WO2012124483A1 - 金属錯体色素組成物、光電変換素子及び光電気化学電池並びに金属錯体色素の製造方法 - Google Patents

金属錯体色素組成物、光電変換素子及び光電気化学電池並びに金属錯体色素の製造方法 Download PDF

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WO2012124483A1
WO2012124483A1 PCT/JP2012/055142 JP2012055142W WO2012124483A1 WO 2012124483 A1 WO2012124483 A1 WO 2012124483A1 JP 2012055142 W JP2012055142 W JP 2012055142W WO 2012124483 A1 WO2012124483 A1 WO 2012124483A1
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general formula
group
metal complex
represented
complex dye
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PCT/JP2012/055142
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English (en)
French (fr)
Japanese (ja)
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征夫 谷
達也 薄
小林　克
木村　桂三
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富士フイルム株式会社
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Priority to CN201280011121.5A priority Critical patent/CN103403099B/zh
Priority to KR1020137026226A priority patent/KR101640974B1/ko
Publication of WO2012124483A1 publication Critical patent/WO2012124483A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • C07F15/0053—Ruthenium compounds without a metal-carbon linkage
    • 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
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • 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
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M14/00—Electrochemical current or voltage generators not provided for in groups H01M6/00 - H01M12/00; Manufacture thereof
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a metal complex dye composition having high solubility in a solvent, a photoelectric conversion element and a photoelectrochemical cell having high photoelectric conversion efficiency.
  • the photoelectric conversion element is used in various optical sensors, copying machines, photoelectrochemical cells (for example, 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.
  • a photoelectric conversion element using an inexpensive organic dye as a sensitizer has been reported.
  • Patent Documents 2 and 3 a technique for improving the photoelectric conversion efficiency by adsorbing a photosensitizing dye having a specific structure to semiconductor fine particles has been proposed (for example, see Patent Documents 2 and 3).
  • the photosensitizing dyes (pure products) described in Patent Documents 2 and 3 have low solubility in a solvent, the amount of the dye adsorbed on the semiconductor fine particles is insufficient under certain conditions, which is sufficient in terms of photoelectric conversion efficiency
  • An object of the present invention is to provide a metal complex dye composition having high solubility in a solvent, a photoelectric conversion element and a photoelectrochemical cell having high photoelectric conversion efficiency. Moreover, the subject of this invention is providing the manufacturing method of a metal complex pigment
  • the present inventors have been able to improve the adsorption amount of the dye to the semiconductor fine particles because the metal complex dye containing a specific ligand has high solubility in a solvent. It has been found that a photoelectric conversion element and a photoelectrochemical cell having high efficiency can be provided. The present invention has been made based on this finding.
  • a metal complex dye represented by the following general formula (1) a metal complex dye represented by the following general formula (5) and / or a metal complex dye represented by the following general formula (6)
  • the content of the metal complex dye represented by the general formula (5) and the metal complex dye represented by the general formula (6) is an area detected at 254 nm of HPLC (High Performance Liquid Chromatography).
  • HPLC High Performance Liquid Chromatography
  • M 1 represents a metal atom
  • LL 1 is a bidentate ligand represented by the following General Formula (2)
  • LL 2 is represented by the following General Formula (3). This is a bidentate ligand.
  • M1 represents 1.
  • m2 represents 1.
  • Z 1 represents a ligand and is at least one selected from an isothiocyanato group, an isocyanato group and an isoselenocyanato group.
  • CI 1 represents a counter ion when a counter ion is necessary to neutralize the charge, and m3 is an integer of 0 or more.
  • R 11 to R 14 and R 21 to R 24 independently represent an acidic group or a salt thereof, or a hydrogen atom, and R 11 to R 14 and R 21 to R 24 are the same or different. It may be. However, at least one of R 11 to R 14 and R 21 to R 24 is an acidic group or a salt thereof. ]
  • n1 and n2 independently represent an integer of 0 to 3
  • Y 1 and Y 2 independently represent a hydrogen atom or a heteroaryl group represented by the following general formula (4) .
  • Ar 1 and Ar 2 independently represent a heteroaryl group represented by the following general formula (4).
  • R 31 to R 33 independently represent a hydrogen atom, an alkyl group, an alkoxy group, or an alkynyl group, and at least one of R 31 to R 33 represents an alkyl group, an alkoxy group, or an alkynyl group. It is a group.
  • X is a sulfur atom, an oxygen atom, a selenium atom or NR 4
  • R 4 is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
  • LL 2 is represented by the following general formula (7), wherein the metal complex dye composition according to ⁇ 1>.
  • R 41 to R 43 and R 51 to R 53 independently represent a hydrogen atom, an alkyl group, an alkoxy group, or an alkynyl group. At least one of R 41 to R 43 is an alkyl group, an alkoxy group, or an alkynyl group. At least one of R 51 to R 53 is an alkyl group, an alkoxy group, or an alkynyl group.
  • X 1 and X 2 are each independently a sulfur atom, an oxygen atom, a selenium atom or NR 7 , and R 7 is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
  • R 7 is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
  • X 1 and X 2 in the general formula (7) are sulfur atoms.
  • ⁇ 4> The metal complex dye composition according to any one of ⁇ 1> to ⁇ 3>, wherein the metal complex dye represented by the general formula (1) is represented by the following general formula (8): object.
  • R 61, R 62 represents an alkyl group, an alkoxy group or an alkynyl group independently, A 1, A 2 represents a carboxyl group or a salt thereof independently.
  • the metal complex dye represented by the general formula (5) is represented by the following general formula (9), and the metal complex dye represented by the general formula (6) is represented by the following general formula (10).
  • R 71 and R 72 independently represent an alkyl group, an alkoxy group or an alkynyl group, and A 5 and A 6 each independently represent a carboxyl group or a salt thereof.
