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WO2012017874A1 - Colorant complexe métallique, élément de conversion photoélectrique et cellule photoélectrochimique - Google Patents

Colorant complexe métallique, élément de conversion photoélectrique et cellule photoélectrochimique Download PDF

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Publication number
WO2012017874A1
WO2012017874A1 PCT/JP2011/067011 JP2011067011W WO2012017874A1 WO 2012017874 A1 WO2012017874 A1 WO 2012017874A1 JP 2011067011 W JP2011067011 W JP 2011067011W WO 2012017874 A1 WO2012017874 A1 WO 2012017874A1
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Prior art keywords
group
dye
ring
general formula
layer
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English (en)
Japanese (ja)
Inventor
小林　克
達也 薄
木村　桂三
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Fujifilm Corp
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Fujifilm Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
    • C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
    • C09B47/0673—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having alkyl radicals linked directly to the Pc skeleton; having carbocyclic groups linked directly to the skeleton
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
    • C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
    • C09B47/0678—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having-COOH or -SO3H radicals or derivatives thereof directly linked to the skeleton
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
    • C09B47/24—Obtaining compounds having —COOH or —SO3H radicals, or derivatives thereof, directly bound to the phthalocyanine radical
    • C09B47/26—Amide radicals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/311—Phthalocyanine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/371—Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/381—Metal complexes comprising a group IIB metal element, e.g. comprising cadmium, mercury or zinc
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Definitions

  • the present invention relates to a metal complex dye, a photoelectric conversion element, and a photoelectrochemical cell that have high conversion efficiency and excellent durability.
  • Photoelectric conversion elements are used in various optical sensors, copiers, solar cells and the like.
  • Various types of photoelectric conversion elements have been put to practical use, such as those using metals, semiconductors, organic pigments and dyes, or combinations thereof.
  • a solar cell using non-depleting solar energy does not require fuel, and its full-scale practical use is expected greatly as it uses inexhaustible clean energy.
  • silicon solar cells have been researched and developed for a long time. It is spreading due to the policy considerations of each country. However, silicon is an inorganic material, and its throughput and molecular modification are naturally limited.
  • Patent Document 1 describes a dye-sensitized photoelectric conversion element using semiconductor fine particles sensitized with a ruthenium complex dye by applying this technique.
  • ruthenium complex dyes are very expensive.
  • ruthenium has concerns about supply, and it is not yet enough to respond in earnest as a technology that supports the next generation of clean energy. Therefore, it is desired to develop a photoelectric conversion element having sufficient conversion efficiency using an inexpensive organic dye as a sensitizer, and a report using an organic dye as a sensitizer has been reported.
  • Patent Document 2 The photoelectric conversion element is required to have high initial conversion efficiency, low decrease in conversion efficiency even after use, and excellent durability. However, in terms of durability, the photoelectric conversion element described in Patent Document 2 is not yet satisfactory.
  • An object of the present invention is to provide a metal complex dye, a photoelectric conversion element, and a photoelectrochemical cell having high conversion efficiency and excellent durability.
  • a metal complex dye formed by binding at least one acidic group to a phthalocyanine-like compound and providing a conjugated group on the outer surface side of the phthalocyanine-like compound has the following effects. I found out that One of them is that it is less likely to be attacked by water or a nucleophilic species that decomposes the dye that causes the dye to peel off by closely adsorbing and adsorbing to the porous semiconductor fine particles. Second, since the movement and concentration of electrons excited by light absorbed by the dye are promoted, a photoelectric conversion element and a photoelectrochemical cell having high photoelectric conversion efficiency and excellent durability can be provided. . The present invention has been made based on this finding. According to the present invention, the following means are provided.
  • Z 1 , Z 2 , Z 3 , and Z 4 represent an aromatic ring structure or a heterocyclic structure.
  • R 1 , R 2 , R 3 , and R 4 each independently represent a substituent.
  • m1 to m4 represent an integer of 0 to 4, and when m1 to m4 is 2 or more, the plurality of R 1 to R 4 may be the same or different.
  • At least one of R 1 to R 4 includes a linking group Y, and the linking group Y is directly connected to at least one of Z 1 to Z 4 and is conjugated. Further, at least one of R 1 , R 2 , R 3 and R 4 has an acidic group.
  • M represents a hydrogen atom, a metal atom, or a substituted metal atom.
  • n1 to n8 represent 1 to 10.
  • m7 and m9 represent 0-4.
  • m8, m11, m12, m14, and m15 each represents 0-2.
  • R 5 and R 6 represent a hydrogen atom or a substituent.
  • R 7 to R 15 represent a substituent.
  • X 1 to X 4 are CH or N.
  • ⁇ 4> The dye compound according to any one of ⁇ 1> to ⁇ 3>, wherein a group other than the group containing an acidic group of R 1 to R 4 in the general formula (1) has a hydrophobic group.
  • a photoelectric conversion device comprising a photoreceptor layer, wherein the photoreceptor layer is sensitized with at least one dye compound according to any one of ⁇ 1> to ⁇ 4> and thereby A photoelectric conversion element containing semiconductor fine particles.
  • ⁇ 6> The photoelectric conversion element according to ⁇ 5>, wherein the photosensitive layer further contains a dye represented by the following general formula (14).
  • Mz represents a metal atom
  • LL 1 is a bidentate or tridentate ligand represented by the following general formula (15)
  • LL 2 is the following general formula (16).
  • X represents a ligand of monodentate or bidentate non-LL 1 and LL 2.
  • m1 represents an integer of 0 to 3, and when m1 is 2 or more, LL 1 may be the same or different.
  • m2 represents an integer of 0 to 3, and when m2 is 2, LL 2 may be the same or different. However, at least one of m1 and m2 is an integer of 1 or more.
  • n3 represents an integer of 0 to 2, and when m3 is 2, Xs may be the same or different, and Xs may be linked together.
  • CI represents a counter ion in the general formula (14) when a counter ion is necessary to neutralize the charge.
  • R 101 and R 102 each independently represent a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group, a phosphoryl group, or a phosphonyl group.
  • R 103 and R 104 each independently represent a substituent, and R 105 and R 106 each independently represent an alkyl group, an aryl group, or a heterocyclic group.
  • d1 and d2 each represents an integer of 0 or more.
  • L 1 and L 2 each independently represent a conjugated chain.
  • a1 and a2 each independently represent an integer of 0 to 3, and when a1 is 2 or more, R 101 may be the same or different, and when a2 is 2 or more, R 102 may be the same or different, b1 And b2 each independently represents an integer of 0 to 3.
  • R 103 may be the same or different, R 103 may be linked to each other to form a ring, and when b2 is 2 or more, R 4 may be the same or different.
  • 104 may be connected to each other to form a ring. When b1 and b2 are both 1 or more, may be linked to form a ring R 103 and R 104 are.
  • d3 represents 0 or 1.
  • Za, Zb and Zc each independently represent a non-metallic atom group capable of forming a 5- or 6-membered ring, and may each independently have an acidic group.
  • c represents 0 or 1;
  • the metal complex dye of the present invention By using the metal complex dye of the present invention, a photoelectric conversion element and a photoelectrochemical cell having high conversion efficiency and excellent durability can be provided.
  • the metal complex dye of the present invention has a long absorption range and a high ⁇ , and can obtain high conversion efficiency when used in a photoelectric conversion element or a photoelectrochemical cell.
  • the metal complex dye of the present invention since the metal complex dye of the present invention has a phthalocyanine compound nucleus structure and has an acidic group in the molecule and a conjugated group, it is closely aligned with the porous semiconductor fine particles formed on the conductive support. Adsorption increases the electron injection efficiency, and the electrons excited by light in the metal complex dye easily move to the semiconductor fine particles due to the conjugated structure and suppress reverse electron transfer. It is thought that an electrochemical cell can be obtained.
  • the semiconductor fine particle layer to which the metal complex dye of the present invention is adsorbed is more preferably subjected to an attack by water or a nucleophilic species that decomposes the dye, which causes the dye to peel off, by having a hydrophobic group. Therefore, it is considered that a photoelectric conversion element and a photoelectrochemical cell having excellent durability can be provided.
  • the photoelectric conversion element 10 includes a conductive support 1, a photosensitive layer 2, a charge transfer layer 3, and a counter electrode 4 arranged in that order on the conductive support 1.
  • the conductive support 1 and the photoreceptor 2 constitute a light receiving electrode 5.
  • the photoreceptor 2 has conductive fine particles 22 and a sensitizing dye 21, and the dye 21 is adsorbed on the conductive fine particles 22 at least in part (the dye is in an adsorption equilibrium state, It may be present in the partial charge transfer layer.)
  • the conductive support 1 on which the photoreceptor 2 is formed functions as a working electrode in the photoelectric conversion element 10.
  • the photoelectric conversion element 10 can be operated as the photoelectrochemical cell 100 by causing the external circuit 6 to work.
  • the upper and lower sides of the photoelectric conversion element do not need to be defined in particular, but in this specification, based on what is illustrated, the side of the counter electrode 4 serving as the light receiving side is the upper (top) direction, and the support The side of 1 is the lower (bottom) direction.
  • the light-receiving electrode 5 is an electrode composed of a conductive support 1 and a photosensitive layer (semiconductor film) 2 of semiconductor fine particles 22 adsorbed with a dye 21 coated on the conductive support.
  • the light incident on the photoreceptor (semiconductor film) 2 excites the dye.
  • the excited dye has high energy electrons. Therefore, the electrons are transferred from the dye 21 to the conduction band of the semiconductor fine particles 22 and further reach the conductive support 1 by diffusion.
  • the molecule of the dye 21 is an oxidant.
  • the electrons on the electrode return to the oxidized dye while working in an external circuit, thereby acting as a photoelectrochemical cell.
  • the light receiving electrode 5 functions as a negative electrode of the battery.
  • the photoelectric conversion element of the present invention has a photoreceptor having a porous semiconductor fine particle layer on which a dye described later is adsorbed on a conductive support.
  • the photoreceptor is designed according to the purpose, and may have a single layer structure or a multilayer structure.
  • the dye in the photoreceptor may be one kind or a mixture of many kinds, but at least one of them uses a metal complex dye described later.
  • the photoconductor of the photoelectric conversion element of the present invention contains semiconductor fine particles adsorbed with the dye, has high sensitivity, and can be used as a photoelectrochemical cell, and high conversion efficiency can be obtained.
  • Z 1 , Z 2 , Z 3 and Z 4 in the general formula (1) represent an aromatic ring structure or a heterocyclic structure.
  • the aromatic ring is preferably a monocyclic or bicyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms, more preferably a monocyclic or bicyclic aromatic hydrocarbon ring having 6 to 20 carbon atoms, and a carbon number of 6 More preferred are ⁇ 12 monocyclic or bicyclic aromatic hydrocarbon rings, and particularly preferred are a benzene ring and a naphthalene ring.
  • benzene ring biphenyl ring, 1,3-diphenylbenzene ring, anthracene ring, naphthalene ring, 1-phenylnaphthalene ring, 2-phenylnaphthalene ring, anthracene ring, phenanthrene ring, naphthacene ring, chrysene ring, triphenylene ring , Tetraphen ring, pyrene ring, pentacene ring, picene ring, perylene ring and the like.
  • a benzene ring and a naphthalene ring are particularly preferred.
  • Z 1 , Z 2 , Z 3 , and Z 4 preferably represent at least one naphthalene ring. More preferably, at least two of Z 1 , Z 2 , Z 3 and Z 4 represent a naphthalene ring, and more preferably at least 3 of Z 1 , Z 2 , Z 3 and Z 4. Is the case of representing a naphthalene ring.
  • the aromatic hydrocarbon ring may have a substituent, and examples of the substituent include the substituent T described below.
  • the heterocycle may have a substituent, and examples of the substituent include the substituent T described later.
  • the aromatic heterocyclic ring containing an oxygen atom, a nitrogen atom, a sulfur atom, and / or a selenium atom as a hetero atom is preferable.
  • the aromatic heterocycle is preferably a 5- to 7-membered ring, and more preferably a 5- to 6-membered ring.
  • furan ring pyrrole ring, thiophene ring, imidazole ring, pyrazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazole ring, triazine ring, indole ring, indazole ring, purine ring, thiazoline ring.
  • Heterocycle is preferably furan ring, pyrrole ring, thiophene ring, imidazole ring, pyrazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazole ring, triazine ring, indole ring, indazole ring, purine ring, thiazoline ring , Thiazole ring, thiadiazole ring, benzothiophene ring, thienothiophene ring, bithiophene ring, oxazoline ring, oxazole ring, oxadiazole ring, quinoline ring, isoquinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, cinnoline ring, Pteridine ring, acribidazine ring, pyridine
  • R 1 , R 2 , R 3 , and R 4 each independently represent a substituent, and specific examples thereof include a substituent represented by the following substituent T.
  • m1 to m4 represent an integer of 0 to 4, preferably 1 to 4.
  • At least one of R 1 to R 4 includes a linking group Y.
  • the linking group Y is conjugated with Z 1 ⁇ Z 4 bonded directly to Z 1 ⁇ Z 4.
  • At least one of R 1 to R 4 has an acidic group.
  • the acidic group may be substituted via a linking group within a range that exhibits a desired effect, and this linking group is referred to as an acidic group.
  • R 1 to R 4 include a linking group Y directly connected to Z 1 to Z 4, and three of the R 1 to R 4 include a linking group Y. More preferably, it is a group.
  • R 1 to R 4 are not a group containing a linking group Y or an acidic group or a group having an acidic group, it is preferably represented by a substituent T.
  • Preferred substituents T include an alkyl group, an alkoxy group, Examples thereof include an alkoxycarbonyl group, an aryloxycarbonyl group, a monoalkylcarbamoyl group, a dialkylcarbamoyl group, a monoalkylsulfamoyl group, a dialkylsulfamoyl group, an acylamino group, and an acyloxy group. More preferred are an alkyl group, an alkoxy group, an alkoxycarbonyl group, and an aryloxycarbonyl group.
  • Y represents a conjugated group conjugated with the above Z 1 to Z 4 , preferably a site represented by the following general formulas (2) to (9) or a site comprising a combination of one or more of these units Preferred units are those represented by the general formulas (4) to (6).
  • Y being a conjugated group means that the group itself has a conjugated structure, but there is also a conjugated relationship with the group Z 1 , Z 2 , Z 3 or Z 4 to which Y is bonded. Is preferred. Electrons excited by light absorbed by the dye due to the presence of the conjugated group Y move toward the conductive fine particles by the conjugated structure.
  • Groups that can be further substituted on the linking group Y include an alkyl group (preferably having 1 to 30 carbon atoms), an alkoxy group (preferably having 1 to 30 carbon atoms), an amino group, an alkoxycarbonyl group.
  • the hydrophobic group including an aliphatic group having 5 or more carbon atoms, a case where the hydrophobic group is substituted at a plurality of positions of the conjugated group, the total number of carbon atoms of the hydrophobic group is 5 or more, More preferably, the total carbon number is 15 or more.
  • the upper limit is not particularly limited but is 200 or less. By introducing this hydrophobic group, the action is further enhanced.
  • the number of substituents on Y is not limited and may be introduced into all of Z 1 , Z 2 , Z 3 or Z 4 other than those having an acidic group.
  • the terminal group of the linking group Y is not particularly limited, and examples thereof include a hydrogen atom or a group that can be further substituted.
  • the site constituting Y is preferably the general formulas (2) to (7), and more preferably the general formulas (2) to (5).
  • Y is preferably a case having at least one site represented by the general formulas (2) to (7), more preferably the general formula (2), (4), (6), or (7).
  • n1 to n8 represent 1 to 10, preferably 1 to 5, m7 and m9 represent 0 to 4, and m8, m11, m12, m14, and m15 represent 0 to 2, preferably 0 or 1.
  • R 5 to R 15 are substituents, and are an alkyl group (preferably having 1 to 30 carbon atoms), an alkoxy group (preferably having 1 to 30 carbon atoms), an amino group, an alkoxycarbonyl group, an alkylthio group, a carbamoyl group.
