamino group, benzoylamide group, etc.), carbamoyl group (N, N-dimethylcarbamoyl group, N-phenylcarbamoyl group, etc.), alkyl group (methyl group, ethyl group, propyl group, isopropyl group, cycloalkyl group) Propyl, butyl, 2-
Carboxyethyl group, benzyl group, etc., aryl group (phenyl group, toluyl group, etc.), heterocyclic group (pyridyl group, imidazolyl group, furanyl group, etc.), alkenyl group (vinyl group, 1-propenyl group, etc.) and the like. Can be

These room temperature molten salts may be used alone or
May be used in combination.^-
Used in combination with a salt in which is replaced by another anion
Can also. I^-Halogenated as an anion to replace
Matter ion (Cl^-, Br^-Etc.), NCS^-, BF_Four ^-, PF₆ ^-, ClO_Four ^-,
(CF_ThreeSO_Two)_TwoN^-, (CF_ThreeCF_TwoSO_Two)_TwoN^-, CF_ThreeSO_Three ^-, CF_ThreeCOO^-, Ph _Four
B^-And the like are preferred examples. More preferably,
Halide ion, (CF_ThreeSO_Two)_TwoN^-Or BF_Four ^-It is.

When these room temperature molten salts are added to the electrolyte composition, it is preferable that the room temperature molten salt itself is an iodine salt, or that the above-mentioned iodine salt is added in addition to the room temperature molten salt. When the room temperature molten salt is added and the amount of the solvent is 10% or less,
The content of the iodine salt is preferably at least 10% by weight, more preferably at least 50% by weight, based on the whole electrolyte composition.

When iodine is added to the electrolyte composition containing the molten salt at room temperature, the preferred amount of iodine is 0.1 to 2
0% by weight, more preferably 0.5 to 5% by weight.

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

As the solvent, a compound that can exhibit excellent ionic conductivity because it has low viscosity and high ion mobility, or has high dielectric constant and increases the effective carrier concentration, or both. 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, crotlactone, γ-caprolactone, δ-valerolactone and the like are preferable.

(C) Ethers 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 are preferable.

(D) Alcohols For example, methanol, ethanol, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, polyethylene glycol monoalkyl ether, and polypropylene glycol monoalkyl ether are preferred.

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

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

(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.

The concentration of the nitrogen-containing polymer compound in the reaction solution was 100% by weight of [solvent + nitrogen-containing polymer compound + salt].
Is preferably 1 to 80% by weight, and 3 to 70% by weight.
Is more preferred. If the content of the nitrogen-containing polymer compound is less than 1% by weight, the strength becomes insufficient, and if it exceeds 80% by weight, the mobility of the carrier is undesirably reduced. The nitrogen-containing polymer compound may be used alone or in combination of two or more.

The concentration of the electrophile in the reaction solution is preferably set so that the molar ratio of the electrophilic site to the number of moles of the reactive nitrogen atom of the nitrogen-containing polymer compound is 0.02 to 2, more preferably. Preferably it is 0.05-1.5. The electrophiles may be used alone or in combination of two or more.

The concentration of the salt in the reaction solution is 0.05 to 2 mol / L
And more preferably 0.1 to 1.5 mol / L. Further, iodine (bromine in the case of a bromine salt) may be added to the electrolyte composition of the present invention to previously generate a redox couple. In this case, the preferred concentration of iodine or bromine is 0.01 to 0.3 mol. / L.

The proportion of the crosslinked polymer in the electrolyte composition of the present invention is preferably from 2 to 80% by weight.

The electrolyte layer comprising the electrolyte composition of the present invention is formed by forming a reaction solution layer on the electrode by a casting method, a coating method, an immersion method, an impregnation method, a permeation method, etc., and then crosslinking by heating reaction. Can be manufactured.

[2] Photoelectric Conversion Element The photoelectric conversion element of the present invention has the above-mentioned electrolyte composition in the charge transfer layer. Preferably, as shown in FIG.
The conductive layer 10, the photosensitive layer 20, the charge transfer layer 30, and the counter electrode conductive layer 40 were stacked in this order, and the photosensitive layer 20 was filled in the gap between the semiconductor fine particles 21 sensitized by the dye 22 and the semiconductor fine particles 21. And an electrolyte 23. The electrolyte 23 is a charge transfer layer
It consists of the same components as the material used for 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”. A photoelectrochemical cell in which the photoelectric conversion element is connected to an external circuit to perform a work is provided. Note that the conductive layer 10, the counter electrode conductive layer 40, and the substrate 50 in FIG. 1 may be a transparent conductive layer 10a, a transparent counter electrode conductive layer 40a, and a transparent substrate 50a, respectively.

In the photoelectric conversion device of the present invention shown in FIG. 1, light incident on the photosensitive layer 20 containing the semiconductor fine particles 21 sensitized by the dye 22 excites the dye 22 and the like, and the excited dye
High-energy electrons in 22 and the like are transferred to the conduction band of the semiconductor fine particles 21 and further reach the conductive layer 10 by diffusion. At this time, molecules such as the dye 22 are oxidized. In a photoelectrochemical cell, the electrons in the conductive layer 10 work in an external circuit while passing through the counter electrode conductive layer 40 and the charge transfer layer 30 to the dye 22.
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, such as metal, and having conductivity is used.