  • R 73 and R 74 independently represent an alkyl group, an alkoxy group, or an alkynyl group, and A 7 and A 8 are each independently a carboxyl group or a salt thereof.
  • the metal complex dye represented by the general formula (5) is represented by the following general formula (11), and the metal complex dye represented by the general formula (6) is represented by the following general formula (12).
  • R 81 to R 84 independently represent an alkynyl group.
  • a 13 to A 16 independently represent a carboxyl group or a salt thereof.
  • M 1 , LL 1 , LL 2 , CI 1 , m1 and m2 have the same meanings as in General Formula (1).
  • Z 2 is a monodentate or bidentate ligand.
  • m4 represents an integer of 1 or 2
  • Z 2 represents m4 is 2 when the monodentate ligands, when Z 2 is a bidentate ligand m4 represents 1.
  • m5 is an integer of 0 or more.
  • M 11 QCN general formula (14) [In the general formula (14), M 11 is an inorganic or organic ammonium ions, represents a proton or an alkali metal ion, Q is a sulfur atom, an oxygen atom or a selenium atom. ]
  • M 1 represents a metal atom
  • LL 1 is a bidentate ligand represented by the following General Formula (2)
  • LL 2 is represented by the following General Formula (3). This is a bidentate ligand.
  • M1 represents 1, m2 represents 1, and m3 is an integer of 0 or more.
  • Z 1 represents a ligand and is at least one selected from an isothiocyanato group, an isocyanato group and an isoselenocyanato group.
  • CI 1 represents a counter ion when a counter ion is required to neutralize the charge.
  • R 11 to R 14 and R 21 to R 24 independently represent an acidic group or a salt thereof, or a hydrogen atom, and R 11 to R 14 and R 21 to R 24 are the same or different. It may be. However, at least one of R 11 to R 14 and R 21 to R 24 is an acidic group or a salt thereof. ]
  • n1 and n2 independently represent an integer of 0 to 3
  • Y 1 and Y 2 independently represent a hydrogen atom or a heteroaryl group represented by the following general formula (4) .
  • Ar 1 and Ar 2 independently represent a heteroaryl group represented by the following general formula (4).
  • R 31 to R 33 independently represent a hydrogen atom, an alkyl group, an alkoxy group, or an alkynyl group, and at least one of R 31 to R 33 represents an alkyl group, an alkoxy group, or an alkynyl group. It is a group.
  • X is a sulfur atom, an oxygen atom, a selenium atom or NR 4
  • R 4 is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
  • R 41 to R 43 and R 51 to R 53 independently represent a hydrogen atom, an alkyl group, an alkoxy group, or an alkynyl group. At least one of R 41 to R 43 is an alkyl group, an alkoxy group, or an alkynyl group. At least one of R 51 to R 53 is an alkyl group, an alkoxy group, or an alkynyl group.
  • X 1 and X 2 are each independently a sulfur atom, an oxygen atom, a selenium atom or NR 7 , and R 7 is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
  • R 61 , R 62 , R 91 , R 92 independently represent a hydrogen atom, an alkyl group, an alkoxy group, or an alkynyl group, and A 1 to A 4 are independently Represents a carboxyl group or a salt thereof.
  • M 12 represents an inorganic or organic ammonium ion, proton, or alkali metal ion.
  • the general formula (1) is represented by the following general formula (17)
  • the general formula (13) is represented by the following general formula (18)
  • the general formula (14) is represented by the following general formula (19).
  • the method for producing a metal complex dye according to any one of ⁇ 7> to ⁇ 9>, wherein
  • R 101 , R 102 , R 111 , R 112 independently represent an alkynyl group, and A 9 to A 12 independently represent a carboxyl group or a salt thereof.
  • M 13 represents an inorganic or organic ammonium ion, proton or alkali metal ion.
  • ⁇ 12> A photoelectric conversion element using the metal complex dye composition according to any one of ⁇ 1> to ⁇ 6> as a sensitizing dye.
  • ⁇ 13> A photoelectric conversion element comprising a metal complex dye produced by the method for producing a metal complex dye according to any one of ⁇ 7> to ⁇ 11>.
  • ⁇ 14> A photoelectrochemical cell comprising the photoelectric conversion element according to any one of ⁇ 1> to ⁇ 13>.
  • the present inventors have been able to improve the adsorption amount of the dye to the semiconductor fine particles because the metal complex dye containing a specific ligand has high solubility in a solvent. It has been found that a photoelectric conversion element and a photoelectrochemical cell having high efficiency can be provided. The present invention has been made based on this finding.
  • 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 layer 2 constitute a light receiving electrode 5.
  • the photoreceptor layer 2 has semiconductor fine particles 22 and a sensitizing dye (hereinafter also simply referred to as a dye) 21. At least a part of the sensitizing dye 21 is adsorbed on the semiconductor fine particles 22 (the sensitizing dye 21 is in an adsorption equilibrium state and may be partially present in the charge transfer layer 3).
  • the charge transfer body layer 3 functions as, for example, a hole transport layer that transports holes.
  • the conductive support 1 on which the photoreceptor layer 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 light receiving electrode 5 is an electrode composed of a conductive support 1 and a photosensitive layer 2 (semiconductor film) of semiconductor fine particles 22 adsorbed by a sensitizing dye 21 coated on the conductive support 1.
  • a photosensitive layer 2 semiconductor film
  • the excited dye has high energy electrons. Therefore, the electrons are transferred from the sensitizing dye 21 to the conduction band of the semiconductor fine particles 22 and reach the conductive support 1 by diffusion.
  • the molecule of the sensitizing dye 21 is an oxidant.
  • the electrons on the electrode return to the oxidant while working in the external circuit 6, thereby acting as the photoelectrochemical cell 100.