  • X 1 to X 4 are CH or N.
  • M represents two atoms selected from the group consisting of a hydrogen atom and a monovalent metal atom, a divalent metal atom, or a substituted metal atom in which the coordination position containing a trivalent or tetravalent metal atom is divalent.
  • Eg -AlCl- is preferred.
  • M is preferably a metal capable of tetracoordinate or hexacoordinate, and more preferably Ru, Fe, Os, Cu, W, Cr, Mo, Ni, Pd, Pt, Co, Ir, Rh, Re, Mn Or it is Zn. Particularly preferred is Ru, Os, Zn or Cu.
  • At least one of the R 1 to R 4 has at least one acidic group (group having a dissociable proton), but preferable acidic groups are COOH, PO 3 H 2 , PO 4 H 2 , A group selected from SO 3 H 2 , SO 3 H, and CONHOH, and more preferably COOH and SO 3 H.
  • the number of acidic groups in the metal complex dye is preferably 1 to 8, more preferably 1 to 4.
  • the acidic group includes those used in the form of a salt.
  • R 1 to R 4 may contain Y and an acidic group at the same time, but it is preferable that the substituent containing Y is different from the substituent having an acidic group.
  • the substituent T is, for example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12, particularly preferably 1 to 8, such as a methyl group, an ethyl group, an isopropyl group, or tert-butyl.
  • an alkyl group preferably having 1 to 20 carbon atoms, more preferably 1 to 12, particularly preferably 1 to 8, such as a methyl group, an ethyl group, an isopropyl group, or tert-butyl.
  • alkenyl group preferably 2-20 carbon atoms, more preferably 2-20 carbon atoms.
  • alkynyl group preferably 2 to 20 carbon atoms, more preferably 2 To 12, particularly preferably 2 to 8, and examples thereof include a propargyl group and a 3-pentynyl group
  • an aryl group preferably 6 to 30, more preferably 6 to 20, particularly preferably 6 to 12, and examples thereof include a phenyl group, a biphenyl group, and a naphthyl group.
  • a substituted or unsubstituted amino group (preferably carbon The number of atoms is 0 to 20, more preferably 0 to 10, particularly preferably 0 to 6, and examples thereof include an amino group, a methylamino group, a dimethylamino group, a diethylamino group, and a dibenzylamino group.
  • An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms such as a methoxy group, an ethoxy group, and a butoxy group), an aryloxy group (preferably The number of carbon atoms is 6 to 20, more preferably 6 to 16, and particularly preferably 6 to 12, and examples thereof include phenyloxy group and 2-naphthyloxy group.)
  • Acyl group (preferably having 1 to 1 carbon atom) 20, more preferably 1 to 16, particularly preferably 1 to 12, and examples thereof include an acetyl group, a benzoyl group, a formyl group, and a pivaloyl group), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, More preferably, it is 2 to 16, particularly preferably 2 to 12, and examples thereof include a methoxycarbonyl group and an ethoxycarbonyl group.
  • An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms such as a phenyloxycarbonyl group), an acyloxy group (preferably ) Has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include an acetoxy group and a benzoyloxy group.
  • An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms such as an acetylamino group and a benzoylamino group), an alkoxycarbonylamino group (preferably 2-20 carbon atoms, more preferably 2-16 carbon atoms, particularly preferably 2-12 carbon atoms, such as a methoxycarbonylamino group), an aryloxycarbonylamino group (preferably having 7-20 carbon atoms, More preferably, it is 7 to 16, particularly preferably 7 to 12, and examples thereof include a phenyloxycarbonylamino group, etc.), a sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, especially Preferably, it is 1 to 12, for example, methanesulfonylamino group, benzenesulfonyla ), Sulfamoyl groups (preferably having 0 to 20, more
  • a carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms such as a carbamoyl group and a methylcarbamoyl group). , Diethylcarbamoyl group, phenylcarbamoyl group, etc.),
  • alkylthio group preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms such as a methylthio group and an ethylthio group
  • arylthio group preferably having 6 carbon atoms
  • a sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12, for example, mesyl group, tosyl group, etc.), sulfinyl group (preferably 1 to 20, more preferably 1 to 16, particularly preferably 1 to 12, such as methane Sulfinyl group, benzenesulfinyl group, etc.), ureido group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, particularly preferably 1 to 12, for example, ureido group, methylureido group, phenylureido group, etc.), phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms) 16, particularly preferably 1 to 12, such as diethyl phosphate amide, phenyl phosphate amide,
  • those having a hydrogen atom may be substituted with the above groups after removing this.
  • Such functional groups include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group.
  • Examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.
  • substituents when there are two or more substituents, they may be the same or different. If possible, they may be linked together to form a ring.
  • the metal complex dye represented by the general formula (1) has a maximum absorption wavelength in a solution of 500 to 800 nm, more preferably 500 to 750 nm.
  • Specific preferred examples (A-1 to A-20) of the metal complex dye represented by the general formula (1) are shown below, but the present invention is not limited to the following specific examples.
  • the metal complex dye represented by the general formula (1) can be prepared by a method in which a phthalonitrile substituted with a conjugated group is closed by a usual method to form a phthalocyanine ring and coordinate the metal.
  • a phthalonitrile substituted with a conjugated group is closed by a usual method to form a phthalocyanine ring and coordinate the metal.
  • it can be carried out with reference to the method described in Ryo Takahashi, Keiichi Sakamoto, Eiko Okumura, “Phthalocyanine as a functional pigment” published by IPC 2004.
  • the salt, complex when it is other than a complex
  • a substituent that does not specify substitution / non-substitution means that the group may have an arbitrary substituent. This is also synonymous for compounds that do not specify substitution / non-substitution.
  • the above-mentioned substituent T can be mentioned.
  • the photoelectric conversion element may contain at least one dye compound and semiconductor fine particles sensitized by at least one compound represented by the following general formula (14).
  • the photoelectric conversion layers containing the semiconductor fine particles sensitized by the two kinds of sensitizing dyes can be formed as separate layers.
  • Mz represents a metal atom
  • LL 1 is a bidentate or tridentate ligand represented by the following general formula (15)
  • LL 2 is the following general formula (16). The bidentate or tridentate ligand represented.
  • X is a monodentate or bidentate ligand other than LL 1 and LL 2 and is preferably an acyloxy group, acylthio group, thioacyloxy group, thioacylthio group, acylaminooxy group, thiocarbamate group, dithiocarbamate group , Thiocarbonate group, dithiocarbonate group, trithiocarbonate group, acyl group, thiocyanate group, isothiocyanate group, cyanate group, isocyanate group, cyano group, alkylthio group, arylthio group, alkoxy group and aryloxy group
  • a monodentate or bidentate ligand coordinated by a group selected from the group, or a monodentate or bidentate comprising a halogen atom, carbonyl, dialkyl ketone, 1,3-diketone, carbonamide, thiocarbonamide or thiourea Represents a ligand.
  • m1 represents an integer of 0 to 3, and when m1 is 2 or more, LL 1 may be the same or different.
  • m2 represents an integer of 0 to 3, and when m2 is 2, LL 2 may be the same or different. However, at least one of m1 and m2 is an integer of 1 or more.
  • m3 represents an integer of 0 to 2, and when m3 is 2, Xs may be the same or different, and Xs may be linked together.
  • CI represents a counter ion in the general formula (14) when a counter ion is necessary to neutralize the charge.
  • Preferable pigments that can be used in combination include those having a structure represented by the general formula (14). As a result, the inefficient association was suppressed, and there was an unexpected effect that the absorption light conversion efficiency (APCE) was higher than that of the single substance.
  • Metal atom Mz Mz represents a metal atom.
  • M is preferably a metal capable of tetracoordinate or hexacoordinate, and more preferably Ru, Fe, Os, Cu, W, Cr, Mo, Ni, Pd, Pt, Co, Ir, Rh, Re, Mn Or it is Zn. Particularly preferred is Ru, Os, Zn or Cu, and most preferred is Ru.
  • the ligand LL 1 is a bidentate or tridentate ligand represented by the bidentate or tridentate ligand represented by the following general formula (15), preferably a bidentate ligand. is there.
  • M1 representing the number of the ligand LL 1 is an integer of 0 to 3, preferably 1 to 3, and more preferably 1.
  • LL 1 may be the same or different.
  • the m1, at least one of m2 representing the number of ligands LL 2 below is an integer of 1 or more.
  • the metal atom, the ligand LL 1 and / or ligand LL 2 is coordinated.
  • R 101 and R 102 in the general formula (15) each independently represent an acidic group, for example, a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group (preferably a hydroxamic acid group having 1 to 20 carbon atoms, such as , —CONHOH, —CONCH 3 OH, etc.), phosphoryl groups (eg —OP (O) (OH) 2 etc.) and phosphonyl groups (eg —P (O) (OH) 2 etc.), preferably carboxyl groups A phosphonyl group, more preferably a carboxyl group.
  • R 101 and R 102 may be substituted on any carbon atom on the pyridine ring. Further, these acidic groups may be introduced into the pyridine ring via a linking group.
  • R 103 and R 104 each independently represent a substituent, preferably an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, pentyl, heptyl, 1 -Ethylpentyl, benzyl, 2-ethoxyethyl, 1-carboxymethyl, etc.), alkenyl groups (preferably alkenyl groups having 2 to 20 carbon atoms such as vinyl, allyl, oleyl, etc.), alkynyl groups (preferably carbon atoms) Alkynyl groups having 2 to 20 carbon atoms such as ethynyl, butadiynyl, phenylethynyl, etc., cycloalkyl groups (preferably cycloalkyl groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl,
  • acylamino groups such as acetylamino, benzoylamino, etc.
  • a cyano group, or a halogen atom for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.
  • a halogen atom for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.
  • an alkyl group an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkoxy group.
  • a carbonyl group, an amino group, an acylamino group, a cyano group or a halogen atom particularly preferably an alkyl group, an alkenyl group, a heterocyclic group, an alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group or a cyano group.
  • the ligand LL 1 contains an alkyl group, an alkenyl group or the like, these may be linear or branched, and may be substituted or unsubstituted. Further, when the ligand LL 1 contains an aryl group, a heterocyclic group or the like, they may be monocyclic or condensed and may be substituted or unsubstituted.
  • R 105 and R 106 are each independently an alkyl group or an aromatic group (preferably an aromatic group having 6 to 30 carbon atoms, such as phenyl, substituted phenyl, naphthyl, substituted naphthyl, etc.) Or a heterocyclic group (preferably a heterocyclic group having 1 to 30 carbon atoms, such as 2-thienyl, 2-pyrrolyl, 2-imidazolyl, 1-imidazolyl, 4-pyridyl, 3-indolyl), preferably 1 A heterocyclic group having ⁇ 3 electron donating groups, more preferably thienyl.
  • an aromatic group having 6 to 30 carbon atoms such as phenyl, substituted phenyl, naphthyl, substituted naphthyl, etc.
  • a heterocyclic group preferably a heterocyclic group having 1 to 30 carbon atoms, such as 2-thienyl, 2-pyrrolyl, 2-imidazolyl, 1-imidazolyl, 4-pyr
  • the electron donating group is an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an amino group, an acylamino group (preferred examples are the same as those for R 103 and R 104 ) or a hydroxyl group. And more preferably an alkyl group, an alkoxy group, an amino group or a hydroxyl group, and particularly preferably an alkyl group.
  • R 105 and R 106 may be the same or different, but are preferably the same.
  • R 105 and R 106 may be directly bonded to the benzene ring.
  • R 105 and R 106 may be bonded to the benzene ring via L 1 and / or L 2 .
  • L 1 and L 2 each independently represent a conjugated chain.
  • the substituent is preferably an alkyl group, and more preferably methyl.
  • L 1 and L 2 are each independently preferably a conjugated chain having 2 to 6 carbon atoms, and a substituted or unsubstituted thiophenediyl group, ethenylene, butadienylene, ethynylene, butadienylene, methylethenylene, or dimethylethenyl It is more preferred to have lenth, groups having ethenylene or butadienylene are particularly preferred, and most preferred to have ethenylene.
  • L 1 and L 2 may be the same or different, but are preferably the same.
  • each double bond may be a trans isomer, a cis isomer, or a mixture thereof.
  • d1 and d2 are each an integer of 0 or more, preferably an integer of 1 to 3.
  • d3 is 0 or 1
  • a1 and a2 each independently represent an integer of 0 to 3.
  • a1 is R 101 when 2 or more may be the same or different
  • a2 is 2 or more when R 102 may be the same or different.
  • a1 is preferably 0 or 1
  • a2 is preferably an integer of 0-2.
  • a2 is preferably 1 or 2
  • d3 is 1, a2 is preferably 0 or 1.
  • the sum of a1 and a2 is preferably an integer of 0-2.
  • b1 and b2 each independently represents an integer of 0 to 3, preferably an integer of 0 to 2.
  • R 103 may be the same or different and may be connected to each other to form a ring.
  • R 104 may be the same or different, and may be connected to each other to form a ring.
  • R 103 and R 104 may be linked to form a ring.
  • the ring to be formed include a benzene ring, a pyridine ring, a thiophene ring, a pyrrole ring, a cyclohexane ring, a cyclopentane ring and the like.
  • A is the sum of a1 and a2 is 1 or more, when the ligand LL 1 is having at least one acidic group, m1 in formula (14) is preferably 2 or 3, the two Is more preferable.
  • the ligand LL 1 in the general formula (14) is preferably represented by the following general formula (17-1), (17-2) or (17-3).
  • R 101 to R 104 , a1, a2, b1, b2, d1, d2, and d3 have the same meanings as in the general formula (15).
  • b3 represents an integer of 0 to 3, preferably an integer of 0 to 2.
  • R 107 represents an acidic group, preferably a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group, a phosphoryl group, or a phosphonyl group, more preferably a carboxyl group or a phosphoryl group. Yes, particularly preferably a carboxyl group.
  • R 108 represents a substituent, preferably an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an amino group or an acylamino group (above preferred examples are R 103 and R 104 in general formula (15)), and more preferably an alkyl group, an alkoxy group, an amino group, or an acylamino group.
  • R 121 to R 124 each independently represents hydrogen, an alkyl group, an alkenyl group, or an aryl group. Preferred examples of R 121 to R 124 are the same as the preferred examples of R 103 and R 104 in formula (15). R 121 to R 124 are more preferably an alkyl group or an aryl group, and more preferably an alkyl group. When R 121 to R 124 are alkyl groups, they may further have a substituent, and the substituent is preferably an alkoxy group, a cyano group, an alkoxycarbonyl group or a carbonamido group, particularly preferably an alkoxy group.
  • R 121 and R 122 and R 123 and R 124 may be connected to each other to form a ring.
  • a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring or the like is preferable.
  • R 125 , R 126 , R 127 and R 128 each independently represent a substituent, preferably an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, An alkoxy group, an aryloxy group, an amino group, an acylamino group (preferred examples are the same as those for R 101 in the general formula (14)) or a hydroxyl group, more preferably an alkyl group, an alkoxy group, an amino group, or an acylamino group. Group, particularly preferably an alkyl group.
  • a3 represents an integer of 0 to 3, preferably an integer of 0 to 2.
  • a3 is preferably 1 or 2
  • a3 is preferably 0 or 1.
  • a3 is the R 107 when two or more may be the same or different.
  • d1 and d2 each independently represents an integer of 0 to 4.
  • R 125 may be linked to R 121 and / or R 122 to form a ring.
  • the ring formed is preferably a piperidine ring or a pyrrolidine ring.
  • R 125 may be the same or different, and may be linked to each other to form a ring.
  • R 126 may be linked to R 123 and / or R 124 to form a ring.
  • the ring formed is preferably a piperidine ring or a pyrrolidine ring.
  • R 126 may be the same or different, and may be linked to each other to form a ring.
  • LL 2 represents a bidentate or tridentate ligand.
  • M2 representing the number of the ligand LL 2 is an integer of 0 to 2, and is preferably 0 or 1.
  • m2 is LL 2 when the two may be the same or different. However, the m2, at least one of which is an integer of 1 or more of the m1 representing the number of ligands LL 1 above.