In the case of (2), a substrate having a conductive layer containing a conductive agent on the photosensitive layer side can be used. Preferred conductive agents include metals (for example, platinum, gold, silver, copper, aluminum, rhodium, indium, etc.), carbon, and conductive metal oxides (indium-tin composite oxides, tin oxide doped with fluorine, etc.) and the like. Is mentioned. The thickness of the conductive layer is
It 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 polysterene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), polyarylate (PAr), polysulfone (PSF), polyester sulfone (PES) , Polyetherimide (PEI), cyclic polyolefin, brominated phenoxy and the like. 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 a dye, the semiconductor fine particles act as a so-called photoreceptor, absorb light to separate electric charges, and generate electrons and holes. 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 The 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 include titanium, tin, zinc, iron, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium or tantalum oxide, cadmium, zinc, lead and silver. , Antimony or bismuth sulfide, cadmium or lead selenide, cadmium telluride and the like. 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
Is Si, TiO_Two, SnO_Two, Fe_TwoO_Three, WO_Three, ZnO, Nb_TwoO_Five, CdS, Z
nS, PbS, Bi_TwoS_Three, CdSe, CdTe, GaP, InP, GaAs, CuIn
S_Two, CuInSe_TwoEtc., more preferably TiO_Two, ZnO, Sn
O_Two, Fe_TwoO_Three, WO_Three, Nb_TwoO_Five, CdS, PbS, CdSe, InP, GaAs,
CuInS_TwoOr CuInSe_TwoAnd particularly preferably TiO_TwoAlso
Is Nb _TwoO_FiveAnd most preferably TiO_TwoIt is.

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 Shizuo'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 De
Also preferred is a method developed by Gussa to produce oxides by high temperature hydrolysis of chlorides in oxyhydrogen salts.

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 preferable. 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.
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, besides the method of applying a dispersion or colloid solution of the semiconductor fine particles on the conductive support, the above-mentioned sol-gel 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 with 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.

The application method includes a roller method and a dipping method as an application system, an air knife method and a blade method as a metering system.
-4589, the wire bar method, US Patent 268
The slide hopper method, extrusion method, curtain method and the like described in Nos. 1294, 2761419 and 2761791 are preferred. 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 of semiconductor fine particles is greatly affected by the type and dispersibility of the semiconductor fine particles, the type of 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 used 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 photoelectrochemical cell, the thickness of the semiconductor fine particle layer is preferably 1 to 30 μm, and 2 to 25 μm.
Is more preferred. The coating amount of the semiconductor fine particles per m ² of the support 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 to 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) Dye The dye used in the photosensitive layer is preferably a metal complex dye, a phthalocyanine dye or a methine dye. Two or more dyes can be mixed in order to widen the wavelength range of photoelectric conversion as much as possible and to increase the conversion efficiency. The dyes to be mixed and their proportions can be selected so as to match the wavelength range and intensity distribution of the desired light source.

The dye preferably has a suitable interlocking group for the surface of the semiconductor fine particles. Preferred linking groups include COOH groups, SO ₃ H
Group, cyano group, -P (O) (OH) ₂ group, -OP (O) (OH) ₂ group, or π-conducting chelation such as oxime, dioxime, hydroxyquinoline, salicylate and α-ketoenolate Groups. Above all, COOH group, -P (O)
Particularly preferred are _two (OH) groups and _two -OP (O) (OH) groups. These groups may form a salt with an alkali metal or the like, or may form an inner salt. In the case of polymethine dye,
If the methine chain contains an acidic group as in the case of forming a squarylium ring or a croconium ring, this portion may be used as a bonding group.

Hereinafter, preferred dyes used in the photosensitive layer will be specifically described.

(A) Metal Complex Dye When the dye is a metal complex dye, the metal atom is ruthenium
Ru is preferred. Ruthenium complex dyes include:
For example, U.S. Pat.Nos. 4,492,721, 4,684,537, 5,084,365
No. 5,350,644, No. 5463057, No. 5,525,440, JP-A-7
-249790 and the like.

The ruthenium complex dye used in the present invention is preferably represented by the following general formula (I): (A ₁ ) _p Ru (Ba) (Bb) (Bc) (I) In the general formula (I), A ₁ is C
1, represents a ligand selected from the group consisting of SCN, H ₂ O, Br, I, CN, NCO and SeCN, and p is an integer of 0 to 2, preferably 2. Ba, Bb and Bc are each independently the following formulas B-1 to B-8:

Embedded image (However, R ₁₁ is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms,
Represents a substituted or unsubstituted aralkyl group of up to 12 or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms,
The alkyl part of the alkyl group and the aralkyl group may be linear or branched, and the aryl part of the aryl group and the aralkyl group may be monocyclic or polycyclic (condensed ring, ring assembly). ) Represents an organic ligand selected from the compounds represented by Ba, Bb and Bc may be the same or different.

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

[0124]

Embedded image

[0125]

Embedded image

[0126]

Embedded image

(B) Methine Dye The methine dye used in the photosensitive layer in the present invention is preferably a dye represented by the following formula (II), (III), (IV) or (V).

1. Dye represented by general formula (II)

Embedded image In the general formula (II), R ₂₁ and R ₂₅ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group;
_{22 to} R ₂₄ each independently represent a hydrogen atom or a substituent, R _{21 to} R ₂₅ may combine with each other to form a ring,
₁₁ and L ₁₂ each independently represent a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom, n1 and
n3 independently represents an integer of 0 to 2; n2 represents an integer of 1 to 6; The dye may have a counterion depending on the charge on the entire molecule.