  • the light receiving electrode 5 functions as a negative electrode of the battery.
  • the photoreceptor layer 2 is composed of a porous semiconductor layer composed of a layer of semiconductor fine particles 22 to which a dye described later is adsorbed. This dye may be partially dissociated in the electrolyte.
  • the photoreceptor layer 2 is designed according to the purpose and has a multilayer structure.
  • the photosensitive layer 2 includes the semiconductor fine particles 22 on which a specific dye is adsorbed, the light receiving sensitivity is high, and when used as the photoelectrochemical cell 100, high photoelectric conversion efficiency can be obtained. Furthermore, it has high durability.
  • Metal complex dye composition The metal complex dye composition of the present invention is represented by a metal complex dye represented by the following general formula (1), a metal complex dye represented by the following general formula (5) and / or the following general formula (6).
  • a metal complex dye The content of the metal complex dye represented by the general formula (5) and the metal complex dye represented by the general formula (6) is an area detected at 254 nm of HPLC (High Performance Liquid Chromatography). 5 to 5%.
  • M 1 represents a metal atom
  • LL 1 is a bidentate ligand represented by the following General Formula (2)
  • LL 2 is represented by the following General Formula (3). This is a bidentate ligand.
  • M1 and m2 are both 1.
  • m3 is an integer of 0 or more.
  • Z 1 represents a ligand and is at least one selected from an isothiocyanato group, an isocyanato group and an isoselenocyanato group. Z 1 may be the same or different, but is preferably the same.
  • CI 1 represents a counter ion when a counter ion is required to neutralize the charge.
  • R 11 to R 14 and R 21 to R 24 independently represent an acidic group or a salt thereof, or a hydrogen atom, and R 11 to R 14 and R 21 to R 24 are the same or different. It may be. However, at least one of R 11 to R 14 and R 21 to R 24 is an acidic group or a salt thereof. ]
  • n1 and n2 independently represent an integer of 0 to 3
  • Y 1 and Y 2 independently represent a hydrogen atom or a heteroaryl group represented by the following general formula (4)
  • Ar1 and Ar2 independently represent a heteroaryl group represented by the following general formula (4).
  • R 31 to R 33 independently represent a hydrogen atom, an alkyl group, an alkoxy group, or an alkynyl group, and at least one of R 31 to R 33 represents an alkyl group, an alkoxy group, or an alkynyl group. It is a group.
  • X is a sulfur atom, an oxygen atom, a selenium atom or NR 4
  • R 4 is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
  • Metal complex dye represented by general formula (1) Metal atom M 1 M 1 represents a metal atom.
  • M 1 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 Zn. Particularly preferred is Ru, OsFe or Cu, and most preferred is Ru. Of Ru, divalent Ru is preferable.
  • the ligand LL 1 is a bidentate represented by the following general formula (2).
  • M1 representing the number of ligands LL 1 is 1.
  • R 11 to R 14 and R 21 to R 24 in the general formula (2) independently represent an acidic group or a salt thereof, or a hydrogen atom, and R 11 to R 14 and R 21 to R 24 are the same or different. May be.
  • R 11 to R 14 and R 21 to R 24 include a hydrogen atom, 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).
  • the acidic group may be bonded via a linking group, and those having an acidic group such as a carboxyl group, a sulfonic acid group, a hydroxyl group, or a hydroxamic acid group bonded via the linking group are also included in the acidic group.
  • At least one of R 11 to R 14 and R 21 to R 24 is an acidic group or a salt thereof.
  • the acidic group is preferably an acidic group such as a carboxyl group, a sulfonic acid group, or a phosphonyl group, or a salt thereof, more preferably A carboxyl group or a phosphonyl group or a salt thereof, more preferably a carboxyl group or a salt thereof.
  • R 11 to R 14 and R 21 to R 24 are an acidic group or a salt thereof, or a hydrogen atom, the metal complex dye can be effectively adsorbed on the semiconductor fine particles.
  • Ligand LL 2 is a bidentate ligand represented by the following general formula (3).
  • M2 representing the number of ligands LL 2 ligand LL 2 represents 1.
  • the double bond may be E-form or Z-form.
  • n1 and n2 independently represent an integer of 0 to 3. n1 and n2 are preferably 0 to 3, and more preferably 0 to 1.
  • Y 1 and Y 2 independently represent a hydrogen atom or a heteroaryl group represented by the following general formula (4).
  • Ar 1 and Ar 2 independently represent a heteroaryl group represented by the following general formula (4).
  • R 31 to R 33 independently represent a hydrogen atom, an alkyl group, an alkoxy group or an alkynyl group, and at least one of R 31 to R 33 is an alkyl group, an alkoxy group or an alkynyl group.
  • an alkyl group and an alkynyl group More preferred are an alkyl group and an alkynyl group, and particularly preferred is an alkynyl group. These may be linear or branched, and preferably have 2 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, and particularly preferably 4 to 8 carbon atoms.
  • Y 1 or Y 2 is represented by the general formula (4), it is preferable that Y 1 or Y 2 is conjugated with a pyridine ring, and Ar 1 and Ar 2 are conjugated with a pyridine ring. Along with the electron donating property of Y 1 or Y 2 represented by the general formula (4), these are conjugated to improve the HOMO level to the metal atom M 1 in the metal complex dye. Light can be absorbed (lengthened).
  • X is a sulfur atom, an oxygen atom, a selenium atom, or NR 4
  • R 4 is a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.
  • X in the general formula (4) is preferably a sulfur atom or a selenium atom, more preferably a sulfur atom, from the viewpoints of stability to nucleophilic species, difficulty in oxidation and difficulty in synthesis.
  • the ligand LL 2 are represented by the following general formula (7).