  • Ligand LL 2 is a bidentate or tridentate ligand represented by the following general formula (16).
  • Za, Zb, and Zc each independently represent a nonmetallic atom group that can form a 5-membered ring or a 6-membered ring.
  • the formed 5-membered or 6-membered ring may be substituted or unsubstituted, and may be monocyclic or condensed.
  • Za, Zb and Zc are preferably composed of a carbon atom, a hydrogen atom, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom and / or a halogen atom, and preferably form an aromatic ring.
  • an imidazole ring, an oxazole ring, a thiazole ring or a triazole ring is preferably formed.
  • a 6-membered ring a pyridine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring is preferably formed.
  • an imidazole ring or a pyridine ring is more preferable.
  • c represents 0 or 1.
  • c is preferably 0, and LL 2 is preferably a bidentate ligand.
  • the ligand LL 2 is preferably represented by any one of the following general formulas (18-1) to (18-8), and the general formulas (18-1), (18-2), (18-4) ) Or (18-6), more preferably represented by formula (18-1) or (18-2), and represented by formula (18-1). Is most preferred.
  • R 151 to R 166 are described as substituted on one ring for the sake of illustration, but even on the ring, Or you may substitute on the ring different from what was illustrated.
  • R 151 to R 158 each independently represent an acidic group.
  • R 151 to R 158 are, for example, a carboxyl group, a sulfonic acid group, a hydroxyl group, a hydroxamic acid group (preferably a hydroxamic acid group having 1 to 20 carbon atoms, such as —CONHOH, —CONCH 3 OH, etc.), a phosphoryl group ( For example, —OP (O) (OH) 2 etc.) or a phosphonyl group (eg —P (O) (OH) 2 etc.) is represented.
  • R 151 to R 158 are preferably a carboxyl group, a phosphoryl group, or a phosphonyl group, more preferably a carboxyl group or a phosphonyl group, and more preferably a carboxyl group.
  • the acidic group may be accompanied by any linking group.
  • R 159 to R 166 each independently represent a substituent, preferably an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or an alkoxy group.
  • An aryloxy group, an alkoxycarbonyl group, an amino group, an acyl group, a sulfonamido group, an acyloxy group, a carbamoyl group, an acylamino group, a cyano group, or a halogen atom the preferred examples are R 103 and R 104 in the general formula (15)).
  • R 167 to R 171 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group bonded with a carbon atom, An aliphatic group, and more preferably an aliphatic group having a carboxyl group.
  • the ligand LL 2 contains an alkyl group, an alkenyl group or the like, they may be linear or branched and may be unsubstituted substituted.
  • LL 2 is an aryl group, when containing heterocyclic group, they may be a condensed ring may be monocyclic or unsubstituted substituted.
  • R 151 to R 166 may be bonded to any position on the ring.
  • E1 to e6 each independently represents an integer of 0 to 4, preferably an integer of 0 to 2.
  • e7 and e8 each independently represents an integer of 0 to 4, preferably an integer of 0 to 3.
  • e9 to e12 and e15 each independently represents an integer of 0 to 6, and e13, e14 and e16 each independently represents an integer of 0 to 4. It is preferable that e9 to e16 are each independently an integer of 0 to 3.
  • R 151 to R 158 may be the same or different.
  • R 159 to R 166 may be the same or different and are connected to each other. To form a ring.
  • X represents a monodentate or bidentate ligand.
  • M3 representing the number of ligands X represents an integer of 0 to 2, and m3 is preferably 1 or 2.
  • m3 is preferably 2.
  • X is a bidentate ligand, m3 is preferably 1.
  • Xs may be the same or different, and Xs may be linked together.
  • the ligand X is preferably an acyloxy group (preferably an acyloxy group having 1 to 20 carbon atoms, such as acetyloxy, benzoyloxy, salicylic acid, glycyloxy, N, N-dimethylglycyloxy, oxalylene (—OC ( O) C (O) O—)), acylthio groups (preferably acylthio groups having 1 to 20 carbon atoms, such as acetylthio, benzoylthio, etc.), thioacyloxy groups (preferably thios having 1 to 20 carbon atoms).
  • acyloxy group preferably an acyloxy group having 1 to 20 carbon atoms, such as acetyloxy, benzoyloxy, salicylic acid, glycyloxy, N, N-dimethylglycyloxy, oxalylene (—OC ( O) C (O) O—)
  • acylthio groups preferably
  • thioacylthio groups such as thioacetyloxy groups (CH 3 C (S) O—), etc.)
  • thioacylthio groups preferably thioacylthio groups having 1 to 20 carbon atoms, such as thioacetylthio (CH 3 C (S)) S-), thiobenzoylthio (PhC (S) S-) etc.
  • acylaminooxy group preferably the number of carbon atoms 1-20 acylaminooxy groups such as N-methylbenzoylaminooxy (PhC (O) N (CH 3 ) O—), acetylaminooxy (CH 3 C (O) NHO—), etc.)
  • thiocarbamate A group preferably a thiocarbamate group having 1 to 20 carbon atoms such as N, N-diethylthiocarbamate
  • a dithiocarbamate group preferably a dithiocarbamate group having 1 to 20 carbon atom
  • the ligand X is preferably an acyloxy group, a thioacylthio group, an acylaminooxy group, a dithiocarbamate group, a dithiocarbonate group, a trithiocarbonate group, a thiocyanate group, an isothiocyanate group, a cyanate group, an isocyanate group, a cyano group, A ligand coordinated by a group selected from the group consisting of an alkylthio group, an arylthio group, an alkoxy group and an aryloxy group, or a ligand consisting of a halogen atom, carbonyl, 1,3-diketone or thiourea, More preferably, a ligand coordinated by a group selected from the group consisting of acyloxy group, acylaminooxy group, dithiocarbamate group, thiocyanate group, isothiocyanate group, cyanate group, isocyanate group, cyano
  • the ligand X contains an alkyl group, an alkenyl group, an alkynyl group, an alkylene group or the like, these may be linear or branched, and may be substituted or unsubstituted.
  • an aryl group, a heterocyclic group, a cycloalkyl group, etc. may be substituted or unsubstituted, and may be monocyclic or condensed.
  • X is a bidentate ligand
  • X is an acyloxy group, acylthio group, thioacyloxy group, thioacylthio group, acylaminooxy group, thiocarbamate group, dithiocarbamate group, thiocarbonate group, dithiocarbonate group, trithio
  • a ligand composed of urea is preferable.
  • X is a monodentate ligand
  • X is a ligand coordinated by a group selected from the group consisting of a thiocyanate group, an isothiocyanate group, a cyanate group, an isocyanate group, a cyano group, an alkylthio group, and an arylthio group, or A ligand composed of a halogen atom, carbonyl, dialkyl ketone, or thiourea is preferred.
  • Counter ion CI CI in the general formula (14) represents a counter ion when a counter ion is necessary to neutralize the charge.
  • a dye is a cation or an anion or has a net ionic charge depends on the metal, ligand and substituent in the dye.
  • the dye of the general formula (14) may be dissociated and have a negative charge because the substituent has a dissociable group. In this case, the charge of the whole dye of the general formula (14) is electrically neutralized by CI.
  • the counter ion CI is a positive counter ion
  • the counter ion CI is an inorganic or organic ammonium ion (for example, tetraalkylammonium ion, pyridinium ion, etc.), an alkali metal ion, or a proton.
  • the counter ion CI is a negative counter ion
  • the counter ion CI may be an inorganic anion or an organic anion.
  • halogen anions eg, fluoride ions, chloride ions, bromide ions, iodide ions, etc.
  • substituted aryl sulfonate ions eg, p-toluene sulfonate ions, p-chlorobenzene sulfonate ions, etc.
  • aryl disulfones Acid ions for example, 1,3-benzenedisulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion, etc.
  • alkyl sulfate ions for example, methyl sulfate ion
  • sulfate ions thiocyanate ions
  • an ionic polymer or another dye having a charge opposite to that of the dye may be used, and a metal complex ion (for example, bisbenzene-1,2-dithiolatonickel (III)) can also be used. is there.
  • the dye having the structure represented by the general formula (14) preferably has at least one suitable bonding group (interlocking group) for the surface of the semiconductor fine particles. It is more preferable that the bonding group has 1 to 6 bonding groups, and it is particularly preferable that the bonding group has 1 to 4 bonding groups. Carboxyl group, sulfonic acid group, hydroxyl group, hydroxamic acid group (for example, —CONHOH), phosphoryl group (for example, —OP (O) (OH) 2, etc.), phosphonyl group (for example, —P (O) (OH) 2, etc.) It is preferable that the dye has an acidic group (substituent having a dissociable proton).
  • the dye having the structure represented by the general formula (14) used in the present invention is shown below, but the present invention is not limited thereto.
  • dye in the following specific example contains the ligand which has a proton dissociable group, this ligand may dissociate as needed and may discharge
  • the dye represented by the general formula (14) can be synthesized with reference to Japanese Patent Application Laid-Open No. 2001-291534 and the methods cited in the publication.
  • the maximum absorption wavelength in the solution is preferably in the range of 300 to 1000 nm, more preferably in the range of 350 to 950 nm, and particularly preferably in the range of 370 to 900 nm.
  • the dye having the structure of the general formula (1) has a maximum absorption wavelength in the solution of preferably 500 to 800 nm, more preferably 500 to 750 nm.
  • a dye containing (A1) a metal complex dye having the structure of the general formula (1) as an essential component is used. More preferably, by using a dye having a structure of the general formula (14), high conversion efficiency can be ensured by utilizing light having a wide range of wavelengths. Furthermore, the combined use of these dyes can reduce the decrease in conversion efficiency.
  • a preferable blending ratio of the metal complex dye having the structure represented by the general formula (14) and the dye having the structure represented by the general formula (1) is R in the former and S in the latter.
  • iodine and iodide for example, lithium iodide, tetrabutylammonium iodide, tetrapropylammonium iodide, etc.
  • alkyl viologen for example, methyl viologen chloride, hexyl viologen bromide, benzyl viologen tetrafluoroborate
  • polyhydroxybenzenes for example, hydroquinone, naphthohydroquinone, etc.
  • divalent and trivalent iron complexes for example, red blood salt and yellow blood salt
  • the cation of the iodine salt is preferably a 5-membered or 6-membered nitrogen-containing aromatic cation.
  • the compound represented by the general formula (2) is not an iodine salt, it is described in WO95 / 18456, JP-A-8-259543, Electrochemistry, Vol. 65, No. 11, page 923 (1997), etc. It is preferable to use iodine salts such as pyridinium salts, imidazolium salts, and triazolium salts.
  • the electrolyte composition used for the photoelectric conversion element of the present invention preferably contains iodine together with the heterocyclic quaternary salt compound.
  • the iodine content is preferably from 0.1 to 20% by mass, more preferably from 0.5 to 5% by mass, based on the entire electrolyte composition.
  • the electrolyte composition used for the photoelectric conversion element of the present invention may contain a solvent.
  • the solvent content in the electrolyte composition is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 10% by mass or less of the entire composition.
  • a solvent having a low viscosity and high ion mobility, a high dielectric constant and capable of increasing the effective carrier concentration, or both is preferable because it exhibits excellent ion conductivity.
  • Such solvents include carbonate compounds (ethylene carbonate, propylene carbonate, etc.), heterocyclic compounds (3-methyl-2-oxazolidinone, etc.), ether compounds (dioxane, diethyl ether, etc.), chain ethers (ethylene glycol dialkyl ether, Propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, etc.), alcohols (methanol, ethanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, etc.), Polyhydric alcohols (ethylene glycol, propylene glycol, polyethylene glycol , Polypropylene glycol, glycerol, etc.), nitrile compounds (acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, benzonitrile, biscyanoethyl
  • an electrochemically inert salt that is in a liquid state at room temperature and / or has a melting point lower than room temperature may be used as the electrolyte solvent.
  • the electrolyte solvent For example, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, etc., nitrogen-containing heterocyclic quaternary salt compounds such as imidazolium salts and pyridinium salts, or tetraalkylammonium salts Is mentioned.
  • the electrolyte composition used in the photoelectric conversion element of the present invention may be added with a polymer or an oil gelling agent, or may be gelled (solidified) by a technique such as polymerization of polyfunctional monomers or polymer crosslinking reaction. .
  • the blending amount of the polyfunctional monomer is preferably 0.5 to 70% by mass, and more preferably 1.0 to 50% by mass with respect to the whole monomer.
  • the above-mentioned monomers are commonly used in Takayuki Otsu and Masato Kinoshita “Experimental Methods for Polymer Synthesis” (Chemical Doujin) and Takatsu Otsu “Lecture Polymerization Reaction Theory 1 Radical Polymerization (I)” (Chemical Doujin).
  • Polymerization can be performed by radical polymerization which is a polymer synthesis method.
  • the monomer for gel electrolyte used in the present invention can be radically polymerized by heating, light or electron beam, or electrochemically, and is particularly preferably radically polymerized by heating.
  • polymerization initiators are 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2-methylpropyl). Pionate), azo initiators such as dimethyl 2,2′-azobisisobutyrate, peroxide initiators such as lauryl peroxide, benzoyl peroxide, and t-butyl peroctoate.
  • a preferable addition amount of the polymerization initiator is 0.01 to 20% by mass, and more preferably 0.1 to 10% by mass with respect to the total amount of monomers.
  • the weight composition range of the monomer in the gel electrolyte is preferably 0.5 to 70% by mass.
  • the content is 1.0 to 50% by mass.
  • a polymer having a crosslinkable reactive group and a crosslinking agent is added to the composition.
  • Preferred reactive groups are nitrogen-containing heterocycles such as pyridine ring, imidazole ring, thiazole ring, oxazole ring, triazole ring, morpholine ring, piperidine ring, piperazine ring, and the preferred crosslinking agent is a functional group capable of nucleophilic attack by the nitrogen atom.
  • the electrolyte composition of the present invention metal iodides (LiI, NaI, KI, CsI , CaI 2 , etc.), a metal bromide (LiBr, NaBr, KBr, CsBr , CaBr 2 , etc.), quaternary ammonium bromine salt (tetraalkylammonium Ammonium bromide, pyridinium bromide, etc.), metal complexes (ferrocyanate-ferricyanate, ferrocene-ferricinium ion, etc.), sulfur compounds (sodium polysulfide, alkylthiol-alkyl disulfides, etc.), viologen dye, hydroquinone-quinone Etc. may be added. These may be used as a mixture.
  • J.P. Am. Ceram. Soc. 80, (12), 3157-3171 (1997), or basic compounds such as 2-picoline and 2,6-lutidine may be added.
  • a preferred concentration range is 0.05 to 2M.
  • a charge transport layer containing a hole conductor material may be used as the hole conductor material.
  • 9,9′-spirobifluorene derivatives and the like can be used.
  • an electrode layer, a photoelectric conversion layer, a hole transport layer, a conductive layer, and a counter electrode layer can be sequentially stacked.
  • a hole transport material that functions as a p-type semiconductor can be used as a hole transport layer.
  • an inorganic or organic hole transport material can be used as a preferred hole transport layer.
  • the inorganic hole transport material include CuI, CuO, and NiO.
  • the organic hole transport material include high molecular weight materials and low molecular weight materials. Examples of the high molecular weight material include polyvinyl carbazole, polyamine, and organic polysilane.
  • the organic polysilane is a polymer having a main chain Si chain unlike the conventional carbon-based polymer. And since ⁇ electrons delocalized along the main chain Si contribute to photoconduction, it has high hole mobility [Phys. Rev. B, 35, 2818 (1987)].
  • the conductive layer in the present invention is not particularly limited as long as it has good conductivity, and examples thereof include inorganic conductive materials, organic conductive materials, conductive polymers, and intermolecular charge transfer complexes. Of these, intermolecular charge transfer complexes are preferred.
  • the intermolecular charge transfer complex is formed from a donor material and an acceptor material.
  • an organic donor and an organic acceptor can be used preferably.