The above alkyl group, aryl group and heterocyclic group may have a substituent. The alkyl group may be linear or branched, and the aryl group and the heterocyclic group may be monocyclic or polycyclic (condensed ring, ring assembly). The ring formed by R _{21 to} R ₂₅ may have a substituent, and may be a single ring or a condensed ring.

[0130] 2. Dye represented by general formula (III)

Embedded image In the general formula (III), Z _a represents a non-metallic atomic group necessary to form a nitrogen-containing heterocyclic ring, R ₃₁ represents an alkyl group or an aryl group. Q _a compound represented by the general formula (III) represents a methine group or polymethine group necessary to act as a methine dye may form multimers through Q _a. X ₃ represents a counter ion, n4 is an integer of 0.

[0131] nitrogen-containing heterocyclic ring formed by the Z _a may have a substituent, may be a condensed ring may be a single ring. The alkyl group and the aryl group may have a substituent, the alkyl group may be linear or branched,
The aryl group may be monocyclic or polycyclic (condensed ring, ring assembly).

Among the dyes represented by the general formula (III), the following general formulas (III-a) to (III-d):

Embedded image (However, R _{41 to} R ₄₅ , R _{51 to} R ₅₄ , R _{61 to} R ₆₃ , and R ₇₁
To R ₇₃ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and L ₂₁ , L ₂₂ , L ₃₁ , L ₃₂ , L ₄₁
~L ₄₅ and L ₅₁ ~L ₅₆ each independently represent an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, -CRR'- or -NR- (R
And R ′ represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and may be the same or different. ) Represents, L _{3 3} is ^{O -, S -, Se -} , Te - or -N ^- represents a R. Y ₁₁ , Y ₁₂ , Y ₂₁ , Y ₂₂ , Y ₃₁ and Y ₄₁ each independently represent a substituent, and n5, n6 and n7 each independently represent 1 to 1.
Represents an integer of 6. ) Are more preferred.

The compounds represented by the general formulas (III-a) to (III-d) may have a counter ion depending on the charge of the whole molecule, and may have the above-mentioned alkyl group, aryl group and heterocyclic group. May have a substituent, the alkyl group may be linear or branched, and the aryl group and the heterocyclic group may be monocyclic or polycyclic (condensed ring, ring assembly).

Specific examples of the above polymethine dyes include:
Organi by M. Okawara, T. Kitao, T. Hirasima, M. Matuoka
c It is described in detail in Colorants (Elsevier) and the like.

[0135] 3. Dye represented by general formula (IV)

Embedded image In the general formula (IV), Q _b represents an atomic group necessary for forming a nitrogen-containing heterocycle of 5 or 6-membered, Z _b is necessary atoms to form either a 3-9-membered ring Delegation, L ₆₁ , L
₆₂ , L ₆₃ , L ₆₄ and L ₆₅ each independently represent a methine group optionally having a substituent, n8 is an integer of 0 to 4, and n9
Is 0 or 1, R ₈₁ represents a substituent, and X ₄ represents a counter ion when a counter ion is required to neutralize the charge.

The ring formed by Q _b may be condensed, and may have a substituent. Preferred examples of the nitrogen-containing heterocycle include a benzothiazole ring, a benzoxazole ring, a benzoselenazole ring, a benzotellurazole ring, a 2-quinoline ring, a 4-quinoline ring, a benzimidazole ring, a thiazoline ring, an indolenine ring, and an oxalate. Diazole ring, thiazole ring, and imidazole ring, more preferably benzothiazole ring, benzoxazole ring, benzimidazole ring, benzoselenazole ring,
2-quinoline ring, 4-quinoline ring, indolenine ring,
Particularly preferred are a benzothiazole ring, a benzoxazole ring, a 2-quinoline ring, a 4-quinoline ring and an indolenine ring.

Examples of the substituent on the nitrogen-containing hetero ring include:
Carboxyl group, phosphonyl group, sulfonyl group, halogen atom (F, Cl, Br, I etc.), cyano group, alkoxy group (methoxy group, ethoxy group, methoxyethoxy group etc.),
Aryloxy group (phenoxy group etc.), alkyl group (methyl group, ethyl group, cyclopropyl group, cyclohexyl group, trifluoromethyl group, methoxyethyl group, allyl group, benzyl etc.), alkylthio group (methylthio group, ethylthio group And the like, an alkenyl group (vinyl group, 1-propenyl group, etc.), an aryl group, a heterocyclic group (phenyl group, thienyl group, toluyl group, chlorophenyl group, etc.).

Z _b is constituted by an atom selected from a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom and a hydrogen atom. The ring formed by Z _b is preferably a ring whose skeleton is formed by 4 to 6 carbons, and more preferably the following (A) to (E):

Embedded image And most preferably (a).