  • R 41 to R 43 and R 51 to R 53 independently represent a hydrogen atom, an alkyl group, an alkoxy group, or an alkynyl group. At least one of R 41 to R 43 is an alkyl group, an alkoxy group, or an alkynyl group. At least one of R 51 to R 53 is an alkyl group, an alkoxy group, or an alkynyl group.
  • X 1 and X 2 are each independently a sulfur atom, an oxygen atom, a selenium atom or NR 7 , and R 7 is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
  • the double bond may be E-form or Z-form.
  • R 41 to R 43 are preferably an alkyl group or an alkynyl group.
  • R 51 to R 53 are preferably an alkyl group or an alkynyl group.
  • X 1 and X 2 in the general formula (7) are preferably a sulfur atom and a selenium atom, and more preferably a sulfur atom.
  • n1 and n2 in the general formula (3) are 1, and therefore, there is an effect that the ligand LL2 is less likely to be oxidized and stable as compared with the case of 2 or more. be able to.
  • the metal complex dye represented by the general formula (1) is preferably represented by the following general formula (8).
  • R 61 and R 62 independently represent an alkyl group, an alkoxy group, or an alkynyl group, and A 1 and A 2 independently represent a carboxyl group or a salt thereof.
  • R 61 and R 62 are preferably an alkyl group or an alkynyl group.
  • desorption of the dye from the semiconductor fine particles can be suppressed by eliminating the approach of water by the vinylthiophene bonded to the bipyridine ring and the substituent bonded to the thiophene.
  • electrons can be efficiently injected by a carboxyl group or a salt thereof, and light in a long wavelength region can be absorbed by a highly electron-donating isothiocyanate group.
  • the dye is adsorbed on the surface of the semiconductor fine particles by the acidic group part of LL 1 , and an alkyl group, an alkoxy group or
  • LL 2 having a hydrophobic group such as an alkynyl group on the side opposite to the semiconductor fine particle layer, it is possible to effectively suppress the approach of water and suppress the desorption of the dye.
  • Ligand Z 1 is at least one selected from isothiocyanato group, an isocyanato group and iso seleno cyanatophenyl group. These groups have high electron donating properties and contribute to the long wave of the dye.
  • the ligand Z 1 is preferably an isothiocyanato group or an isoselenocyanato group.
  • Counter ion CI 1 CI 1 in the general formula (1) 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 number m3 of the counter ion CI 1 is an integer of 0 or more.
  • the dye of the general formula (1) may be dissociated and have a negative charge because the substituent has a dissociable group.
  • the charge of the whole dye of the general formula (1) is electrically neutralized by the counter ion CI 1 .
  • the counter ion CI 1 is a positive counter ion
  • the counter ion CI 1 is an inorganic or organic ammonium ion (for example, a tetraalkylammonium ion, a pyridinium ion, etc.), an alkali metal ion, or a proton.
  • the counter ion CI 1 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 metal complex dye composition of the present invention has the following general formula (A specific amount of at least one of the metal complex dye represented by 5) and the metal complex dye represented by the following general formula (6) is included.
  • the content of the metal complex dye represented by the general formula (5) and the metal complex dye represented by the general formula (6) is detected at 254 nm of HPLC (high performance liquid chromatography).
  • the area% is 0.5 to 5% in the metal complex dye composition.
  • the metal complex dye of the general formula (5) has one cyano group as a ligand
  • the metal complex dye of the general formula (6) has two cyano groups as a ligand.
  • M 1 , LL 1 , LL 2 , Z 1 , CI 1 , m1, m2 and m3 are the same as those in the general formula (1), and in the general formula (6), M 1 , LL 1 , LL 2 , Z 1 , CI 1 , m 1 , m 2 , and m 3 have the same meanings as those in the general formula (1), and are not described because they are redundantly described.
  • M 1 , LL 1 , LL 2 , Z 1 , CI 1 , m1, m2 and m3 are the same as in general formula (1).
  • the cyano group has a lower electron donating property than the aforementioned isothiocyanato group. Therefore, the metal complex dye represented by the general formula (5) having one cyano group and the metal complex dye represented by the general formula (6) having two cyano groups have a reduced HOMO level and absorption. When the wavelength is shortened and adsorbed on semiconductor fine particles and used as a sensitizing dye, the light on the long wave side cannot be used effectively, and the conversion efficiency tends to decrease. However, the content of the metal complex dye represented by the general formula (5) and the metal complex dye represented by the general formula (6) is an area detected at 254 nm of HPLC (High Performance Liquid Chromatography).
  • the solubility of the dye in the solution can be dramatically improved without causing a decrease in conversion efficiency, and the amount of dye adsorbed on the semiconductor fine particles can be reduced. And high photoelectric conversion efficiency can be obtained. Moreover, a dye solution can be prepared in a short time, and the productivity of photoelectric conversion element production improves. Although the reason for the improvement of the solubility of the dye in the solution is not clear, a metal complex dye having a cyano group having a chemically different property is used in common with the metal complex dye represented by the general formula (1). This is probably because when 0.5 to 5% is contained, the crystal arrangement of the metal complex dye is different from that when the purity is 0.5% or less.
  • the content of the metal complex dye represented by the general formula (5) and the metal complex dye represented by the general formula (6) is an area detected at 254 nm of HPLC (High Performance Liquid Chromatography).
  • the metal complex dye represented by the general formula (5) is represented by the following general formula (9)
  • the metal complex dye represented by the general formula (6) is represented by the following general formula (10)
  • the general formula The total content of the metal complex dye represented by (9) and the metal complex dye represented by the general formula (10) is an area detected at 254 nm of HPLC (High Performance Liquid Chromatography). It is preferably 5%.