  • a photosensitive member 2 in which a dye 21 is adsorbed on porous semiconductor fine particles 22 is formed on a conductive support 1.
  • the photosensitive layer can be produced by immersing the dispersion of semiconductor fine particles in the dye solution of the present invention after coating and drying on a conductive support.
  • the conductive support there can be used a glass or a polymer material having a conductive film layer on the surface, such as a metal that is conductive in the support itself. It is preferable that the conductive support is substantially transparent. Substantially transparent means that the light transmittance is 10% or more, preferably 50% or more, particularly preferably 80% or more.
  • a glass or polymer material coated with a conductive metal oxide can be used as the conductive support.
  • the coating amount of the conductive metal oxide at this time is preferably 0.1 to 100 g per 1 m 2 of glass or polymer material support.
  • light is preferably incident from the support side.
  • polymer materials examples include tetraacetyl cellulose (TAC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), syndiotactic polystyrene (SPS), polyphenylene sulfide (PPS), polycarbonate (PC), Examples include polyarylate (PAR), polysulfone (PSF), polyester sulfone (PES), polyetherimide (PEI), cyclic polyolefin, and brominated phenoxy.
  • TAC tetraacetyl cellulose
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • SPS syndiotactic polystyrene
  • PPS polyphenylene sulfide
  • PC polycarbonate
  • Examples include polyarylate (PAR), polysulfone (PSF), polyester sulfone (PES), polyetherimide (PEI), cyclic polyolefin, and brominated phenoxy
  • an antireflection film in which a high refractive film and a low refractive index oxide film described in JP-A-2003-123859 are alternately laminated The light guide function described in 2002-260746 is raised.
  • a metal support can also be preferably used. Examples thereof include titanium, aluminum, copper, nickel, iron, stainless steel, and copper. These metals may be alloys. More preferably, titanium, aluminum, and copper are preferable, and titanium and aluminum are particularly preferable.
  • the conductive support has a function of blocking ultraviolet light.
  • a method of allowing a fluorescent material capable of changing ultraviolet light to visible light in the transparent support or on the surface of the transparent support, or a method using an ultraviolet absorber is also included.
  • a function described in JP-A-11-250944 may be further provided on the conductive support.
  • Preferred conductive films include metals (eg, platinum, gold, silver, copper, aluminum, rhodium, indium, etc.), carbon, or conductive metal oxides (indium-tin composite oxide, tin oxide doped with fluorine, etc.) ).
  • the thickness of the conductive film layer is preferably 0.01 to 30 ⁇ m, more preferably 0.03 to 25 ⁇ m, and particularly preferably 0.05 to 20 ⁇ m.
  • the range of the surface resistance is preferably 50 ⁇ / cm 2 or less, more preferably 10 ⁇ / cm 2 or less. Although there is no restriction
  • a collecting electrode may be disposed.
  • a gas barrier film and / or an ion diffusion prevention film may be disposed between the support and the transparent conductive film.
  • the gas barrier layer a resin film or an inorganic film can be used.
  • the transparent conductive layer may have a laminated structure, and as a preferable method, for example, FTO can be laminated on ITO.
  • (D) Semiconductor Fine Particles As shown in FIG. 1, in the photoelectric conversion element 10 of the present invention, a photosensitive layer 2 in which a sensitizing dye 21 is adsorbed on porous semiconductor fine particles 22 is formed on a conductive support 1. Has been. As will be described later, for example, a dispersion of semiconductor fine particles is applied to the conductive support and dried, and then immersed in the dye solution of the present invention to produce a photoreceptor.
  • the semiconductor fine particles metal chalcogenides (for example, oxides, sulfides, selenides, etc.) or perovskite fine particles are preferably used.
  • Preferred examples of the metal chalcogenide include titanium, tin, zinc, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, tantalum oxide, cadmium sulfide, cadmium selenide, and the like.
  • Preferred perovskites include strontium titanate and calcium titanate. Of these, titanium oxide, zinc oxide, tin oxide, and tungsten oxide are particularly preferable.
  • n-type In semiconductors, there are an n-type in which carriers involved in conduction are electrons and a p-type in which carriers are holes. In the element of the present invention, n-type is preferable in terms of conversion efficiency. In an n-type semiconductor, in addition to an intrinsic semiconductor (or an intrinsic semiconductor) having no impurity level and having the same carrier concentration due to conduction band electrons and valence band holes, the electron carrier concentration is reduced by structural defects derived from impurities. There are high n-type semiconductors.
  • the n-type inorganic semiconductor preferably used in the present invention is TiO 2 , TiSrO 3 , ZnO, Nb 2 O 3 , SnO 2 , WO 3 , Si, CdS, CdSe, V 2 O 5 , ZnS, ZnSe, SnSe, KTaO. 3 , FeS 2 , PbS, InP, GaAs, CuInS 2 , CuInSe 2 and the like.
  • the most preferred n-type semiconductors are TiO 2 , ZnO, SnO 2 , WO 3 , and Nb 2 O 3 .
  • a semiconductor material in which a plurality of these semiconductors are combined is also preferably used.
  • the average particle size of the primary particles is 2 nm to 50 nm, and the average primary particle size is 2 nm to 30 nm. More preferably, it is a fine particle. Two or more kinds of fine particles having different particle size distributions may be mixed. In this case, the average size of the small particles is preferably 5 nm or less.
  • large particles having an average particle size exceeding 50 nm can be added to the ultrafine particles at a low content, or another layer can be applied.
  • the content of the large particles is preferably 50% or less, more preferably 20% or less of the mass of particles having an average particle size of 50 nm or less.
  • the average particle size of the large particles added and mixed for the above purpose is preferably 100 nm or more, and more preferably 250 nm or more.
  • the haze ratio is preferably 60% or more.
  • the haze ratio is expressed by (diffuse transmittance) / (total light transmittance).
  • the gel-sol method described in Sakuo Sakuo's “Science of Sol-Gel Method”, Agne Jofu Co., Ltd. (1998) and the like is preferable. Also preferred is a method of producing an oxide by high-temperature hydrolysis of a chloride developed by Degussa in an oxyhydrogen salt.
  • the above sol-gel method, gel-sol method, and high-temperature hydrolysis method in oxyhydrogen salt of chloride are preferred, but Kiyoshi Manabu's “Titanium oxide properties and applied technology”
  • the sulfuric acid method and the chlorine method described in Gihodo Publishing (1997) can also be used.
  • the sol-gel method the method described in Journal of American Ceramic Society, Vol. 80, No. 12, 3157-3171 (1997), or the chemistry of Burnside et al. -The method described in Materials, Vol. 10, No. 9, pages 2419-2425 is also preferable.
  • a method for producing semiconductor fine particles for example, as a method for producing titania nanoparticles, preferably, a method by flame hydrolysis of titanium tetrachloride, a combustion method of titanium tetrachloride, hydrolysis of a stable chalcogenide complex, orthotitanic acid Of semiconductor, forming semiconductor fine particles from soluble and insoluble parts, then dissolving and removing soluble parts, hydrothermal synthesis of peroxide aqueous solution, or production of core / shell structured titanium oxide fine particles by sol-gel method A method is mentioned.
  • titania examples include anatase type, brookite type, and rutile type, and anatase type and brookite type are preferable. Titania nanotubes, nanowires, and nanorods may be mixed with titania fine particles.
  • ⁇ Titania may be doped with a nonmetallic element or the like.
  • an additive may be used on the surface to improve the necking or to prevent reverse electron transfer.
  • preferred additives include ITO, SnO particles, whiskers, fibrous graphite / carbon nanotubes, zinc oxide necking binders, fibrous materials such as cellulose, metals, organic silicon, dodecylbenzenesulfonic acid, silane compounds, etc. Examples thereof include a mobile binding molecule and a potential gradient dendrimer.
  • titania may be acid-base or redox treated before dye adsorption. Etching, oxidation treatment, hydrogen peroxide treatment, dehydrogenation treatment, UV-ozone, oxygen plasma, or the like may be used.
  • a semiconductor fine particle dispersion in which the solid content other than the semiconductor fine particles is 10% by mass or less of the entire semiconductor fine particle dispersion is applied to the conductive support.
  • a porous semiconductor fine particle coating layer can be obtained by heating to a high temperature.
  • a method of preparing a semiconductor fine particle dispersion is a method of depositing fine particles in a solvent and using them as they are when synthesizing a semiconductor. Ultrafine particles are irradiated with ultrasonic waves. Or a method of mechanically pulverizing and grinding using a mill or a mortar.
  • the dispersion solvent water and / or various organic solvents can be used.
  • organic solvent examples include alcohols such as methanol, ethanol, isopropyl alcohol, citronellol and terpineol, ketones such as acetone, esters such as ethyl acetate, dichloromethane, acetonitrile and the like.
  • alcohols such as methanol, ethanol, isopropyl alcohol, citronellol and terpineol
  • ketones such as acetone
  • esters such as ethyl acetate, dichloromethane, acetonitrile and the like.
  • a small amount of, for example, a polymer such as polyethylene glycol, hydroxyethyl cellulose, carboxymethyl cellulose, a surfactant, an acid, or a chelating agent may be used as a dispersion aid.
  • the solid content other than the semiconductor fine particles can be 10% by mass or less of the total dispersion. This concentration is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less. More preferably, it is 0.5% or less, and particularly preferably 0.2%. That is, in the semiconductor fine particle dispersion, the solid content other than the solvent and the semiconductor fine particles can be 10% by mass or less of the entire semiconductor fine particle dispersion.
  • the viscosity of the semiconductor fine particle dispersion is preferably 10 to 300 N ⁇ s / m 2 at 25 ° C. More preferably, it is 50 to 200 N ⁇ s / m 2 at 25 ° C.
  • a roller method, a dip method, or the like can be used as an application method.
  • an air knife method, a blade method, etc. can be used as a metering method.
  • the application method and the metering method can be made the same part.
  • the wire bar method disclosed in Japanese Patent Publication No. 58-4589, the slide hopper method described in US Pat. No. 2,681,294, etc., the extrusion The method and the curtain method are preferable. It is also preferable to apply by a spin method or a spray method using a general-purpose machine.
  • the wet printing method intaglio, rubber plate, screen printing and the like are preferred, including the three major printing methods of letterpress, offset and gravure. From these, a preferred film forming method is selected according to the liquid viscosity and the wet thickness. Further, since the semiconductor fine particle dispersion of the present invention has a high viscosity and has a viscous property, it may have a strong cohesive force and may not be well adapted to the support during coating. In such a case, by performing cleaning and hydrophilization of the surface by UV ozone treatment, the binding force between the applied semiconductor fine particle dispersion and the surface of the conductive support increases, and the semiconductor fine particle dispersion can be easily applied.
  • the preferred thickness of the entire semiconductor fine particle layer is 0.1 to 100 ⁇ m.
  • the thickness of the semiconductor fine particle layer is further preferably 1 to 30 ⁇ m, and more preferably 2 to 25 ⁇ m.
  • the amount of the semiconductor fine particles supported per 1 m 2 of the support is preferably 0.5 g to 400 g, more preferably 5 to 100 g.
  • the applied semiconductor fine particle layer is subjected to heat treatment to enhance the electronic contact between the semiconductor fine particles and to improve the adhesion to the support, and to dry the applied semiconductor fine particle dispersion. .
  • heat treatment By this heat treatment, a porous semiconductor fine particle layer can be formed.
  • light energy can also be used.
  • the surface may be activated by applying light absorbed by the semiconductor fine particles such as ultraviolet light, or only the surface of the semiconductor fine particles may be activated by laser light or the like. Can do.
  • the impurities adsorbed on the particle surface are decomposed by the activation of the particle surface, and can be brought into a preferable state for the above purpose.
  • heat treatment and ultraviolet light it is preferable that heating be performed at 100 ° C. or higher and 250 ° C. or lower, or preferably 100 ° C. or higher and 150 ° C. or lower, while irradiating the semiconductor fine particles with light absorbed by the fine particles.
  • the semiconductor fine particle dispersion may be applied to the conductive support, and other treatments may be performed in addition to heating and light irradiation.
  • Examples of preferred methods include energization and chemical treatment.
  • a pressure may be applied after the application, and a method for applying the pressure includes Japanese Patent Publication No. 2003-500857.
  • Examples of light irradiation include JP-A No. 2001-357896.
  • Examples of plasma, microwave, and energization include JP-A No. 2002-353453.
  • Examples of the chemical treatment include JP-A-2001-357896.
  • the method for coating the above-mentioned semiconductor fine particles on the conductive support is not only the method for applying the above-mentioned semiconductor fine particle dispersion on the conductive support, but also the semiconductor fine particle precursor described in Japanese Patent No. 2664194.
  • a method such as a method of obtaining a semiconductor fine particle film by applying on a conductive support and hydrolyzing with moisture in the air can be used.
  • the precursor include (NH 4 ) 2 TiF 6 , titanium peroxide, metal alkoxide / metal complex / metal organic acid salt, and the like.
  • a method of forming a semiconductor film by applying a slurry in which a metal organic oxide (alkoxide, etc.) coexists, and heat treatment, light treatment, etc., a slurry in which an inorganic precursor coexists, titania dispersed in the pH of the slurry The method which specified the property of particle
  • a binder may be added in a small amount, and examples of the binder include cellulose, fluoropolymer, crosslinked rubber, polybutyl titanate, carboxymethyl cellulose and the like.
  • Techniques related to the formation of semiconductor fine particles or precursor layers thereof include corona discharge, plasma, a method of hydrophilizing by a physical method such as UV, a chemical treatment with alkali, polyethylenedioxythiophene and polystyrenesulfonic acid, polyaniline, etc. For example, formation of an interlayer film for bonding may be mentioned.
  • Examples of the dry method include vapor deposition, sputtering, and aerosol deposition method. Further, electrophoresis or electrodeposition may be used. Moreover, after producing a coating film once on a heat-resistant board
  • the semiconductor fine particles preferably have a large surface area so that many dyes can be adsorbed.
  • the surface area is preferably 10 times or more, more preferably 100 times or more the projected area.
  • limiting in particular in this upper limit Usually, it is about 5000 times. JP-A-2001-93591 and the like are preferable as the structure of semiconductor fine particles.
  • the thickness of the semiconductor fine particle layer increases, the amount of dye that can be supported per unit area increases, so that the light absorption efficiency increases.
  • the preferred thickness of the semiconductor fine particle layer varies depending on the use of the device, but is typically 0.1 to 100 ⁇ m. When used as a photoelectrochemical cell, the thickness is preferably 1 to 50 ⁇ m, more preferably 3 to 30 ⁇ m.
  • the semiconductor fine particles may be heated at a temperature of 100 to 800 ° C. for 10 minutes to 10 hours in order to adhere the particles to each other after being applied to the support.
  • the film forming temperature is preferably 400 to 600 ° C.
  • a polymer material is used as the support, it is preferably heated after film formation at 250 ° C.
  • the film forming method may be any of (1) a wet method, (2) a dry method, and (3) an electrophoresis method (including an electrodeposition method), and preferably (1) a wet method or ( 2) A dry method, more preferably (1) a wet method.
  • the coating amount of semiconductor fine particles per 1 m 2 of support is preferably 0.5 to 500 g, more preferably 5 to 100 g.
  • the well-dried semiconductor fine particles are placed in a dye adsorption dye solution comprising the solution and the dye of the present invention for a long time (a sufficient time for the adsorption reaction to reach equilibrium).
  • a dye adsorption dye solution comprising the solution and the dye of the present invention for a long time (a sufficient time for the adsorption reaction to reach equilibrium).
  • it is preferably immersed at 0 to 150 ° C. for 5 seconds or more and 72 hours or less, preferably 10 ° C. to 80 ° C. for 1 minute or more and 48 hours or less.
  • any solution that can dissolve the dye of the present invention can be used without any particular limitation, for example, ethanol, methanol, isopropanol, toluene, t-butanol, acetonitrile, acetone, n-butanol, etc.
  • Ethanol and toluene can be preferably used.