As the substituents that L ₆₁ , L ₆₂ , L ₆₃ , L ₆₄ and L ₆₅ each independently optionally have, a substituted or unsubstituted alkyl group (preferably having 1 to 12 carbon atoms, more preferably It has 1 to 7 atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, a 2-carboxyethyl group, a benzyl group, etc., a substituted or unsubstituted aryl group (preferably carbon It has 6, 8 to 10, more preferably 6 to 8 carbon atoms, such as phenyl, toluyl,
Chlorophenyl group, o-carboxyphenyl group, etc.), heterocyclic group (eg, pyridyl group, thienyl group, furanyl group, barbituric acid, etc.), halogen atom (eg, chlorine atom, bromine atom, etc.), alkoxy group (eg, methoxy group, An ethoxy group or the like), an amino group (preferably having 1 to 12 carbon atoms, more preferably having 6 to 12 carbon atoms, for example, a diphenylamino group, a methylphenylamino group, a 4-acetylpiperazin-1-yl group) Etc.), oxo group and the like. These substituents may combine with each other to form a ring such as a cyclopentene ring, a cyclohexene ring, or a squarylium ring, or may form a ring with an auxochrome. N8 is 0
And is an integer of 0 to 4, preferably 0 to 3. N9 is 0 or 1.

The substituent R ₈₁ is preferably an aromatic group (which may have a substituent) or an aliphatic group (which may have a substituent). The number of carbon atoms of the aromatic group is preferably 1 to 1
6, more preferably 5-6. The number of carbon atoms of the aliphatic group is preferably 1 to 10, more preferably 1 to 6.
Unsubstituted aliphatic and aromatic groups include a methyl group,
Examples include an ethyl group, an n-propyl group, an n-butyl group, a phenyl group, and a naphthyl group.

Whether the dye is a cation or an anion,
Alternatively whether with net ionic charge depends on its auxochrome and substituents, the charge of the whole molecule is a counter ion X ₄
Neutralized by Counterion X ₄ Typical cations are inorganic or organic ammonium ion (tetraalkylammonium ion, pyridinium ion, etc.) and and alkali metal ions, while the anions be either inorganic or organic anion Also, halide ion (fluoride ion, chloride ion, bromide ion, iodide ion, etc.), substituted arylsulfonate ion (p-toluenesulfonate ion, p-chlorobenzenesulfonate ion, etc.), aryldisulfonate ion (1,
3-benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion, etc.), alkyl sulfate ion (methyl sulfate ion, etc.), sulfate ion, thiocyanate ion, perchlorate ion, tetra Fluoroborate ion, picrate ion, acetate ion, trifluoromethanesulfonic acid ion and the like.

Further, as the charge-balancing counter ion, an ionic polymer or another dye having a charge opposite to that of the dye may be used, or a metal complex such as bisbenzene-1,2-dithiolatonickel (III) may be used. Ions may be used.

4. Dye represented by general formula (V)

Embedded image In the general formula (V), Q _c represents at least 4 or more functional aromatic group, L ₇₁ and L ₇₂ each independently represent a sulfur atom, a selenium atom or CRR '(wherein, R and R' are each independently hydrogen And may be the same or different, and may be the same or different, and are preferably each independently a sulfur atom or CRR ', more preferably CRR'. R ₉₁ and R ₉₂ each independently represent an alkyl group or an aromatic group, and Y ₅₁ and Y ₅₂
Each independently represents a nonmetallic atomic group necessary for forming a polymethine dye. X ₅ represents a counter ion.

[0144] Examples of the aromatic group Q _c, benzene, naphthalene, anthracene, those derived from an aromatic hydrocarbon phenanthrene or anthraquinone, carbazole, pyridine, quinoline, thiophene, furan, xanthene, etc. thianthrene Examples thereof include those derived from an aromatic hetero ring, and these may have a substituent other than the connecting portion. Q _c is preferably an aromatic hydrocarbon deriving group, more preferably a benzene or naphthalene deriving group.

[0145] It is also possible to form any methine dye by Y ₅₁ and Y _52, it is preferably exemplified cyanine dyes, merocyanine dyes, rhodacyanine dyes, trinuclear merocyanine dyes, allopolar dyes, hemicyanine dyes, styryl dyes and the like . Cyanine dyes include those in which the substituent on the methine chain forming the dye forms a squarium ring or a croconium ring. For details of these dyes, see "Heterocyclic Compounds-C" by FM Harmer.
yanine Dyes and Related Compounds, ”John Wiley &
Sons, New York, London, 1964, DMStur
`` Heterocyclic Compounds-Special Topics in He ''
terocyclic Chemistry ", Chapter 18, Section 14, pages 482 to 515 and the like. Cyanine dyes, merocyanine dyes and rhodacyanine dyes are described in U.S. Pat.
No., pages 21 to 22, (XI), (XII) and (XIII) are preferred. Also preferably it has a squarylium ring in at least one of the methine chain moiety of the polymethine dye formed by Y ₅₁ and Y _5, which has both are more preferred.

R ₉₁ and R ₉₂ are an aromatic group or an aliphatic group, and these may have a substituent. The number of carbon atoms in the aromatic group is preferably 5 to 16, more preferably 5 to 6
It is. The number of carbon atoms of the aliphatic group is preferably 1 to 10, more preferably 1 to 6. Examples of the unsubstituted aliphatic group and aromatic group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a phenyl group, and a naphthyl group.

It is preferred that at least one of R ₉₁ , R ₉₂ , Y ₅₁ and Y ₅₂ has an acidic group. Here, the acidic group is a substituent having a dissociable proton, and examples thereof include a carboxylic acid group, a phosphonic acid group, a sulfonic acid group, and a boric acid group, and a carboxylic acid group is preferable. Further, the proton on such an acidic group may be dissociated.

Specific examples (1) to (43) and S-1 to S-42 of the polymethine dyes represented by formulas (II) to (V) are shown below, but the present invention is not limited thereto. Not something.