  • R 71 and R 72 independently represent an alkyl group, an alkoxy group or an alkynyl group
  • a 5 and A 6 independently represent a carboxyl group or a salt thereof.
  • R 73 and R 74 independently represent an alkyl group, an alkoxy group, or an alkynyl group, and A 7 and A 8 independently represent a carboxyl group or a salt thereof.
  • R 71 and R 72 are preferably an alkyl group or an alkynyl group.
  • R 73 and R 74 are preferably an alkyl group or an alkynyl group.
  • the metal complex dye represented by the general formula (5) and the metal complex dye represented by the general formula (6) have such a structure, and the total content of these metal complex dyes is HPLC (high speed In the area detected at 254 nm in liquid chromatography), 0.5 to 5%, the absorption of the dye becomes longer due to the electron donating property of the thiophene ring, and because of the cyano group, it is significantly converted by shortening the wavelength. The efficiency can be improved without causing a decrease in efficiency.
  • the total content of the metal complex dye represented by the general formula (5) and the metal complex dye represented by the general formula (6) is preferably an area detected at 254 nm of HPLC (high performance liquid chromatography). Is 0.5 to 4.5%, more preferably 0.5 to 4%, and particularly preferably 0.5 to 3.5%.
  • the metal complex dye represented by the general formula (5) is represented by the following general formula (11), and the metal complex dye represented by the general formula (6) is represented by the following general formula (12). preferable.
  • R 81 to R 84 independently represent an alkynyl group, and A 13 to A 16 independently represent a carboxyl group or a salt thereof.
  • R 81 to R 84 are alkynyl groups, the effect of increasing the wave length of absorption derived from the ⁇ - ⁇ * transition of LL 2 due to conjugated elongation and the improvement of ⁇ can be achieved.
  • R 81 to R 84 are alkynyl groups, the metal complex dye having this structure improves the planarity of R 81 to R 84 with respect to the thiophene ring or increases the number of ⁇ electrons on the surface of the semiconductor fine particles. It is expected that a favorable association that contributes to longer waves may be easily formed between molecules in a state where the dye is adsorbed.
  • R 81 to R 84 are preferably linear or branched alkynyl groups having 3 to 13 carbon atoms, more preferably linear or branched alkynyl groups having 3 to 8 carbon atoms, and particularly preferably 4 to 7 carbon atoms. Or a linear or branched alkynyl group.
  • the metal complex dye composition is preferably a metal complex dye of the general formula (1), a metal complex dye represented by the general formula (5) and / or a metal complex represented by the general formula (6) in an organic solvent. It can be dissolved in the dye.
  • organic solvents include alcohol solvents (methanol, ethanol, isopropanol, etc.), nitrile solvents (acetonitrile, propionitrile, methoxypropionitrile, valeronitrile, etc.), ester solvents (ethyl acetate, ⁇ -butyrolactone, etc.) ), Amide solvents (dimethylformamide, dimethylacetamide, NMP), halogen solvents (dichloromethane, dichloroethane, chlorobenzene, chloroform, etc.), benzene, toluene, xylene, and the like, but are not particularly limited.
  • the mixed solvent which consists of a some solvent may be sufficient.
  • the metal complex dye of the general formula (1) of the present invention is obtained by externally heating a mixed solution containing a metal complex dye of the following general formula (13) and a compound of the following general formula (14). It can be produced by a method including a step of increasing the temperature of the mixed solution.
  • M 1 , LL 1 , LL 2 , CI 1 , m1 and m2 have the same meaning as in general formula (1).
  • Z 2 is a monodentate or bidentate ligand.
  • Z 2 is preferably a halogen atom (F, Cl, Br, I), water, a dimethylformamide group, —O—C ( ⁇ O) — (CH 2 ) p —C ( ⁇ O) —O— (p is And represents an integer of 0 or more, preferably 0 to 6, more preferably 0 to 4, and particularly preferably 0 to 2. More preferred are a chlorine atom, water, and a dimethylformamide group, and particularly preferred is a chlorine atom.
  • m4 represents an integer of 1 or 2
  • Z 2 represents m4 is 2 when the monodentate ligands, when Z 2 is a bidentate ligand m4 represents 1. When m4 is 2, Z 2 may be the same or different, but is preferably the same.
  • m5 is an integer of 0 or more.
  • M 11 is an inorganic or organic ammonium ions, represents a proton or an alkali metal ion, Q is a sulfur atom, an oxygen atom or a selenium atom.
  • M 11 is preferably an inorganic or organic ammonium ion (eg, NH 4 + , NBu 4 + , NEt 3 H + ) or an alkali metal ion (eg, Na + , K + , Li + ), more preferably NH 4 +. , NBu 4 + , K + , particularly preferably NH 4 + , K + .
  • Q is preferably a sulfur atom or a selenium atom, more preferably a sulfur atom, from the viewpoint of the absorption wavelength of the metal complex dye of the general formula (1), that is, the electron donating property of QCN as a ligand.
  • the metal complex dye represented by the general formula (1) is represented by the following formula as described above.
  • M 1 represents a metal atom
  • LL 1 is a bidentate ligand represented by the following general formula (2)
  • LL 2 is represented by the following general formula (3). It is a bidentate ligand.
  • m1 and m2 both represent 1.
  • Z 1 represents a ligand and is at least one selected from an isothiocyanato group, an isocyanato group and an isoselenocyanato group. Z 1 may be the same or different, but is preferably the same.
  • CI 1 represents a counter ion when a counter ion is required to neutralize the charge.
  • m3 is an integer of 0 or more.