  • the dye solution for dye adsorption comprising the solution and the sensitizing dye of the present invention may be heated to 50 ° C. to 100 ° C. as necessary. The adsorption of the dye may be performed before or after application of the semiconductor fine particles. Further, the semiconductor fine particles and the dye may be applied and adsorbed simultaneously. Unadsorbed dye is removed by washing.
  • suck a pigment
  • One kind of adsorbing dye may be used, or several kinds may be mixed and used. When mixing, 2 or more types of the pigment
  • the dye to be mixed is selected so as to make the wavelength range of photoelectric conversion as wide as possible. When mixing the dyes, it is necessary to prepare a dye solution for dye adsorption by dissolving all the dyes.
  • the total amount of the dye used is preferably 0.01 to 100 mmol, more preferably 0.1 to 50 mmol, and particularly preferably 0.1 to 10 mmol per 1 m 2 of the support.
  • the amount of the dye of the present invention is preferably 5 mol% or more.
  • the adsorption amount of the dye to the semiconductor fine particles is preferably 0.001 to 1 mmol, more preferably 0.1 to 0.5 mmol, with respect to 1 g of the semiconductor fine particles.
  • a colorless compound may be co-adsorbed for the purpose of reducing the interaction between dyes such as association.
  • the hydrophobic compound to be co-adsorbed include steroid compounds having a carboxyl group (for example, cholic acid, pivalic acid) and the like.
  • the surface of the semiconductor fine particles may be treated with amines.
  • Preferred amines include 4-tert-butylpyridine, polyvinylpyridine and the like. These may be used as they are in the case of a liquid, or may be used by dissolving in an organic solvent.
  • the counter electrode serves as the positive electrode of the photoelectrochemical cell.
  • the counter electrode is usually synonymous with the conductive support described above, but the support is not necessarily required in a configuration in which the strength is sufficiently maintained. However, having a support is advantageous in terms of hermeticity.
  • the material for the counter electrode include platinum, carbon, conductive polymer, and the like. Preferable examples include platinum, carbon, and conductive polymer.
  • the structure of the counter electrode a structure having a high current collecting effect is preferable.
  • Preferred examples include JP-A-10-505192.
  • a composite electrode such as titanium oxide and tin oxide (TiO 2 / SnO 2 ) may be used.
  • TiO 2 / SnO 2 titanium oxide and tin oxide
  • a mixed electrode of titania for example, Japanese Patent Application Laid-Open No. 2000-11913 is cited.
  • Examples of mixed electrodes other than titania include Japanese Patent Application Laid-Open Nos. 2001-185243 and 2003-282164.
  • the structure of the element may have a structure in which a first electrode layer, a first photoelectric conversion layer, a conductive layer, a second photoelectric conversion layer, and a second electrode layer are sequentially stacked.
  • the dyes used for the first photoelectric conversion layer and the second photoelectric conversion layer may be the same or different, and when they are different, it is preferable that the absorption spectra are different.
  • the light receiving electrode may be a tandem type in order to increase the utilization rate of incident light.
  • Examples of preferred tandem type configurations include those described in JP-A Nos. 2000-90989 and 2002-90989.
  • a light management function for efficiently performing light scattering and reflection inside the light receiving electrode layer may be provided.
  • Preferable examples include those described in JP-A-2002-93476.
  • a short-circuit prevention layer between the conductive support and the porous semiconductor fine particle layer in order to prevent reverse current due to direct contact between the electrolyte and the electrode.
  • Preferable examples include Japanese Patent Application Laid-Open No. 06-507999.
  • a spacer or a separator In order to prevent contact between the light receiving electrode and the counter electrode, it is preferable to use a spacer or a separator.
  • a preferable example is JP-A-2001-283941.
  • Cell and module sealing methods include polyisobutylene thermosetting resin, novolak resin, photo-curing (meth) acrylate resin, epoxy resin, ionomer resin, glass frit, method using aluminum alkoxide for alumina, low melting point glass paste It is preferable to use a laser melting method. When glass frit is used, powder glass mixed with acrylic resin as a binder may be used.
  • the photoelectric conversion element 10 shown in FIG. 1 was produced as follows. On the glass substrate, tin oxide doped with fluorine was formed as a transparent conductive film by sputtering, and this was scribed with a laser to divide the transparent conductive film into two parts. Next, 32 g of anatase-type titanium oxide (P-25 (trade name) manufactured by Nippon Aerosil Co., Ltd.) is mixed with 100 ml of a mixed solvent having a volume ratio of water and acetonitrile of 4: 1, and a rotating / revolving mixing conditioner is prepared. The resulting mixture was uniformly dispersed and mixed to obtain a semiconductor fine particle dispersion.
  • P-25 trade name
  • a mixed solvent having a volume ratio of water and acetonitrile of 4: 1
  • This dispersion was applied to a transparent conductive film and heated at 500 ° C. to produce a light receiving electrode. Thereafter, similarly, a dispersion containing 40:60 (mass ratio) of silica particles and rutile-type titanium oxide is prepared, and this dispersion is applied to the light receiving electrode and heated at 500 ° C. to form an insulating porous material. Formed body. Next, a carbon electrode was formed as a counter electrode. Next, the glass substrate on which the insulating porous material was formed was immersed in an ethanol solution (3 ⁇ 10 ⁇ 4 mol / l) of a sensitizing dye described in Table 1 below at 40 ° C. for 48 hours.
  • the glass dyed with the sensitizing dye was immersed in a 10% ethanol solution of 4-tert-butylpyridine for 30 minutes, then washed with ethanol and naturally dried.
  • the thickness of the photosensitive layer thus obtained was 10 ⁇ m, and the coating amount of semiconductor fine particles was 20 g / m 2 .
  • As the electrolytic solution a methoxypropionitrile solution of dimethylpropylimidazolium iodide (0.5 mol / l) and iodine (0.1 mol / l) was used.
  • a comparative dye having the following structure was used.
  • the evaluation criteria of the experimental results are ⁇ for conversion efficiency of 3.5% or more, ⁇ for 2.5% or more and less than 3.5%, ⁇ for 2.0% or more and less than 2.5%, Those with less than 2.0% were evaluated as x.
  • the reduction rate of the conversion efficiency after 300-hour dark storage at 70 degreeC and the reduction rate of the conversion efficiency after 500-hour continuous light irradiation were measured.
  • the conversion efficiency decrease rate was less than 3% of fresh, ⁇ , 3% to less than 5%, ⁇ , 5% to less than 10%, ⁇ , 10% or more to x.
  • the results are shown in the column of wet heat durability (darkness storage durability) in Table 8-2.
  • the following sensitizing dye S-1 was used.
  • the electrochemical cell produced using the dye of the present invention particularly when A2 to A4, A11 to A13, A-15, and A-16 are used as the dye Shows a high conversion efficiency of 3.5% or more. Even when other dyes of the present invention were used, the conversion efficiency was at a relatively high level of 2.5% or more and less than 3.5%. On the other hand, the experimental result of Sample No. 17 was insufficient with a conversion efficiency of less than 2.0%.
  • Example 2 An ITO film was produced on a glass substrate, and an FTO film was laminated thereon to produce a transparent conductive film. Then, a transparent electrode plate was obtained by forming an oxide semiconductor porous film on the transparent conductive film. And the photoelectrochemical cell 100 was produced using the transparent electrode plate, and the conversion efficiency was measured.
  • the detailed method is as follows (1) to (5).
  • the FTO membrane raw material compound solution obtained in (2) was sprayed for 2 minutes 30 seconds under the same conditions.
  • a transparent electrode plate was obtained in which an ITO film having a thickness of 530 nm and an FTO film having a thickness of 170 nm were sequentially formed on the heat-resistant glass plate.
  • a transparent electrode plate in which only a 530 nm thick ITO film is formed on a heat resistant glass plate having a thickness of 2 mm and a transparent electrode plate in which only a 180 nm thick FTO film is similarly formed are formed.
  • These three kinds of transparent electrode plates were heated in a heating furnace at 450 ° C. for 2 hours.
  • the oxide semiconductor porous film 15 is formed by dispersing fine particles of titanium oxide having an average particle size of about 230 nm in 100 ml of acetonitrile to form a paste, applying this to the transparent electrode 11 to a thickness of 15 ⁇ m by a bar coating method, and drying.
  • the oxide semiconductor porous film 15 was loaded with the dyes listed in Table 2 by baking at 450 ° C. for 1 hour.
  • the immersion conditions in the dye solution were the same as in Experiment 1.
  • a conductive substrate in which an ITO film and an FTO film were laminated on a glass plate was used for the counter electrode 16, and an electrolytic solution made of a non-aqueous solution of iodine / iodide was used for the electrolyte layer 17.
  • the planar dimension of the photoelectrochemical cell was 25 mm ⁇ 25 mm.
  • the conversion efficiency decrease rate was less than 3% of the fresh, ⁇ , 3% to less than 5%, ⁇ , 5% to less than 10%, and 10% or more to x.
  • Sample No. using sensitizing dye A 11 to 13 the conversion efficiency is low, whereas sample No. From 1 to 9, it was found that both the initial value of the conversion efficiency and the durability were excellent.
  • the conversion efficiency is particularly high as compared with the case where only an ITO film or only an FTO film is used. It was found that those using these dyes were highly effective.
  • test cell (i) A collecting electrode was arranged on the FTO film to produce a photoelectrochemical cell, and the conversion efficiency was evaluated. Evaluation was made into two types, test cell (i) and test cell (iv) as follows.
  • etching was performed using hydrofluoric acid.
  • a metal conductive layer (seed layer) was formed thereon by sputtering to enable plating formation, and a metal wiring layer 3 was further formed by additive plating.
  • the metal wiring layer 3 was formed in a convex lens shape from the surface of the transparent substrate 2 to a height of 3 ⁇ m.
  • the circuit width was 60 ⁇ m.
  • an FTO film having a thickness of 400 nm was formed as the shielding layer 5 by the SPD method to obtain an electrode substrate (i).
  • the cross-sectional shape of the electrode substrate (i) was as shown in FIG. 2 in JP-A No. 2004-146425.
  • a dispersion obtained by dispersing titanium oxide having an average particle diameter of 25 nm in 100 ml of acetonitrile was applied and dried, and heated and sintered at 450 ° C. for 1 hour.
  • a methoxyacetonitrile solution containing 0.5M iodide and 0.05M iodine as the main components was injected from the electrolyte solution inlet previously opened on the platinum sputter electrode side, and filled between the electrodes. It was. Further, the peripheral part and the electrolyte solution injection port were finally sealed with an epoxy-based sealing resin, and a silver paste was applied to the current collecting terminal part to obtain a test cell (i). The photoelectric conversion characteristics of the test cell (i) were evaluated using pseudo sunlight of AM1.5. The results are shown in Table 3.
  • Test cell (iv) A glass substrate with a 100 ⁇ 100 mm FTO film was prepared in the same manner as in the test cell (i).
  • a metal wiring layer 3 (gold circuit) was formed on the FTO glass substrate by additive plating.
  • the metal wiring layer 3 (gold circuit) was formed in a lattice shape on the substrate surface, and had a circuit width of 50 ⁇ m and a circuit thickness of 5 ⁇ m.
  • an FTO film having a thickness of 300 nm was formed as a shielding layer 5 by the SPD method to obtain a test cell (iv).
  • a test cell (iv) was produced in the same manner as the test cell (i) using the electrode substrate (iv).
  • the photoelectric conversion characteristics of the test cell (iv) were evaluated by AM1.5 artificial sunlight, and the results are shown in Table 3. As a result, conversion efficiency of 3.5% or more is ⁇ , 2.5% or more and less than 3.5% is ⁇ , 2.0% or more and less than 2.5% is ⁇ , 2.0% Those less than were evaluated as x.
  • the reduction rate of the conversion efficiency after 300-hour dark storage at 80 degreeC and the reduction rate of the conversion efficiency after 500-hour continuous light irradiation were measured.
  • the conversion efficiency decrease rate was less than 3% of the fresh, ⁇ , 3% to less than 5%, ⁇ , 5% to less than 10%, and 10% or more to x.
  • Example 4 Tests were conducted on a method for producing peroxotitanic acid and titanium oxide fine particles and a method for producing an oxide semiconductor film using the peroxotitanic acid and titanium oxide fine particles, and a photoelectrochemical cell was produced and evaluated.
  • Photovoltaic cell (A) (1) Preparation of coating liquid (A) for forming an oxide semiconductor film 5 g of titanium hydride is suspended in 1 liter of pure water, 400 g of a 5 mass% hydrogen peroxide solution is added over 30 minutes, and then 80 A solution of peroxotitanic acid was prepared by heating to ° C and dissolution. 90% by volume was taken from the total amount of this solution, adjusted to pH 9 by adding concentrated aqueous ammonia, placed in an autoclave, hydrothermally treated at 250 ° C. for 5 hours under saturated vapor pressure, and titania colloidal particles (A) Was prepared. The obtained titania colloidal particles were anatase type titanium oxide having high crystallinity by X-ray diffraction.
  • the obtained titania colloidal particles (A) was concentrated to 10 wt%, the peroxotitanic acid solution were mixed, the titanium of the mixed solution TiO 2 terms, TiO 2 mass of 30 mass% Then, hydroxypropylcellulose was added as a film formation aid so that a coating solution for forming a semiconductor film was prepared.
  • oxide semiconductor film (A) Next, the coating solution was applied on a transparent glass substrate on which fluorine-doped tin oxide was formed as an electrode layer, dried naturally, and subsequently 6000 mJ using a low-pressure mercury lamp. The peroxoacid was decomposed by irradiating with / cm 2 of ultraviolet rays, and the coating film was cured. The coating film was heated at 300 ° C. for 30 minutes to decompose and anneal the hydroxypropyl cellulose to form an oxide semiconductor film (A) on the glass substrate.
  • photoelectric cell (A) The glass substrate on which the oxide semiconductor film (A) adsorbed with the dye produced in (2) was formed was used as one electrode, and the other electrode was fluorine-doped. A transparent glass substrate carrying tin oxide as an electrode and carrying platinum on it is placed facing it, the sides are sealed with resin, the electrolyte solution (4) is sealed between the electrodes, and the electrodes are lead between them. Photoelectric cells (A) were prepared by connecting with wires.
  • Photoelectric cell (A) was irradiated with light of 100 W / m 2 with a solar simulator, measured ⁇ (conversion efficiency), and the results are shown in Table 4. Indicated.
  • titania colloidal particles (D) are concentrated to 10% by mass, and hydroxypropyl cellulose is added as a film forming aid so as to be 30% by mass in terms of TiO 2 to form a semiconductor film.
  • a coating solution was prepared.
  • the coating solution is applied onto a transparent glass substrate on which fluorine-doped tin oxide is formed as an electrode layer, dried naturally, and subsequently irradiated with 6000 mJ / cm 2 of ultraviolet rays using a low-pressure mercury lamp to form a film. Cured. Furthermore, it heated at 300 degreeC for 30 minute (s), decomposed
  • the dye of the present invention was adsorbed as a spectral sensitizing dye in the same manner as the oxide semiconductor film (A). Then, the photoelectric cell (D) was created by the method similar to a photoelectric cell (A), and (eta) was measured.
  • the experimental results are shown in Table 4. As a result, conversion efficiency of 3.5% or more is ⁇ , 2.5% or more and less than 3.5% is ⁇ , 2.0% or more and less than 2.5% is ⁇ , 2.0% Less than were shown as x.
  • the reduction rate of the conversion efficiency after 300-hour dark storage at 80 degreeC and the reduction rate of the conversion efficiency after 600 hours continuous light irradiation were measured. As a result of evaluating the durability, the conversion efficiency decrease rate was less than 3% of the fresh, ⁇ , 3% to less than 5%, ⁇ , 5% to less than 10%, and 10% or more to x.
  • Titanium oxide was prepared or synthesized by changing the method, an oxide semiconductor film was prepared from the obtained titanium oxide, and a photoelectrochemical cell was evaluated.