[0149]

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[0150]

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[0151]

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[0152]

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[0153]

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[0154]

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[0155]

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[0156]

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[0157]

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[0158]

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[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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[0166]

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[0167]

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[0168]

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[0169]

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The compounds represented by the general formulas (II) and (III) are described in "Heterocyclic Compounds-Cyanine D" by FM Harmer.
yes and Related Compounds, ”John Wiley & Sons,
New York, London, 1964, DMSturmer, "H
eterocyclic Compounds-Special Topics in Heterocycl
ic Chemistry, "Chapter 18, Section 14, Pages 482-515, John
Wiley & Sons, New York, London, 1977, "Rodd's Chemistry of Carbon Compounds", 2nd.E
d., vol.IV, part B, Chapter 15, pages 369-422, Elsevier
Science Publishing Company Inc., New York,
It can be synthesized by the method described in British Patent No. 1,077,611 published in 1977.

The compound represented by the general formula (IV) is Dy
es and Pigments, Vol. 21, pp. 227 to 234, and the like. The compound represented by the general formula (V) is described in Ukrainskii Khimicheskii Zhurna
l, Volume 40, Issue 3, Pages 253-258, Dyes and Pigment
s, Vol. 21, pp. 227-234 and the references cited in these documents can be synthesized.

(4) Adsorption of Dye on Semiconductor Fine Particles The dye is adsorbed on the semiconductor fine particles by immersing a conductive support having a well-dried semiconductor fine particle layer in a dye solution or by dissolving the dye solution in a semiconductor solution. A method of applying to the 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 dye may be adsorbed at room temperature,
It may be carried out 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 dye. For example, alcohols (methanol, ethanol,
t-butanol, benzyl alcohol, etc.), nitriles (acetonitrile, propionitrile, 3-methoxypropionitrile, etc.), nitromethane, halogenated hydrocarbons (dichloromethane, dichloroethane, chloroform, chlorobenzene, etc.), ethers (diethyl ether, Tetrahydrofuran), 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, 2-butanone, cyclohexanone, etc.), hydrocarbons (hexane, petroleum ether, benzene, toluene, etc.) And mixed solvents of these You.

Regarding the viscosity of the solution of the dye, a high-viscosity liquid (for example, 0.01 to 500
For se), various printing methods other than the extrusion method are suitable, and for low-viscosity liquids (for example, 0.1 Poise or less), the slide hopper method, the wire bar method, or the spin method are suitable. It is possible.

Thus, the viscosity of the coating solution of the dye, the coating amount,
The method for adsorbing the dye may be appropriately selected according to the conductive support, the coating 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 unadsorbed dye causes disturbance of device performance, it is preferable to remove the dye by washing immediately after adsorption. Using a wet cleaning tank, polar solvents such as acetonitrile,
It is preferable to perform washing with an organic solvent such as an alcohol solvent. Further, in order to increase the adsorption amount of the dye, it is preferable to perform a heat treatment before the adsorption. After the heat treatment, do not return to room temperature to avoid water adsorbing on the surface of the semiconductor fine particles.
Preferably, the dye is adsorbed quickly between 40 and 80 ° C.

The total amount of the dye used is preferably from 0.01 to 100 mmol per unit surface area (1 m ² ) of the conductive support. The amount of dye adsorbed on the semiconductor fine particles is 1 g of the semiconductor fine particles.
It is preferably 0.01 to 1 mmol per unit. By using such a dye adsorption amount, a sufficient sensitizing effect in a 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 can 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.

For the purpose of reducing the interaction between 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 dye, the surface of the semiconductor fine particles may be treated with amines after the dye is adsorbed. Preferred amines are 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 dye with electrons. Although the electrolyte composition of the present invention is used for the charge transfer layer, a solid electrolyte or a hole transport material may be used in combination.

In order to form the charge transfer layer, an electrolyte solution may be applied on the photosensitive layer by a casting method, a coating method, an immersion method, an impregnation method or the like, and then crosslinked by a heating reaction. According to a preferred embodiment, as shown in FIG. 1, a solution containing more electrolyte than the amount that completely fills the voids in the photosensitive layer 20 is applied, so that the obtained electrolyte layer is substantially conductive on the conductive support. Counter electrode conductive layer from the boundary with layer 10
It can be said that it exists between the boundaries of 40. Here, assuming that the electrolyte layer existing between the boundary with the photosensitive layer 20 containing the dye-sensitized semiconductor and the boundary with the counter electrode 40 is the charge transfer layer 30, the thickness is preferably 0.001 to 200 μm, and 0.1 to 200 μm. ~ 100
μm is more preferable, and 0.1 to 50 μm is particularly preferable. If the charge transfer layer 30 is thinner than 0.001 μm, the semiconductor fine particles 21 in the photosensitive layer may come into contact with the counter electrode conductive layer 40. If the charge transfer layer 30 is thicker than 200 μm, the charge transfer distance becomes too large, and the resistance of the element increases. The thickness of the photosensitive layer 20 + the charge transfer layer 30 (substantially equal to the thickness of the electrolyte composition) is preferably from 0.1 to 300 μm, and more preferably from 1 to 130 μm.
Is more preferable, and 2 to 75 μm is particularly preferable.