  • R 11 to R 14 and R 21 to R 24 independently represent an acidic group or a salt thereof, or a hydrogen atom, and R 11 to R 14 and R 21 to R 24 are the same or different. It may be. However, at least one of R 11 to R 14 and R 21 to R 24 is an acidic group or a salt thereof. ]
  • n1 and n2 independently represent an integer of 0 to 3
  • Y 1 and Y 2 independently represent a hydrogen atom or a heteroaryl group represented by the following general formula (4)
  • Ar 1 and Ar 2 independently represent a heteroaryl group represented by the following general formula (4).
  • R 31 to R 33 independently represent a hydrogen atom, an alkyl group, an alkoxy group, or an alkynyl group, and at least one of R 31 to R 33 represents an alkyl group, an alkoxy group, or an alkynyl group. It is a group.
  • X is a sulfur atom, an oxygen atom, a selenium atom or NR 4
  • R 4 is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
  • the metal complex dye of the present invention is obtained by heating a mixed solution containing the metal complex dye of the general formula (13) and the compound of the general formula (14) by external heating. It can be produced by a method including a step of raising the temperature of the mixed solution.
  • an organic solvent can be preferably used as the mixed solution containing the metal complex dye of the general formula (13) and the compound of the general formula (14).
  • an alcohol solvent methanol, ethanol, propanol, Isopropanol, butanol, etc.
  • nitrile solvents acetonitrile, propionitrile, methoxypropionitrile, valeronitrile, etc.
  • ester solvents ethyl acetate, ⁇ -butyrolactone, etc.
  • amide solvents dimethylformamide, dimethylacetamide, NMP
  • Halogen solvents diichloromethane, dichloroethane, chlorobenzene, chloroform, etc.
  • benzene, toluene, xylene and the like can be mentioned, but are not particularly limited thereto.
  • the mixed solvent which consists of a some solvent may be sufficient, and a mixed solvent with water may be sufficient.
  • the organic solvent is preferably an alcohol solvent, a nitrile solvent, an amide solvent, more preferably an alcohol solvent, an amide solvent, and particularly preferably an amide solvent.
  • the method of heating the mixed solution containing the metal complex dye of the general formula (13) and the compound of the general formula (14) to increase the temperature of the mixed solution may be a method of heating from the outside. It is essential.
  • the method of heating from the outside means a method of heating by heat transfer from an external heat source. Although it does not specifically limit as a heat source, The heat source which converts an electrical energy into heat, the heat source by combustion, etc. are mentioned. You may heat said liquid mixture through the medium for the heat obtained from those heat sources. Examples of the medium include oil and water (steam).
  • a method of irradiating microwaves or the like is heating by absorption of microwaves into a substance and conversion of microwave energy into heat, so to speak, heating from the inside, not including external heating.
  • the heating principle is different from external heating, and the metal complex is directly heated and the energy of heating is too large. Therefore, the metal complex dye of the general formula (13) contained in the mixture or the general formula ( Since decomposition of the compound 14) or the metal complex dye of the general formula (1) occurs, it is not preferable for producing the metal complex dye of the present invention.
  • a method by external heating a method of heating the mixed solution with an oil bath or steam can be preferably mentioned. The heating temperature and the reaction time can be appropriately selected depending on the metal complex dye to be reacted and the solvent used.
  • the heating temperature is preferably 90 to 170 ° C., more preferably 90 to 160 ° C., particularly preferably 100 to 150 ° C., and most preferably 100 to 140 ° C.
  • the reaction time is preferably 30 minutes to 12 hours, more preferably 1 to 8 hours, and further preferably 2 to 6 hours.
  • the metal complex dye of the general formula (13) can be obtained by introducing LL 1 and LL 2 into a compound having Ru.
  • the Ru source is not particularly limited, and examples thereof include ruthenium chloride and hydrates thereof, d-1-6 described later, and the like. Preferably, d-1-6 described later, in which the valence of Ru is divalent.
  • the order of introduction of LL 1 and LL 2 is not particularly limited, but introduction from LL 2 is preferred.
  • Z 2 is usually determined by the Ru source, but additives (potassium iodide, potassium oxalate, KO—C ( ⁇ O) — (CH 2 ) p —C ( ⁇ O) —OK (p is an integer of 0 or more) Z 2 can be changed by using the like)). Also it is a Z 2 by coordinating solvent. Thereafter, the compound (14) is placed in the obtained solution containing the metal complex dye of the general formula (13), and heated from the outside as described above to obtain the metal complex dye of the general formula (1).
  • the ligand LL 2 is preferably represented by the following general formula (7).
  • R 41 to R 43 and R 51 to R 53 independently represent a hydrogen atom, an alkyl group, an alkoxy group, or an alkynyl group. At least one of R 41 to R 43 is an alkyl group, an alkoxy group, or an alkynyl group. At least one of R 51 to R 53 is an alkyl group, an alkoxy group, or an alkynyl group.
  • X 1 and X 2 are a sulfur atom, an oxygen atom, a selenium atom or NR 7 , and R 7 is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
  • R 41 to R 43 are preferably an alkyl group or an alkynyl group.
  • R 51 to R 53 are preferably an alkyl group or an alkynyl group.
  • X 1 and X 2 in the general formula (7) are preferably a sulfur atom and a selenium atom, and more preferably a sulfur atom.
  • the metal complex dye of the general formula (13) is represented by the following general formula (15), and the compound of the general formula (14) is represented by the following general formula (16).
  • a method for producing the metal complex dye represented is preferred.
  • R 61 , R 62 , R 91 and R 92 independently represent a hydrogen atom, an alkyl group, an alkoxy group or an alkynyl group, and A 1 to A 4 independently Represents a carboxyl group or a salt thereof.
  • M 12 represents an inorganic or organic ammonium ion, proton, or alkali metal ion.