  • titanium oxide by heat treatment Using commercially available anatase-type titanium oxide (trade name ST-01, manufactured by Ishihara Sangyo Co., Ltd.), this is heated to about 900 ° C and converted to blue-kite type titanium oxide. Further, it was heated to about 1,200 ° C. to obtain a rutile type titanium oxide. Respectively, comparative titanium oxide 1 (anatase type), titanium oxide 1 (blue kite type), and comparative titanium oxide 2 (rutile type) are used.
  • the titanium tetrachloride concentration was 0.25 mol / liter (2% by mass in terms of titanium oxide).
  • the reaction solution started to become cloudy immediately after dropping, but kept at the same temperature. After the dropping was completed, the temperature was further raised and heated to the vicinity of the boiling point (104 ° C.). The reaction was terminated. The sol obtained by the reaction was filtered, and then powdered using a vacuum dryer at 60 ° C.
  • Ti content 28% by mass, specific gravity 1.5, purity 99.9%
  • distilled water 500 ml of this solution was put into a reaction tank equipped with a reflux condenser, and ozone gas with a purity of 80% was bubbled from the ozone gas generator at 1 L / min while heating at 85 ° C. to carry out an oxidation reaction. This state was maintained for 2 hours to complete the reaction.
  • the obtained sol was filtered and vacuum-dried to obtain a powder.
  • the ratio of (peak intensity on the surface of blue kite type 121) / (peak intensity at the position where the three overlap) is 0.85, (rutile main peak intensity) /
  • the ratio (peak intensity at the position where the three lines overlap) was 0.
  • the titanium dioxide was about 98% by mass for the blue kite type, 0% by mass for the rutile type, 0% by mass for the anatase type, and about 2% was amorphous.
  • the average particle diameter of the primary particles was 0.05 ⁇ m.
  • a photoelectric conversion element having the structure shown in FIG. 1 of JP-A No. 2000-340269 was produced as follows using titanium oxide prepared by the above titanium oxides 1 to 3 as a semiconductor.
  • a glass substrate was coated with fluorine-doped tin oxide to form a conductive transparent electrode.
  • a paste using each titanium oxide particle as a raw material was formed on the electrode surface, applied to a thickness of 50 ⁇ m by a bar coating method, and then baked at 500 ° C. to form a thin layer having a thickness of about 20 ⁇ m.
  • a 3 ⁇ 10 ⁇ 4 molar ethanol solution of the dye was prepared, and the glass substrate on which the above-mentioned titanium oxide thin layer was formed was immersed therein and kept at room temperature for 12 hours.
  • a photoelectric conversion element having the configuration shown in FIG. 1 of JP-A No. 2000-340269 was prepared using an iodine salt of tetrapropylammonium and an acetonitrile solution of lithium iodide as an electrolytic solution and using platinum as a counter electrode.
  • For photoelectric conversion light from a 160-w high-pressure mercury lamp (the infrared part was cut by a filter) was applied to the above-mentioned element, and the conversion efficiency at that time was measured.
  • the results are shown in Table 5. The results are: conversion efficiency of 3.5% or more ⁇ , 2.5% or more of less than 3.5% ⁇ , 2.0% or more of less than 2.5% ⁇ , 2.0% Less than were shown as x.
  • the reduction rate of the conversion efficiency after 300-hour dark storage at 80 degreeC and the reduction rate of the conversion efficiency after 600 hours continuous light irradiation were measured.
  • the conversion efficiency decrease rate was less than 3% of the fresh, ⁇ , 3% to less than 5%, ⁇ , 5% to less than 10%, and 10% or more to x.
  • a titania slurry was prepared by placing spherical TiO 2 particles (anatase type, average particle size: 25 nm, hereinafter referred to as spherical TiO 2 particles 1) in a nitric acid solution and stirring. Next, a cellulose binder as a thickener was added to the titania slurry and kneaded to prepare a paste.
  • a paste was prepared.
  • a paste was prepared.
  • Photoelectrochemical cell 1 A photoelectrode having the same configuration as that of the photoelectrode 12 shown in FIG. 5 described in JP-A-2002-289274 is prepared by the following procedure, and further a dye-sensitized type using the photoelectrode except for the photoelectrode. A 10 ⁇ 10 mm scale photoelectrochemical cell 1 having the same configuration as that of the solar cell 20 was produced.
  • a transparent electrode in which a fluorine-doped SnO 2 conductive film (film thickness: 500 nm) was formed on a glass substrate was prepared. Then, the paste 2 was screen-printed on the SnO 2 conductive film and then dried. Then, it baked on the conditions of 450 degreeC in the air. Further, by repeating this screen printing and baking using the paste 4, a semiconductor electrode having the same configuration as the semiconductor electrode 2 shown in FIG.
  • dye was made to adsorb
  • an iodine-based redox solution containing iodine and lithium iodide as a platinum electrode (thickness of Pt thin film; 100 nm) having the same shape and size as the above-described photoelectrode as a counter electrode and electrolyte E was prepared. Furthermore, a spacer S (trade name: “Surlin”) manufactured by DuPont having a shape corresponding to the size of the semiconductor electrode was prepared. As shown in FIG. 3 described in JP-A-2002-289274, the photoelectrode 10 and the counter electrode were prepared. The photoelectrochemical cell 1 was completed by facing the CE through the spacer S and filling the above electrolyte therein.
  • Photoelectrochemical cell 2 The photoelectrode 10 shown in FIG. 1 described in JP-A No. 2002-289274 and the diagram described in JP-A No. 2002-289274 are the same as those of the photoelectrochemical cell 1 except that the semiconductor electrode is manufactured as follows.
  • Paste 2 was used as a semiconductor layer forming paste. Then, paste 2 was screen-printed on the SnO 2 conductive film and then dried. Then, it baked on the conditions of 450 degreeC in the air, and formed the semiconductor layer.
  • Paste 3 was used as the innermost layer forming paste of the light scattering layer.
  • the paste 5 was used as the outermost layer forming paste of the light scattering layer. Then, a light scattering layer was formed on the semiconductor layer in the same manner as in the dye-sensitized solar cell 1.
  • a semiconductor electrode having the same configuration as the semiconductor electrode 2 shown in FIG. 1 described in JP-A No. 2002-289274 (light receiving surface area: 10 mm ⁇ 10 mm, layer thickness: 10 ⁇ m, layer thickness of the semiconductor layer) 3 ⁇ m, the thickness of the innermost layer; 4 ⁇ m, the content of rod-like TiO 2 particles 1 contained in the innermost layer; 10% by mass, the thickness of the outermost layer; 3 ⁇ m, contained in the innermost layer
  • the content ratio of the rod-like TiO 2 particles 1 to be formed; 50% by mass) was formed, and a photoelectrode containing no sensitizing dye was produced.
  • the photoelectrochemical cell 2 was completed by making the photoelectrode, the counter electrode CE, and the spacer S face each other and filling the above electrolyte therein.
  • Photoelectrochemical cell 3 The light shown in FIG. 5 was prepared by the same procedure as that of the photoelectrochemical cell 1 except that the paste 1 was used as the semiconductor layer forming paste and the paste 4 was used as the light scattering layer forming paste when the semiconductor electrode was manufactured.
  • a photoelectrode and photoelectrochemical cell 3 having the same configuration as that of the electrode 10 and the photoelectrochemical cell 20 shown in FIG. 3 described in JP-A-2002-289274 were produced.
  • the semiconductor electrode has a light receiving surface area of 10 mm ⁇ 10 mm, a layer thickness of 10 ⁇ m, a semiconductor layer thickness of 5 ⁇ m, a light scattering layer thickness of 5 ⁇ m, and the rod-like TiO 2 particles 1 contained in the light scattering layer. Content rate: 30% by mass.
  • Photoelectrochemical cell 4 In the production of the semiconductor electrode, the light shown in FIG. 5 was obtained by the same procedure as that of the photoelectrochemical cell 1 except that the paste 2 was used as the semiconductor layer forming paste and the paste 6 was used as the light scattering layer forming paste. A photoelectrode and photoelectrochemical cell 4 having the same configuration as the electrode 10 and the photoelectrochemical cell 20 shown in FIG. 3 described in JP-A-2002-289274 were produced.
  • the semiconductor electrode has a light receiving surface area: 10 mm ⁇ 10 mm, layer thickness: 10 ⁇ m, semiconductor layer thickness: 6.5 ⁇ m, light scattering layer thickness: 3.5 ⁇ m, plate-like contained in the light scattering layer
  • the content of mica particles 1 was 20% by mass.
  • Photoelectrochemical cell 5 In the production of the semiconductor electrode, the photoelectrode and the photoelectrochemistry were prepared in the same procedure as in the photoelectrochemical cell 1 except that the paste 2 was used as the semiconductor layer forming paste and the paste 8 was used as the light scattering layer forming paste. Battery 5 was produced. The content ratio of the rod-shaped TiO 2 particles 3 contained in the light scattering layer of the semiconductor electrode; was 30 wt%.
  • Photoelectrochemical cell 6 In the production of the semiconductor electrode, the photoelectrode and the photoelectrochemical process were performed in the same manner as in the photoelectrochemical cell 1 except that the paste 2 was used as the semiconductor layer forming paste and the paste 9 was used as the light scattering layer forming paste. A battery 6 was produced. The content ratio of the rod-shaped TiO 2 particles 4 contained in the light scattering layer of the semiconductor electrode; was 30 wt%.
  • Photoelectrochemical cell 7 In the production of the semiconductor electrode, the photoelectrode and the photoelectrochemistry were prepared in the same procedure as in the photoelectrochemical cell 1 except that the paste 2 was used as the semiconductor layer forming paste and the paste 10 was used as the light scattering layer forming paste. Battery 7 was produced. The content ratio of the rod-shaped TiO 2 particles 5 contained in the light scattering layer of the semiconductor electrode; was 30 wt%.
  • Photoelectrochemical cell 8 In the production of the semiconductor electrode, the photoelectrode and the photoelectrochemistry were prepared in the same procedure as in the photoelectrochemical cell 1 except that the paste 2 was used as the semiconductor layer forming paste and the paste 11 was used as the light scattering layer forming paste. Battery 8 was produced. The content ratio of the rod-shaped TiO 2 particles 6 contained in the light scattering layer of the semiconductor electrode; was 30 wt%.
  • Photoelectrochemical cell 9 In the production of the semiconductor electrode, the photoelectrode and the photoelectrochemistry were prepared in the same procedure as in the photoelectrochemical cell 1 except that the paste 2 was used as the semiconductor layer forming paste and the paste 13 was used as the light scattering layer forming paste. A battery 9 was produced. The content ratio of the rod-shaped TiO 2 particles 8 contained in the light scattering layer of the semiconductor electrode; was 30 wt%.
  • Photoelectrochemical cell 10 In the production of the semiconductor electrode, the photoelectrode and the photoelectrochemical process were performed in the same manner as in the photoelectrochemical cell 1 except that the paste 2 was used as the semiconductor layer forming paste and the paste 14 was used as the light scattering layer forming paste. Battery 10 was produced. The content of the rod-like TiO 2 particles 9 contained in the light scattering layer of the semiconductor electrode was 30% by mass.
  • Photoelectrochemical cell 11 Similar to the photoelectrochemical cell 1 except that a semiconductor electrode (light-receiving surface area: 10 mm ⁇ 10 mm, layer thickness: 10 ⁇ m) made of only the semiconductor layer using only the paste 2 was manufactured in the manufacture of the semiconductor electrode.
  • a photoelectrode and a comparative photoelectrochemical cell 1 were prepared according to the procedure.
  • Electrochemical battery 12 In the production of the semiconductor electrode, the photoelectrode and the comparative photoelectricity were prepared in the same procedure as in the photoelectrochemical cell 1 except that the paste 2 was used as the semiconductor layer forming paste and the paste 7 was used as the light scattering layer forming paste. A chemical battery 2 was produced. The content ratio of the rod-shaped TiO 2 particles 2 contained in the light scattering layer of the semiconductor electrode; was 30 wt%.
  • the reduction rate of the conversion efficiency after 300-hour dark storage at 80 degreeC and the reduction rate of the conversion efficiency after 600 hours continuous light irradiation were measured.
  • the conversion efficiency decrease rate was less than 3% of the fresh, ⁇ , 3% to less than 5%, ⁇ , 5% to less than 10%, and 10% or more to x.
  • the dye of the present invention has high conversion efficiency and excellent durability.
  • Example 7 A slurry obtained by adding metal alkoxide to metal oxide fine particles was applied to a conductive substrate, and then UV ozone irradiation, UV irradiation or drying was performed to produce an electrode. Then, the photoelectrochemical cell was produced and the conversion efficiency was measured.
  • Titanium oxide was used as the metal oxide fine particles.
  • P25 powder (trade name, manufactured by Degussa) having a mass ratio of 30% rutile type and 70% anatase type and an average particle size of 25 nm was used.
  • metal oxide fine particle powder Pretreatment of metal oxide fine particle powder
  • the metal oxide fine particles were previously heat-treated to remove surface organic substances and moisture.
  • the fine particles were heated in an oven at 450 ° C. in the atmosphere for 30 minutes.
  • the metal alkoxide that plays a role in bonding metal oxide fine particles includes titanium (IV) tetraisopropoxide (TTIP) as a titanium raw material, zirconium (IV) tetra n-propoxide as a zirconium raw material, and niobium as a niobium raw material.
  • TTIP titanium
  • IV tetraisopropoxide
  • V Pentaethoxide (all manufactured by Aldrich) was used.
  • the molar concentration ratio between the metal oxide fine particles and the metal alkoxide is appropriately adjusted according to the metal oxide fine particle diameter so that the amorphous layer generated by hydrolysis of the metal alkoxide is not excessively thick and the particles can be sufficiently bonded to each other. did. All metal alkoxides were 0.1M ethanol solutions. When mixing titanium oxide fine particles and titanium (IV) tetraisopropoxide (TTIP), 3.55 g of 0.1M TTIP solution was mixed with 1 g of titanium oxide fine particles. At this time, the titanium oxide concentration in the obtained paste was about 22% by mass, and the viscosity was appropriate for coating.
  • TTIP titanium (IV) tetraisopropoxide
  • the titanium oxide, TTIP, and ethanol at this time were 1: 0.127: 3.42 by mass ratio, and 1: 0.036: 5.92 by molar ratio.
  • a mixed paste of titanium oxide fine particles and an alkoxide other than TTIP was prepared so that the fine particle concentration was 22% by mass.
  • the content was 16% by mass.
  • the metal alkoxide solution was mixed at a ratio of 5.25 g to 1 g of the metal oxide fine particles.
  • the metal oxide fine particles and the metal alkoxide solution were stirred for 2 hours with a magnetic stirrer in a sealed container to obtain a uniform paste.
  • a doctor blade method, a screen printing method, a spray coating method, or the like can be used, and an appropriate paste viscosity is appropriately selected depending on the application method.
  • a method of applying simply with a glass rod similar to the doctor blade method was used.
  • the concentration of the metal oxide fine particles giving an appropriate paste viscosity was approximately in the range of 5 to 30% by mass.
  • the layer thickness of the amorphous metal oxide generated by the decomposition of the metal alkoxide is in the range of about 0.1 to 0.6 nm in this embodiment. A range of about 0.05 to 1.3 nm was appropriate for room temperature film formation by this method.
  • a porous film was prepared by changing the conditions for the presence or absence of UV ozone treatment, UV irradiation treatment, or drying treatment.
  • the film after application to the conductive substrate was air-dried at room temperature in the atmosphere for about 2 minutes.
  • the metal alkoxide in the paste was hydrolyzed by moisture in the atmosphere, and amorphous titanium oxide, zirconium oxide, and niobium oxide were formed from Ti alkoxide, Zr alkoxide, and Nb alkoxide, respectively. Since the produced amorphous metal oxide plays a role of adhering metal oxide fine particles and the film to the conductive substrate, a porous film excellent in mechanical strength and adhesion was obtained only by air drying.
  • UV ozone treatment For UV ozone treatment, NL-UV253 UV ozone cleaner manufactured by Nippon Laser Electronics was used. The UV light source was equipped with three 4.5 W mercury lamps having emission lines at 185 nm and 254 nm, and the sample was placed horizontally at a distance of about 6.5 cm from the light source. Ozone is generated by introducing an oxygen stream into the chamber. In this example, this UV ozone treatment was performed for 2 hours. Note that no decrease in the conductivity of the ITO film and the FTO film due to this UV ozone treatment was observed.