(D) Counter electrode When the photoelectric conversion element is a photoelectrochemical cell, the counter electrode functions as a positive electrode of the photoelectrochemical 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 metal (for example, platinum, gold, silver, copper, aluminum, rhodium, indium, and the like), carbon, and conductive metal oxide (indium-tin composite oxide, tin oxide with fluorine). And the like). Examples of preferred support substrates for the counter electrode are glass or plastic,
The above-mentioned conductive agent is applied or vapor-deposited on this. 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 5 nm to
It is in the range of 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 is substantially transparent in order for the light to reach the photosensitive layer. I just want it. 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 is as follows: (a) when the charge transfer layer is formed and then formed thereon; and (b) when the counter electrode is disposed on the layer of the dye-sensitized semiconductor fine particles via a spacer. There are two cases in which the space is filled with an electrolyte solution. In the case of (a), a conductive material is applied directly on the charge transfer layer,
Plating or vapor deposition (PVD, CVD) or attaching the conductive layer side of the substrate having the conductive layer. In the case of (b), a counter electrode is assembled and fixed on the dye-sensitized semiconductor fine particle layer via a spacer, the open end of the obtained assembly is immersed in an electrolyte solution, and the capillary action or reduced pressure is used. An electrolyte solution is made to penetrate into the gap between the dye-sensitized semiconductor fine particle layer and the counter electrode.
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 10 a 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 further provided on the supporting 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. Is disposed with the metal lead 11 side inside, and has a structure in which light is incident from the counter electrode side. FIG. 5 shows a structure in which a metal lead 11 is partially provided on a transparent substrate 50a, and further, an undercoat layer 60, a photosensitive layer 20, and a charge transfer layer 30 are interposed between the transparent conductive layer 10a and the transparent conductive layer 10a. This is a structure from which light enters. FIG. 6 shows that a transparent conductive layer 10a is provided on a transparent substrate 50a, a photosensitive layer 20 is provided through an undercoat layer 60, and a charge transfer layer 30 is further provided.
In addition, a counter electrode conductive layer 40 is provided, and a support substrate 50 is disposed thereon, and has a structure in which light is incident from the conductive layer side.
FIG. 7 shows that the conductive layer 10 is provided on the supporting 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 transparent substrate 50a is disposed thereon. This is a structure in which light is incident from the counter electrode side. FIG.
Has a transparent conductive layer 10a on a transparent substrate 50a,
And a charge transfer layer 30 and a transparent counter electrode conductive layer 40a, and a transparent substrate 50a is disposed thereon. Light is incident from both sides. FIG. 9 shows that the conductive layer 10 is provided on the support substrate 50 and the undercoat layer is provided.
The photosensitive layer 20 is provided via 60, and the solid charge transfer layer 30 is further provided.
On which a counter electrode conductive layer 40 or a metal lead 11 is provided.
And has a structure in which light is incident from the counter electrode side.

[3] Photoelectrochemical Cell The photoelectrochemical cell of the present invention is one in which the above-mentioned photoelectric conversion element is made to work in an external circuit. It is preferable that the side surface of the photoelectrochemical 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 a 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 that of the above-mentioned 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 regular intervals between supporting substrates which are transparent on one or both sides and have been subjected to antireflection treatment, and adjacent cells are made of metal leads or flexible. It is connected by wiring or the like, and a current collecting electrode is arranged on the outer edge, so that generated power is taken out to the outside. 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 a protective function is provided by curing the above-mentioned filling resin. 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. Also,
If 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.

In the super straight type solar cell module, for example, while a front substrate sent from a substrate supply device is conveyed by a belt conveyor or the like, a cell is formed thereon with a sealing material-cell connection lead wire, 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 from the substrate supply device is conveyed by a belt conveyor or the like, the cells are sequentially laminated thereon with lead wires for connection between cells, a 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 module integrated with a substrate. FIG. 10 has a transparent conductive layer 10a on one surface of a transparent substrate 50a, on which a photosensitive layer 20 containing dye-adsorbed TiO ₂ and a charge transfer layer 30 are further provided.
In addition, the cell provided with the metal counter electrode conductive layer 40 is modularized, and the antireflection layer 70 is provided on the other surface of the substrate 50a. 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 arranged three-dimensionally 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.

Hereinafter, other members and steps will be described in detail.

Examples of the sealing material include liquid EVA (ethylene vinyl acetate), depending on the purpose of imparting weather resistance, imparting electric 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 a support substrate, a roll-shaped support is drawn out to form cells thereon, and then a sealing layer is continuously laminated by the above-described 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 is subjected to an anti-reflection treatment. As the anti-reflection treatment method,
There are 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 light is taken into the module without loss. However, light that has passed through the photoelectric conversion layer and has reached 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 reflectance of light, after polishing the supporting substrate surface to a mirror surface, a method of depositing or plating Ag, Al, or the like, an alloy layer such as Al-Mg or Al-Ti is used as a reflection layer on the lowermost layer of the cell. There are a method of providing a texture structure and a method of forming a texture structure in the lowermost layer by annealing.

In order to increase the power generation efficiency, it is important to reduce the inter-cell connection resistance from the viewpoint of suppressing 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.

[0206]

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.

1. Preparation of Titanium Dioxide Dispersion 15 g of titanium dioxide fine particles (Degussa P-25, manufactured by Nippon Aerosil Co., Ltd.), 45 g of water, and a dispersant (Aldrich, Triton X-) 100) 1 g and 30 g of zirconia beads having a diameter of 0.5 mm (manufactured by Nikkato Co., Ltd.) are added, and the mixture is subjected to 2 g at 1500 rpm using a sand grinder mill (manufactured by Imex).
Time-dispersed. 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 is MA
The measurement was performed using a master sizer manufactured by LVERN.