  • R 61 , R 62 , R 91 and R 92 are preferably an alkyl group or an alkynyl group. Since the metal complex dye (13) and the compound of the general formula (14) have these structures, the metal complex dye (13) has a stable thiophene ring with respect to the nucleophilic compound (14). Therefore, an undesired nucleophilic reaction can be suppressed, and Cl having a high elimination ability and a low nucleophilic ability becomes a leaving group. Complex dyes can be produced efficiently.
  • the metal complex dye of the general formula (13) is represented by the following general formula (18), and the compound of the general formula (14) is represented by the following general formula (19).
  • a method for producing the metal complex dye represented is preferred.
  • R 101 , R 102 , R 111 and R 112 independently represent an alkynyl group, and A 9 to A 12 independently represent a carboxyl group or a salt thereof.
  • M 13 represents an inorganic or organic ammonium ion, proton or alkali metal ion.
  • R 101 , R 102 , R 111 and R 112 are preferably a linear or branched alkynyl group having 3 to 13 carbon atoms, more preferably a linear or branched alkynyl group having 3 to 8 carbon atoms, particularly preferably A linear or branched alkynyl group having 4 to 7 carbon atoms.
  • the dye represented by the general formula (1) has a maximum absorption wavelength in the solution in the range of 500 to 700 nm, and more preferably in the range of 500 to 650 nm.
  • 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 form a salt with a counter ion.
  • isomers based on the double bond site isomers based on the position of the ligand of the complex, and the like, either of which may be a mixture.
  • iodine and iodide for example, lithium iodide, tetrabutylammonium iodide, tetrapropylammonium iodide, etc.
  • alkyl viologens eg methyl viologen chloride, hexyl viologen bromide, benzyl viologen tetrafluoroborate
  • polyhydroxybenzenes eg hydroquinone, naphthohydroquinone, etc.
  • divalent and trivalent iron complexes for example, red blood salt and yellow blood salt.
  • a combination of iodine and iodide is preferred.
  • the cation of the iodine salt is preferably a 5-membered or 6-membered nitrogen-containing aromatic cation.
  • the compound represented by the general formula (1) is not an iodine salt, republished WO95 / 18456, JP-A-8-259543, Electrochemistry, Vol.65, No.11, p.923 (1997) It is preferable to use iodine salts such as pyridinium salts, imidazolium salts, and triazolium salts described in the above.
  • the electrolyte composition used for the photoelectric conversion element 10 of the present invention preferably contains iodine together with a heterocyclic quaternary salt compound.
  • the iodine content is preferably from 0.1 to 20% by mass, more preferably from 0.5 to 5% by mass, based on the entire electrolyte composition.
  • the electrolyte composition used for the photoelectric conversion element 10 of the present invention may contain a solvent.
  • the content of the solvent in the electrolyte composition is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 10% by mass or less based on the entire composition.
  • solvents those having a low viscosity and high ion mobility, a high dielectric constant and capable of increasing the effective carrier concentration, or both are preferable because they can exhibit excellent ion conductivity.
  • solvents include carbonate compounds (ethylene carbonate, propylene carbonate, etc.), heterocyclic compounds (3-methyl-2-oxazolidinone, etc.), ether compounds (dioxane, diethyl ether, etc.), chain ethers (ethylene glycol dialkyl ether, Propylene glycol dialkyl ether, polyethylene glycol dialkyl ether, polypropylene glycol dialkyl ether, etc.), alcohols (methanol, ethanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, etc.), Polyhydric alcohols (ethylene glycol, propylene glycol, polyethylene glycol , Propylene glycol, glycer
  • an electrochemically inert salt that is in a liquid state at room temperature and has a melting point lower than room temperature may be used.
  • an electrochemically inert salt that is in a liquid state at room temperature and has a melting point lower than room temperature
  • 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 polyfunctional monomers are preferably compounds having two or more ethylenically unsaturated groups, such as divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol Ethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate and the like are preferable.
  • divinylbenzene ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol Ethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate and the like are preferable.
  • the gel electrolyte may be formed by polymerization of a mixture containing a monofunctional monomer in addition to the above polyfunctional monomers.
  • Monofunctional monomers include acrylic acid or ⁇ -alkyl acrylic acid (acrylic acid, methacrylic acid, itaconic acid, etc.) or their esters or amides or vinyl esters (vinyl acetate, etc.), maleic acid or fumaric acid or their derivatives.
  • Esters (dimethyl maleate, dibutyl maleate, diethyl fumarate, etc.), sodium salt of p-styrenesulfonic acid, acrylonitrile, methacrylonitrile, dienes (butadiene, cyclopentadiene, isoprene, etc.), aromatic vinyl compounds (Styrene, p-chlorostyrene, t-butylstyrene, ⁇ -methylstyrene, sodium styrenesulfonate, etc.), N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N- Methylacetamide, Vinyl sulfonic acid, sodium vinyl sulfonate, sodium allyl sulfonate, sodium methacryl sulfonate, vinylidene fluoride, vinylidene chloride, vinyl alkyl ethers (such as methyl vinyl ether), ethylene,
  • 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 the same as those described in Takayuki Otsu and Masaaki Kinoshita “Experimental Methods for Polymer Synthesis” (Chemistry Dojin) and Takayuki Otsu “Lecture Polymerization Reaction Theory 1 Radical Polymerization (I)” (Chemical Doujinshi). 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.
  • preferably used 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. More preferably, the content is 1.0 to 50% by mass.
  • a polymer having a reactive group capable of crosslinking is added to the composition and a crosslinking agent.
  • 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. 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.
  • the hole conductor material 9,9'-spirobifluorene derivatives and the like can be used.
  • an electrode layer, a photoreceptor layer (photoelectric conversion layer), a charge transfer layer (hole transport layer), a conductive layer, and a counter electrode layer can be sequentially laminated.
  • a hole transport material that functions as a p-type semiconductor can be used as the hole transport layer.