  • UV treatment Similarly to the UV ozone treatment, the treatment was performed for 2 hours, except that the inside of the chamber was replaced with nitrogen. No decrease in the conductivity of the ITO film and FTO film due to the UV treatment was observed.
  • the dye of the present invention was used as a sensitizing dye, and a 0.5 mM ethanol solution was prepared.
  • the porous film produced by the above process was dried in an oven at 100 ° C. for 1 hour, then immersed in a sensitizing dye solution, and allowed to stand at room temperature for 50 minutes to adsorb the sensitizing dye on the titanium oxide surface. did.
  • the sample after adsorption of the sensitizing dye was washed with ethanol and air-dried.
  • a photoelectrochemical cell was fabricated by using a conductive substrate on which a porous film after dye adsorption was formed as a photoelectrode, and an ITO / PET film or FTO / glass counter electrode in which platinum fine particles were modified by sputtering.
  • the effective area of the photoelectrode was about 0.2 cm 2 .
  • 3-methoxypropionitrile containing 0.5 M LiI, 0.05 M I 2 and 0.5 M t-butylpyridine was introduced into the gap between both electrodes by capillary action.
  • the battery performance was evaluated by measuring the photocurrent action spectrum under irradiation with a constant number of photons (1016 cm ⁇ 2 ) and IV measurement under irradiation with AM1.5 simulated sunlight (100 mW / cm 2 ).
  • a CEP-2000 type spectral sensitivity measuring device manufactured by Spectrometer Co., Ltd. was used for these measurements.
  • the obtained output characteristic values are summarized in Table 7. The results are: conversion efficiency of 2.5% or more ⁇ , 2.0% or more and less than 2.5% ⁇ , 1.5% or more and less than 2.0% ⁇ , 1.5% Less than were shown as x.
  • the columns of “UV ozone”, “UV”, and “dry” indicate the presence / absence of UV ozone treatment, UV irradiation treatment, and drying treatment after formation of the porous film and before sensitizing dye adsorption, respectively.
  • the processed one is “ ⁇ ”, and the unprocessed one is “ ⁇ ”.
  • the column of “ Pretreatment of TiO 2 ” in Table 7 indicates the presence or absence of pretreatment of titanium oxide fine particles (heat treatment in an oven at 450 ° C. for 30 minutes).
  • Samples 6, 14, and 22 represent samples using a paste having a high TTIP concentration (titanium oxide: TTIP molar ratio of 1: 0.356).
  • a conductive film was formed on a glass substrate by sputtering tin oxide doped with fluorine as a transparent conductive film.
  • a dispersion containing anatase-type titanium oxide particles on this conductive film (anatase-type titanium oxide (P-25 (trade name) manufactured by Nippon Aerosil Co., Ltd.)) was added to 100 ml of a mixed solvent having a volume ratio of water and acetonitrile of 4: 1. 32 g of the mixture, and using a rotating / revolving mixing conditioner, uniformly dispersed and mixed to obtain a semiconductor fine particle dispersion), and then sintered at 500 ° C. to form a photosensitive layer having a thickness of 15 ⁇ m. Formed.
  • the conversion efficiency is ⁇ for those with 3.5% or more, ⁇ for 2.5% or more and less than 3.5%, ⁇ for 2.0% or more and less than 2.5%, and less than 2.0%. Things were displayed as x. Table 8 also shows the results of photoelectric conversion elements using an electrolytic solution to which no benzimidazole compound was added.
  • Example 8-2 ⁇ Experiment 8> No.
  • a sealing agent for the photoelectric conversion element using the compound No. 5 as a sealant, a glass sphere having a diameter of 25 ⁇ m is almost uniform in a resin composition comprising Epicoat 828 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), a curing agent and a plastic paste.
  • Epicoat 828 trade name, manufactured by Japan Epoxy Resin Co., Ltd.
  • a dye-sensitized solar cell was prepared in the same manner except that the sealant paste dispersed in was used, and the photoelectric conversion efficiency was measured.
  • the conversion efficiency ( ⁇ ) of each dye-sensitized solar cell obtained by this, the reduction rate of the conversion efficiency after 1000 hours of dark storage at 85 ° C., and the reduction rate of the conversion efficiency after 500 hours of continuous light irradiation were measured. .
  • the conversion efficiency is 7.5% or more for ⁇ , 7.3% to less than 7.5% for ⁇ , 7.1% to less than 7.3% for ⁇ , 7. Those less than 1% were evaluated as x.
  • the conversion efficiency decrease rate was less than 3% of fresh, ⁇ , 3% to less than 5%, ⁇ , 5% to less than 10%, ⁇ , 10% or more to x.
  • the results are shown in the dark storage durability column and continuous light irradiation durability column of Table 8-2.
  • the initial value of the conversion efficiency of the dye-sensitized solar cell of the present invention showed a high value of 7.0% or more. Moreover, it turned out that durability is excellent compared with a comparative example with the reduction rate of 9.0% or less after storage in a dark place and after continuous light irradiation.
  • first layer the layer disposed on the side close to the transparent electrode 1
  • second layer the layer disposed on the side close to the porous body layer PS
  • slurry 1 a slurry for forming a second layer
  • a slurry for forming a first layer (P1 content; 15 mass%; hereinafter, “slurry 2” is prepared by the same preparation procedure as that of the slurry 1 except that only P25 is used without using P200. Was prepared).
  • a transparent electrode (thickness: 1.1 mm) in which a fluorine-doped SnO 2 conductive film (film thickness: 700 nm) was formed on a glass substrate (transparent conductive glass) was prepared. Then, the SnO 2 conductive film, the slurry 2 described above was coated with Bakoda, then dried. Then, it baked for 30 minutes at 450 degreeC in air
  • the second layer was formed on the first layer by repeating the same application and firing as described above using the slurry 1.
  • the semiconductor electrode 2 (light-receiving surface area; 1.0 cm 2 , the total thickness of the first layer and the second layer: 10 ⁇ m (the thickness of the first layer: 3 ⁇ m, the first layer) on the SnO 2 conductive film No. 2 layer thickness: 7 ⁇ m)
  • a photoelectrode 10 containing no sensitizing dye was prepared.
  • an ethanol solution of the dye of the present invention (sensitizing dye concentration; 3 ⁇ 10 ⁇ 4 mol / L) was prepared as a sensitizing dye.
  • the photoelectrode 10 was immersed in this solution and allowed to stand for 20 hours under a temperature condition of 80 ° C. to adsorb the sensitizing dye. Thereafter, in order to improve the open circuit voltage Voc, the dye-adsorbed semiconductor electrode was immersed in an acetonitrile solution of 4-tert-butylpyridine for 15 minutes and then dried in a nitrogen stream maintained at 25 ° C. Was completed.
  • a counter electrode CE having the same shape and size as the above photoelectrode was produced.
  • an isopropanol solution of chloroplatinic acid hexahydrate was dropped on a transparent conductive glass, dried in air, and then baked at 450 ° C. for 30 minutes to obtain a platinum sintered counter electrode CE.
  • the counter electrode CE was previously provided with a hole for injection of the electrolyte E (diameter 1 mm).
  • a spacer S (trade name: “HIMILAN”, ethylene / methacrylic acid random copolymer ionomer film) manufactured by Mitsui Dupont Polychemical Co., Ltd. having a shape matched to the size of the semiconductor electrode was prepared.
  • the photoelectrode and the counter electrode were opposed to each other through a spacer, and each was bonded by thermal welding to obtain a battery casing (no electrolyte filled).
  • the hole is closed with a member made of the same material as the spacer, and this member is thermally welded to the hole of the counter electrode to seal the hole. 1 was completed.
  • Photoelectrochemical cell 2 The photoelectrochemical cell 2 was produced in the same procedure and conditions as the photoelectrochemical cell 1 except that the concentration of zinc iodide in the liquid electrolyte was 50 mmol / L.
  • Photoelectrochemical cell 3 Comparative photoelectrochemistry was performed in the same procedure and conditions as in the photoelectrochemical cell 1 except that lithium iodide was added instead of zinc iodide in the liquid electrolyte, and the concentration of lithium iodide in the liquid electrolyte was 20 mmol / L. A battery 1 was produced.
  • Electrochemical battery 4 Comparative photoelectrochemistry in the same procedure and conditions as in the photoelectrochemical cell 1 except that lithium iodide was added instead of zinc iodide in the liquid electrolyte, and the concentration of lithium iodide in the liquid electrolyte was 100 mmol / L. Battery 2 was produced.
  • the battery characteristic evaluation test was conducted using a solar simulator (trade name; “WXS-85-H type” manufactured by Wacom), and the irradiation conditions of pseudo-sunlight from a xenon lamp light source through an AM filter (AM1.5). The measurement was performed under measurement conditions of 100 mW / cm 2 (so-called “1Sun” irradiation conditions).
  • the current-voltage characteristics were measured at room temperature using an IV tester, and the photoelectric conversion efficiency ⁇ [%] was determined from these.
  • the obtained results are shown as “fresh” in Table 9 (1 Sun irradiation conditions).
  • the photoelectric conversion efficiency ⁇ [%] of the dye-sensitized solar cells 1 and 2 and the comparative dye-sensitized solar cells 1 and 2 is 300 hours at 60 ° C. and 1 Sun irradiation under the operating condition of 10 ⁇ load.
  • Table 9 also shows the results of the durability evaluation test examined after the elapse of time.
  • the conversion efficiency of Fresh is ⁇ for those with 3.5% or more, ⁇ for those with 2.5% to less than 3.5%, ⁇ , 2.0% for those with 2.0% or more but less than 2.5% Less than were shown as x.
  • Example 10 Preparation of Titanium Dioxide Dispersion 15 g of titanium dioxide fine particles (Nippon Aerosil Co., Ltd., Degussa P-25), 45 g of water, dispersant (Triron X, manufactured by Aldrich Co., Ltd.) -100) 1 g, 30 g of zirconia beads having a diameter of 0.5 mm (manufactured by Nikkato Co., Ltd.) were added, and dispersion treatment was performed at 1500 rpm for 2 hours using a sand grinder mill (manufactured by Imex). Zirconia beads were filtered off from the resulting dispersion. The average particle diameter of the titanium dioxide fine particles in the obtained dispersion was 2.5 ⁇ m. The particle size was measured with a master sizer manufactured by MALVERN.
  • Titanium Oxide Fine Particle Layer Adsorbed with Dye 20 mm long and 20 mm wide conductive glass plate coated with fluorine-doped tin oxide (Asahi Glass Co., Ltd., TCO glass-U, surface resistance: (Approx. 30 ⁇ / m 2 ), apply adhesive tape for spacers to both ends of the conductive layer side (3 mm wide from the end), and then apply the dispersion using a glass rod on the conductive layer did. After application of the dispersion, the adhesive tape was peeled off and air-dried at room temperature for 1 day.
  • this semiconductor-coated glass plate was placed in an electric furnace (muffle furnace FP-32 manufactured by Yamato Scientific Co., Ltd.) and baked at 450 ° C. for 30 minutes. After the semiconductor-coated glass plate was taken out and cooled, it was immersed in an ethanol solution of the dyes shown in Table 10 (concentration: 3 ⁇ 10 ⁇ 4 mol / L) for 1 hour. The semiconductor-coated glass plate on which the dye was adsorbed was immersed in 4-tert-butylpyridine for 15 minutes, washed with ethanol, and naturally dried. The thickness of the dye-sensitized titanium oxide fine particle layer thus obtained was 10 ⁇ m, and the coating amount of the titanium oxide fine particles was 20 g / m 2 . The amount of dye adsorbed was in the range of 0.1 to 10 mmol / m 2 depending on the type.
  • Photoelectrochemical Battery 1 Three types of photoelectrochemical batteries 1, A and B were produced by the following method.
  • the photoelectrochemical cells of Sample Nos. 1 to 9 were obtained using the dyes shown in Table 15, the nitrogen-containing polymer compound ⁇ , and the electrophile ⁇ .
  • a photoelectrochemical cell 1-1 (sample number 1) in which the counter electrode 40 composed of 41 was sequentially laminated was obtained.
  • photoelectrochemical cells 1-2 to 1-3 were obtained in the same manner as in the above step except that the dye was changed as shown in the table.
  • Electrode A (20 mm ⁇ 20 mm) composed of a titanium oxide fine particle layer adsorbed with a dye as described above was superimposed on a platinum-deposited glass plate of the same size via a spacer. .
  • an electrolyte (0.05 mol / L of iodine using a mixture of acetonitrile and 3-methyl-2-oxazolidinone in a volume ratio of 90/10 as a solvent, lithium iodide 0 .5 mol / L solution) was infiltrated to produce Photoelectrochemical Cell A-1 (Sample No. 2).
  • Photoelectrochemical cells A-2 to A-3 were obtained in the same manner as in the above step except that the sensitizing dye was changed as shown in the table.
  • the alligator clips were connected to the conductive glass plate 10 and the platinum-deposited glass plate 40 of the photoelectrochemical cell described above, and each alligator clip was connected to a current-voltage measuring device (Keutley SMU238 type). This was irradiated with simulated sunlight from the conductive glass plate 10 side, and the generated electricity was measured with a current-voltage measuring device.
  • Table 10 summarizes the initial value (fresh) of the conversion efficiency ( ⁇ ) of the photoelectrochemical cell determined in this way and the rate of decrease in conversion efficiency after 300 hours of continuous irradiation.
  • the conversion efficiency of Fresh is ⁇ for those with 3.5% or more, ⁇ for those with 2.5% to less than 3.5%, ⁇ , 2.0% for those with 2.0% or more but less than 2.5% Less than were shown as x.
  • the coated support was then attached to a vapor deposition apparatus and further 2,2 ′, 7,7′-tetrakis (diphenylamino) -9,9′-spiro having a thickness of 100 nm by thermal vapor deposition under a vacuum of about 10-5 mbar. A layer of bifluorene was applied. Furthermore, a gold layer having a thickness of 200 nm was coated on the coated support as a counter electrode in a vapor deposition apparatus.
  • the sample thus prepared was attached to an optical device including a high-pressure lamp, an optical filter, a lens and a mounting. The intensity could be changed by using a filter and moving the lens.
  • the gold layer and the SnO 2 layer were contacted and attached to the device shown in the current measuring device while the sample was irradiated.
  • light having a wavelength of less than 430 nm was blocked using an appropriate optical filter.
  • the apparatus was adjusted so that the intensity of the radiation was approximately equal to about 1000 W / m 2 ).
  • Contacts were made on the gold layer and the SnO 2 layer, and both contacts were connected to a potentiostat while the sample was irradiated.
  • the sample using the sensitizing dye S-1 without applying an external voltage produced a current of about 90 nA, whereas the sample using the dye compound A-2 of the present invention produced a current of about 190 nA. In both samples, the current disappeared if not irradiated.
  • Example 13 125 ml of titanium isopropoxide was added dropwise to 750 ml of 0.1M nitric acid aqueous solution (manufactured by Kishida Chemical Co., Ltd.) and heated at 80 ° C. for 8 hours to cause a hydrolysis reaction, thereby preparing a sol solution.
  • the obtained sol solution is kept in a titanium autoclave at 250 ° C. for 15 hours to grow particles, and then subjected to ultrasonic dispersion for 30 minutes to obtain a colloidal solution containing titanium oxide particles having an average primary particle size of 20 nm. It was.
  • the resulting colloidal solution containing titanium oxide particles was slowly concentrated with an evaporator until the titanium oxide concentration reached 10 wt%, and then polyethylene glycol (made by Kishida Chemical Co., Ltd., weight average molecular weight: 200000) was oxidized.
  • a suspension in which titanium oxide particles were dispersed was obtained by adding 40% by weight to titanium and stirring.