2. TiO with adsorbed dye_TwoPreparation of electrodes Conductive glass with fluorine-doped tin oxide layer
(TCO glass-U manufactured by Asahi Glass Co., Ltd.
Cut and processed, conductive surface side with surface resistance of about 30Ω / □)
The dispersion was applied using a glass rod. Semiconductor particles
20g / m ^TwoAnd At that time, a part of the conductive surface side
(3mm from the end) to make a spacer with adhesive tape,
Arrange the glass so that the adhesive tape is
It was applied one by one. After application, peel off the adhesive tape and allow
Air dried for one day. Next, this glass was converted into an electric furnace (Yamato Science
For 30 minutes at 450 ° C.
Calcined and TiO_TwoAn electrode was obtained. This electrode was taken out and cooled
Then, an ethanol solution of the dye (3 × 10^-Fourmol / l) for 3 hours
Dipped. TiO dyed with dye_TwoElectrode is 4-t-butylpyridyl
After immersion in ethanol for 15 minutes, wash with ethanol and air dry.
Was. The thickness of the obtained photosensitive layer was 10 μm. Dye coating
The amount of the cloth is appropriately 0.1 to 10 mmol / m depending on the type of the dye. ^TwoRange of
Selected from the box.

3-a. Production of Photoelectrochemical Battery Using Solvent-Based Electrolyte A solution containing an electrolyte salt at a concentration of 0.5 mol / l and iodine at a concentration of 0.05 mol / l was prepared using the solvents described in Table 1. To this solution, a nitrogen-containing polymer compound (2-4) was added at a weight composition ratio shown in Table 1 (solvent + nitrogen-containing polymer + weight composition ratio when the salt was 100% by weight). The electrophile (1-2) was mixed with the compound at a molar ratio shown in Table 1 (molar ratio of the electrophilic site to the reactive nitrogen atom of the nitrogen-containing polymer compound) to obtain a uniform solution. This solution is impregnated into the gap between the prepared dye-sensitized TiO ₂ electrode substrate (20 mm x 20 mm) and the same size of platinum-deposited glass by using the capillary phenomenon and introduced into the TiO ₂ electrode. did. Thereafter, the substrate is allowed to stand at 25 ° C. for 12 hours to perform a crosslinking reaction, and a conductive support layer made of conductive glass shown in FIG. 1 (a transparent conductive layer 10a is provided on a transparent substrate 50a made of glass). Then, a photoelectrochemical cell in which a photosensitive layer 20 of dye-sensitized TiO ₂ , a charge transfer layer 30, a counter electrode conductive layer 40 made of platinum, and a transparent substrate 50a made of glass were laminated in this order and sealed with an epoxy sealing agent was produced. The above steps were performed by changing the combination of the dye and the electrolyte composition as described in Table 1, and photoelectrochemical cells of Examples 1 to 18 were produced. Table 1 shows details of the electrolyte composition used for each photoelectrochemical cell and the dye used. In Table 1, NMO represents 3-methyl-2-oxazolidinone, PC represents propylene carbonate, AN represents acetonitrile, MHIm represents iodine salt of 1-methyl-3-hexylimidazolium, and MBIm represents Represents the iodine salt of 1-methyl-3-butylimidazolium.

[0210]

[Table 1]

3-b. Preparation of Photoelectrochemical Cell Using Room Temperature Molten Salt Electrolyte At the weight composition described in Table 2, the following molten salts:

Embedded image And iodine. Further, the nitrogen-containing polymer compound (2-4) and the molar ratio (reactivity of the nitrogen-containing polymer compound) shown in Table 2 with respect to the nitrogen-containing polymer compound (2-4) at a weight composition ratio shown in Table 2 The molar ratio of the electrophilic moiety to the nitrogen atom)
2) was mixed to obtain a uniform liquid. 5 μl of this electrolyte was applied on the prepared dye-sensitized TiO ₂ electrode substrate. Next, after allowing the electrolyte to penetrate into the TiO ₂ porous layer by leaving the TiO ₂ electrode substrate coated with the electrolyte for 30 minutes under reduced pressure,
Platinum vapor-deposited glass having the same size as the TiO ₂ electrode substrate was overlaid and left at 50 ° C. for 10 hours to carry out a crosslinking reaction to obtain a photoelectrochemical cell. The above steps were carried out by changing the combination of the dye and the electrolyte composition as shown in Table 2 to obtain photoelectrochemical cells of Examples 19 to 22.

3-c. Molten salt electrolyte comparison photoelectrochemical battery 3 except that the nitrogen-containing polymer of the present invention and the electrophile were not used.
-b. In the same manner as in the above, photoelectrochemical cells of Comparative Examples 1 and 2 in which the dyes and the electrolyte compositions described in Table 2 were combined were produced.

Table 2 shows the details of the electrolyte compositions used in the photoelectrochemical cells of Examples 19 to 22 and Comparative Examples 1 and 2 and the dyes used.

[0214]

[Table 2]

3-d. Preparation of Photoelectrochemical Cell for Comparison (Comparative Example 3: Solution Electrolyte) Iodine (concentration: 0.05 mol) using a mixture of acetonitrile and 3-methyl-2-oxazolidinone (volume ratio: 90/10) as a solvent for an electrolytic solution / l) and lithium iodide (concentration 0.5
mol / l) except 3-a. A photoelectrochemical cell of Comparative Example 3 was produced in the same manner as in Example 1.

3-e. Photoelectrochemical cell for comparison (Comparative Example 4:
(Electrolyte described in Chemical Society of Japan, 7, 484 pages (1997)) On a prepared dye-sensitized TiO ₂ electrode substrate, 500 mg of hexaethylene glycol methacrylate (Blenmer PE-350 manufactured by NOF Chemical Co., Ltd.) and 1 g of propylene 500 mg to a mixture containing carbonate and 2 mg of polymerization initiator AIBN
Of lithium iodide was dissolved, vacuum degassed for 10 minutes, and applied. Next, the TiO ₂ electrode coated with the mixed solution was placed under reduced pressure to remove bubbles in the TiO ₂ porous layer to promote penetration of the monomer, and then heated at 60 ° C. for 1 hour to polymerize. After the polymerization, the electrode was taken out, exposed to an iodine atmosphere at room temperature for 30 minutes to diffuse iodine into the polymer compound, and then superposed on a platinum-deposited counter electrode to obtain a photoelectrochemical cell of Comparative Example 4.

[0217] 4. Measurement of photoelectric conversion efficiency AM light of 500 W xenon lamp (Ushio Electric Co., Ltd.)
Simulated sunlight without ultraviolet rays was generated by passing through a 1.5 filter (manufactured by Oriel) and a sharp cut filter (Kenko L-42). The intensity of this light is 86 mW / cm ²
Met. The simulated sunlight was irradiated at 45 ° C. on each of the photoelectrochemical cells produced in Examples and Comparative Examples, and the generated electricity was measured with a current / voltage measuring device (Keithley SMU238 type). The open-circuit voltage (Voc), short-circuit current density (Jsc), form factor (FF), conversion efficiency (η), and rate of decrease in short-circuit current density after 360 hours of continuous irradiation of each photoelectrochemical cell are obtained. The results are shown in Table 3.

[0218]

[Table 3]

[0219] Compared with the photoelectrochemical cell of Comparative Example 3, the photoelectrochemical cell of the present invention shows less deterioration in photoelectric conversion characteristics. In addition, it is clear that the photoelectrochemical cell of the present invention has a higher short-circuit current density and is excellent in photoelectric conversion characteristics as compared with the photoelectrochemical cell of Comparative Example 4. In particular, in a photoelectrochemical battery using a molten salt at room temperature, the short-circuit current density is slightly lowered but the deterioration is remarkably small.

[0220]

According to the present invention, an electrolyte composition having excellent durability and charge transport ability can be provided. In addition, a photoelectric conversion element and a photoelectrochemical cell which are excellent in photoelectric conversion characteristics using the electrolyte composition and are less deteriorated in characteristics over time can be provided.

[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 photoelectric conversion element of the present invention.

[Explanation of symbols]

 10 conductive layer 10a transparent conductive layer 11 metal lead 20 photosensitive layer 21 fine semiconductor particles 22 dye 23 electrolyte 30 charge transfer layer 40 ..Counter electrode conductive layer 40a ... Transparent counter electrode conductive layer 50 ... Substrate 50a ... Transparent substrate 60 ... Undercoat layer 70 ... Anti-reflective layer

Claims (10)

[Claims] 1. The following general formula (1): (Where X represents a leaving group, Q represents an arylene group or a divalent linking group having a hetero atom, Y represents a s-valent linking group, and s represents an integer of 2 to 4). An electrolyte composition comprising a crosslinked polymer obtained by reacting a nitrogen-containing polymer compound with a compound represented by the formula. 2. The electrolyte composition according to claim 1, wherein the nitrogen-containing polymer compound has the following general formula (2): (However, R ₁ represents a hydrogen atom or an alkyl group, L represents a divalent linking group, Z represents a nitrogen-containing heterocyclic group, and E is a repeating unit derived from a compound having an ethylenically unsaturated group. And t is 0 or 1, x and y represent the weight composition ratio of the repeating unit, x is 5 to 100% by weight, and y is 0
~ 95% by weight. An electrolyte composition comprising a repeating unit represented by the formula: 3. The electrolyte composition according to claim 1, wherein the conjugate acid of the anion formed by elimination of X has a pKa of 10 or less. 4. The electrolyte composition according to claim 1, wherein X is a halogen atom, an alkylcarbonyloxy group, an arylcarbonyloxy group, an alkylsulfonyloxy group, or an arylsulfonyloxy group. A characteristic electrolyte composition. 5. The electrolyte composition according to claim 1, wherein Q is —CO—, —COO—, —SO—, —SO ₂ —, or a phenylene group. Electrolyte composition. 6. The electrolyte composition according to claim 2, wherein Z is a pyridyl group or an imidazolyl group. 7. A photoelectric conversion device having a conductive layer, a photosensitive layer, a charge transfer layer, and a counter electrode, wherein the charge transfer layer contains the electrolyte composition according to any one of claims 1 to 6. Photoelectric conversion element. 8. The photoelectric conversion element according to claim 7, wherein the photosensitive layer contains a fine particle semiconductor sensitized by a dye. 9. The photoelectric conversion device according to claim 8, wherein said fine particle semiconductor is a titanium dioxide fine particle semiconductor. A photoelectrochemical cell comprising the photoelectric conversion device according to any one of claims 7 to 9.