  • the prepared titanium oxide suspension was applied by the doctor blade method to the transparent conductive film 2 side of the glass substrate 1 on which the SnO 2 film was formed as the transparent conductive film 2 to obtain a coating film having an area of about 10 mm ⁇ 10 mm.
  • This coating film is pre-dried at 120 ° C. for 30 minutes, and further baked at 500 ° C. for 30 minutes in an oxygen atmosphere to become the first porous semiconductor layer of the first porous photoelectric conversion layer 4.
  • the film thickness is 10 ⁇ m.
  • About a titanium oxide film was formed.
  • the glass substrate 1 provided with the transparent conductive film 2 and the porous semiconductor layer 3 is immersed in a dye solution for adsorption of the first dye heated to about 50 ° C. for 10 minutes, and the first dye is applied to the porous semiconductor layer 3. Adsorbed. Thereafter, the glass substrate 1 was washed several times with absolute ethanol and dried at about 60 ° C. for about 20 minutes. Next, the glass substrate 1 was immersed in 0.5N hydrochloric acid for about 10 minutes and then washed with ethanol to desorb the first dye adsorbed on the second porous semiconductor layer. Further, the glass substrate 1 was dried at about 60 ° C. for about 20 minutes.
  • the comparative dye S-1 and the dye A-2 of the present invention are dissolved in ethanol, and the concentration is 3 ⁇ 10.
  • a dye solution for adsorption of ⁇ 4 mol / liter of the second dye was prepared.
  • dimethylpropylimidazolium iodide has a concentration of 0.5 mol / liter
  • lithium iodide has a concentration of 0.1 mol / liter
  • iodine has a concentration of 0.05 mol / liter.
  • a redox electrolyte solution was prepared.
  • the porous semiconductor layer 3 side of the glass substrate 1 provided with the porous semiconductor layer 3 on which the first dye and the second dye are adsorbed, and the counter electrode side support 20 made of ITO glass provided with platinum as the counter electrode layer 8. It was installed so as to face the platinum side, and the prepared redox electrolyte solution was injected therebetween, and the periphery was sealed with an epoxy resin sealing material 9 to complete a dye-sensitized solar cell.
  • the second porous semiconductor layer is made the same layer as the first porous semiconductor layer, that is, the second porous semiconductor layer is formed using a titanium oxide suspension that forms the first porous semiconductor layer. Except for this, a titanium oxide film 2 was prepared in the same manner as the titanium oxide film 1, and a solar cell was similarly manufactured and evaluated using the titanium oxide film 2. The haze ratio of the porous photoelectric conversion layer was 15% (when S-1 was used) and 16% (when the dye of the present invention was used).
  • Table 11 shows the results of evaluating the obtained solar cell under measurement conditions: AM-1.5 (100 mW / cm 2).
  • the conversion efficiency is ⁇ for those with 3.5% or more, ⁇ for 2.5% or more and less than 3.5%, ⁇ for 2.0% or more and less than 2.5%, and less than 2.0%. Things were displayed as x.
  • Titanium oxide suspension was prepared by dispersing 4.0 g of commercially available titanium oxide particles (manufactured by Teika Co., Ltd., average particle size 20 nm) and 20 ml of diethylene glycol monomethyl ether for 6 hours with a paint shaker using hard glass beads. . Next, this titanium oxide suspension was applied to a glass plate (electrode layer) to which a tin oxide conductive layer had been previously attached using a doctor blade, pre-dried at 100 ° C. for 30 minutes, and then heated to 500 ° C. in an electric furnace.
  • the sensitizing dye and the comparative dye of the present invention were dissolved in ethanol to obtain a photosensitizing dye solution.
  • This photosensitizing dye solution was 5 ⁇ 10 ⁇ 4 mol / liter.
  • the glass plate on which the film-like titanium oxide is formed is placed in this solution, dye adsorption is performed at 60 ° C. for 60 minutes, and drying is performed.
  • a photoelectric conversion layer made of a dye-sensitive dye was formed (Sample A).
  • a toluene solution (1%) of polyvinylcarbazole (weight average molecular weight 3,000) as a hole transport material was applied and dried under reduced pressure to form a hole transport layer (Sample B). ).
  • first photoelectric conversion layer 4.0 g of commercially available titanium oxide particles (manufactured by Teika Co., Ltd., average particle size 30 nm) and 20 ml of diethylene glycol monomethyl ether were dispersed with a paint shaker for 6 hours using hard glass beads, and titanium oxide. A suspension was made. Next, this titanium oxide suspension was applied to a glass plate to which a tin oxide conductive layer had been previously attached using a doctor blade, preliminarily dried at 100 ° C. for 30 minutes, and then baked at 500 ° C. for 40 minutes. A titanium oxide film was obtained.
  • the dye represented by S-6 below [cis-dithiocyline-N-bis (2,2'-bipyrylyl-4,4'-dicarboxylic acid) ruthenium] was dissolved in ethanol.
  • the concentration of this dye was 3 ⁇ 10 ⁇ 4 mol.
  • the glass plate on which film-like titanium oxide is formed is put in this solution, and after dye adsorption at 720 minutes at 60 ° C., drying is performed to obtain the first photoelectric conversion layer (sample A) of the present invention. It was.
  • the dye of the present invention and the comparative dye S-1 were dissolved in dimethyl sulfoxide.
  • the concentration of this dye was 1 ⁇ 10 ⁇ 4 mol.
  • the glass plate on which film-like titanium oxide is formed is placed in this solution, and after dye adsorption at 70 ° C. for 60 minutes, drying is performed to obtain the second photoelectric conversion layer (sample B) of the present invention. It was.
  • the sample B is positioned on the sample A.
  • a liquid electrolyte was put between these two electrodes, and this side surface was sealed with resin, and then a lead wire was attached to produce a photoelectric conversion element (element configuration C) of the present invention.
  • the liquid electrolyte is a mixed solvent of acetonitrile / ethylene carbonate (volume ratio is 1: 4), tetrapropylammonium iodide and iodine, with respective concentrations of 0.46 mol / l and 0.06 mol / l. What was melt
  • a transparent conductive glass plate provided with the sample A as one electrode and carrying platinum as a counter electrode was used.
  • a liquid electrolyte was placed between the two electrodes, and this side surface was sealed with resin, and then a lead wire was attached to produce a photoelectric conversion element (element configuration D) of the present invention.
  • the obtained photoelectric conversion elements (samples C and D) were irradiated with light having an intensity of 1000 W / m 2 using a solar simulator. Conversion efficiency is 6.5% or more for ⁇ , 6.0% or more but less than 6.5% ⁇ , 5.0% or more but less than 6.0% ⁇ , less than 5.0% Things were displayed as x.
  • the photoelectric conversion element of this invention is excellent in photoelectric conversion efficiency, and it turns out that it is effective also in this type
  • the coating liquid for producing the titanium oxide film was 4.0 g of commercially available titanium oxide particles (manufactured by Teika Co., Ltd., trade name AMT-600, anatase type crystal, average particle size 30 nm, specific surface area 50 m 2 / g) and diethylene glycol monomethyl.
  • 20 ml of ether was dispersed with a paint shaker for 7 hours using glass beads to prepare a titanium oxide suspension.
  • this titanium oxide suspension is formed on a glass substrate 1 having a film thickness of about 11 ⁇ m and an area of about 10 mm ⁇ 10 mm and SnO 2 as a transparent conductive film. And preliminarily dried at 100 ° C. for 30 minutes and then baked under oxygen at 460 ° C. for 40 minutes.
  • a titanium oxide film A having a thickness of about 8 ⁇ m was produced.
  • the dye of the present invention and the comparative dye S-1 were dissolved in absolute ethanol at a concentration of 3 ⁇ 10 ⁇ 4 mol / liter to prepare an adsorption dye solution.
  • the dye solution for adsorption was adsorbed by putting the transparent substrate provided with the titanium oxide film and the transparent conductive film obtained above into a container and allowing it to penetrate for about 4 hours. Thereafter, it was washed several times with absolute ethanol and dried at about 60 ° C. for about 20 minutes.
  • a monomer composed of R as a methyl group, A as eight polyethylene oxide groups, two polypropylene oxide groups, and a butanetetrayl group as a central core Units were used.
  • R is a hydrogen atom or a methyl group
  • A is a residue bonded to an ester group with a carbon atom
  • n is 2 to 4.
  • This monomer unit is dissolved in propylene carbonate (hereinafter referred to as PC) at a concentration of 20 wt%, and azobisisobutyronitrile (AIBN) is used as a thermal polymerization initiator at a concentration of 1 wt% with respect to the monomer unit. Dissolve to make a monomer solution. The procedure for impregnating the above-described titanium oxide film with the monomer solution is described below.
  • a container such as a beaker is placed in the vacuum container, and the titanium oxide film A on the transparent substrate provided with the transparent conductive film is placed therein, and is evacuated by a rotary pump for about 10 minutes.
  • the monomer solution is poured into the beaker while keeping the vacuum container in a vacuum state, and the monomer solution is sufficiently soaked in the titanium oxide 3 by impregnation for about 15 minutes.
  • a polyethylene separator, a PET film and a pressing plate are installed and fixed with a jig. Then, it heat-polymerizes by heating at about 85 degreeC for 30 minutes, and produces a high molecular compound.
  • a redox electrolyte solution to be impregnated into the polymer compound is prepared.
  • the redox electrolyte was prepared by dissolving 0.5 mol / liter of lithium iodide and 0.05 mol / liter of iodine using PC as a solvent.
  • the polymer compound prepared on the above-described titanium oxide film A was immersed in this solution for about 2 hours, so that the polymer compound was impregnated with the redox electrolyte solution to prepare a polymer electrolyte.
  • membrane was installed, the periphery was sealed with the epoxy-type sealing agent, and the element A was created. Further, after the dye adsorption of the titanium oxide film A, the oxidation was performed by dissolving lithium iodide at a concentration of 0.5 mol / liter and iodine at a concentration of 0.05 mol / liter using PC as a solvent without performing monomer treatment. The reduced electrolyte was injected as it was between the counter electrode and sealed to prepare an element B. Using the elements A and B, light having an intensity of 1000 W / m 2 was irradiated with a solar simulator. The results are shown in Table 14. The conversion efficiency is ⁇ for those with 3.5% or more, ⁇ for 2.5% or more and less than 3.5%, ⁇ for 2.0% or more and less than 2.5%, and less than 2.0%. Things were displayed as x.
  • the photoelectric conversion element shown in FIG. 1 was produced as follows. On the glass substrate, tin oxide doped with fluorine was formed as a transparent conductive film by sputtering, and this was scribed with a laser to divide the transparent conductive film into two parts. Next, 32 g of anatase-type titanium oxide (P-25 (trade name) manufactured by Nippon Aerosil Co., Ltd.) is mixed with 100 ml of a mixed solvent having a volume ratio of water and acetonitrile of 4: 1, and a rotating / revolving mixing conditioner is prepared.
  • P-25 trade name
  • the resulting mixture was uniformly dispersed and mixed to obtain a semiconductor fine particle dispersion.
  • This dispersion was applied to a transparent conductive film and heated at 500 ° C. to produce a light receiving electrode.
  • a dispersion containing 40:60 (mass ratio) of silica particles and rutile-type titanium oxide is prepared, and this dispersion is applied to the light receiving electrode and heated at 500 ° C. to form an insulating porous material. Formed body.
  • a carbon electrode was formed as a counter electrode.
  • the glass substrate on which the insulating porous body was formed was immersed in an ethanol solution of a sensitizing dye (mixed or single) described in Table 15 below for 5 hours.
  • the glass dyed with the sensitizing dye was immersed in a 10% ethanol solution of 4-tert-butylpyridine for 30 minutes, then washed with ethanol and naturally dried.
  • the thickness of the photosensitive layer thus obtained was 10 ⁇ m, and the coating amount of semiconductor fine particles was 20 g / m 2 .
  • As the electrolytic solution a methoxypropionitrile solution of dimethylpropylimidazolium iodide (0.5 mol / l) and iodine (0.1 mol / l) was used.
  • sensitizing dyes S-4 and S-5 are shown below.
  • the electrochemical cell produced using the dye of the present invention showed high conversion efficiency when the sensitizing dye of the present invention was used.
  • the conversion efficiency of the photoelectrochemical cell of the comparative example was insufficient at less than 7.1%.

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Abstract

L'invention porte sur un composé colorant représenté par la formule générale (1). Dans la formule générale (1), Z1, Z2, Z3 et Z4 représentent chacun une structure de noyau aromatique ou une structure hétérocyclique ; R1, R2, R3 et R4 représentent chacun respectivement et individuellement un substituant ; m1 à m4 représentent chacun un entier compris entre 0 et 4 et lorsque m1 à m4 est supérieur ou égal à deux, les R1 à R4 peuvent être identiques ou différents les uns des autres ; au moins l'un de R1 à R4 contient un groupe de liaison (Y) et ledit groupe de liaison (Y) est directement lié et conjugué avec au moins l'un de Z1 à Z4 ; de plus, au moins l'un de R1, R2, R3 et R4 a un groupe acide ; M représente un atome d'hydrogène, un atome métallique ou atome métallique substitué.
PCT/JP2011/067011 2010-08-03 2011-07-26 Colorant complexe métallique, élément de conversion photoélectrique et cellule photoélectrochimique Ceased WO2012017874A1 (fr)

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JP2012167189A (ja) * 2011-02-14 2012-09-06 Aisin Seiki Co Ltd フタロシアニン誘導体、フタロシアニン誘導体の製造方法および色素増感型太陽電池
JP2013185029A (ja) * 2012-03-07 2013-09-19 Konica Minolta Inc 光電変換素子用色素、光電変換素子及びその製造方法
WO2020059483A1 (fr) * 2018-09-18 2020-03-26 富士フイルム株式会社 Composition, film, filtre optique, dispositif d'imagerie à semi-conducteurs, capteur infrarouge, procédé de fabrication de filtre optique, module de d'appareil de prise de vues, composé et composition de dispersion
JP2022123689A (ja) * 2021-02-12 2022-08-24 東洋インキＳｃホールディングス株式会社 近赤外線吸収性色素、近赤外線吸収性組成物、および光学フィルタ

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JP2004220974A (ja) * 2003-01-16 2004-08-05 Toyo Ink Mfg Co Ltd 光機能材料
WO2010050574A1 (fr) * 2008-10-29 2010-05-06 富士フイルム株式会社 Cellule photoélectrochimique
WO2010136178A1 (fr) * 2009-05-26 2010-12-02 Corus Uk Limited Préparation d'un composé colorant et un procédé pour préparer celui-ci

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012167189A (ja) * 2011-02-14 2012-09-06 Aisin Seiki Co Ltd フタロシアニン誘導体、フタロシアニン誘導体の製造方法および色素増感型太陽電池
JP2013185029A (ja) * 2012-03-07 2013-09-19 Konica Minolta Inc 光電変換素子用色素、光電変換素子及びその製造方法
WO2020059483A1 (fr) * 2018-09-18 2020-03-26 富士フイルム株式会社 Composition, film, filtre optique, dispositif d'imagerie à semi-conducteurs, capteur infrarouge, procédé de fabrication de filtre optique, module de d'appareil de prise de vues, composé et composition de dispersion
JPWO2020059483A1 (ja) * 2018-09-18 2021-08-30 富士フイルム株式会社 組成物、膜、光学フィルタ、固体撮像素子、赤外線センサ、光学フィルタの製造方法、カメラモジュール、化合物、及び、分散組成物
JP7094379B2 (ja) 2018-09-18 2022-07-01 富士フイルム株式会社 組成物、膜、光学フィルタ、固体撮像素子、赤外線センサ、光学フィルタの製造方法、カメラモジュール、化合物、及び、分散組成物
JP2022123689A (ja) * 2021-02-12 2022-08-24 東洋インキＳｃホールディングス株式会社 近赤外線吸収性色素、近赤外線吸収性組成物、および光学フィルタ
JP7182049B2 (ja) 2021-02-12 2022-12-02 東洋インキＳｃホールディングス株式会社 近赤外線吸収性色素、近赤外線吸収性組成物、および光学フィルタ

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