  • 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, and examples of the high molecular weight materials include polyvinyl carbazole, polyamine, and organic polysilane.
  • organic polysilanes are preferable because, unlike conventional carbon-based polymers, ⁇ electrons delocalized along the main chain Si contribute to photoconduction and have high hole mobility (Phys. Rev. B, 35, 2818 (1987)).
  • the conductive layer 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. Among them, an intermolecular charge transfer complex formed from a donor material and an acceptor material is preferable. Among these, what was formed from the organic donor and the organic acceptor can be used preferably.
  • the thickness of this conductive layer is not particularly limited, but is preferably such that the porous layer can be completely filled.
  • the above donor material is preferably rich in electrons in the molecular structure.
  • organic donor materials include those having an amine group, hydroxyl group, ether group, selenium or sulfur atom in the ⁇ -electron system of the molecule, specifically, phenylamine-based, triphenylmethane-based, carbazole-based , Phenol-based materials, and tetrathiafulvalene-based materials.
  • the acceptor material those lacking electrons in the molecular structure are preferable.
  • organic acceptor materials include fullerenes, those having a substituent such as a nitro group, a cyano group, a carboxyl group or a halogen group in the ⁇ -electron system of the molecule, specifically, PCBM, benzoquinone, naphthoquinone, etc. Quinone, fluoroenone, chloranil, bromanyl, tetracyanoquinodimethane, tetracyanoethylene and the like.
  • the photosensitive layer 2 in which the sensitizing dye 21 is adsorbed on the porous semiconductor fine particles 22 on the conductive support 1. Is formed.
  • the photoreceptor layer 2 can be produced by immersing the dispersion of semiconductor fine particles in the dye solution of the present invention after coating and drying on a conductive support.
  • the conductive support 1 glass or a polymer material having a conductive film on the surface can be used as the support itself, such as metal.
  • the conductive support 1 is preferably substantially transparent. Substantially transparent means that the light transmittance is 10% or more, preferably 50% or more, particularly preferably 80% or more.
  • a glass or polymer material coated with a conductive metal oxide can be used as the conductive support 1, a glass or polymer material coated with a conductive metal oxide can be used. The coating amount of the conductive metal oxide at this time is preferably 0.1 to 100 g per 1 m 2 of the support of glass or polymer material. When a transparent conductive support is used, 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.
  • a surface may be provided with a light management function. For example, an antireflection film in which high refractive films and low refractive index oxide films described in JP-A-2003-123859 are alternately laminated, The light guide function described in JP-A-2002-260746 is improved.
  • 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 1 has a function of blocking ultraviolet light.
  • a method in which a fluorescent material capable of changing ultraviolet light into visible light is present in the transparent support or on the surface of the transparent support, or a method using an ultraviolet absorber is also included.
  • JP-A-11-250944 may be further provided on the conductive support 1.
  • 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 is preferably from 0.01 to 30 ⁇ m, more preferably from 0.03 to 25 ⁇ m, particularly preferably from 0.05 to 20 ⁇ m.
  • the conductive support 1 preferably has a lower surface resistance.
  • the range of the surface resistance is preferably 50 ⁇ / cm 2 or less, more preferably 10 ⁇ / cm 2 or less. This lower limit is not particularly limited, but is usually about 0.1 ⁇ / cm 2 .
  • a collecting electrode may be disposed.
  • One or both of a gas barrier film and an ion diffusion preventing film may be disposed between the conductive support 1 and the transparent conductive film.
  • a resin film or an inorganic film can be used as the gas barrier layer.
  • a transparent electrode and a porous semiconductor electrode photocatalyst containing layer may be provided.
  • the transparent conductive film may have a laminated structure, and as a preferable method, for example, FTO can be laminated on ITO.
  • the photoelectric conversion element 10 of the present invention has a photosensitive layer 2 in which a sensitizing dye 21 is adsorbed on a porous semiconductor fine particle 22 on a conductive support 1. Is formed.
  • the photoreceptor layer 2 can be produced by immersing the dispersion of the semiconductor fine particles 22 on the conductive support 1 and then immersing it in the above dye solution.
  • the semiconductor fine particles 22 are preferably metal chalcogenides (for example, oxides, sulfides, selenides, etc.) or perovskite fine particles.
  • metal chalcogenides for example, oxides, sulfides, selenides, etc.
  • perovskite fine particles 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 semiconductors there are an n-type in which carriers involved in conduction are electrons and a p-type in which carriers are holes.
  • n-type is preferable in terms of conversion efficiency.
  • intrinsic semiconductors for example, intrinsic semiconductors
  • the electron carrier concentration is reduced by structural defects derived from impurities.
  • high n-type semiconductors 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 gel-sol method described in Sakuo Sakuo's “Science of Sol-Gel Method”, Agne Jofusha (1998), etc. is preferable. Also preferred is a method of producing an oxide by high-temperature hydrolysis of chloride developed by Degussa in an oxyhydrogen salt.
  • the semiconductor fine particles 22 are titanium oxide
  • the sol-gel method, the gel-sol method, and the high-temperature hydrolysis method in oxyhydrogen salt of chloride are all preferable. It is also possible to use the sulfuric acid method and the chlorine method described in Gihodo Publishing (1997).
  • 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 Hydrolysis of the soluble part, formation of fine semiconductor particles from soluble and insoluble parts, dissolution and removal of soluble part, hydrothermal synthesis of peroxide aqueous solution, or production of core / shell structured titanium oxide fine particles by sol-gel method A method is mentioned.
  • crystal structure of 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.
  • (G) Semiconductor fine particle dispersion In the present invention, a semiconductor fine particle dispersion having a solid content other than semiconductor fine particles of 10% by mass or less of the entire semiconductor fine particle dispersion is applied to the conductive support 1, 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 one or more of water and various organic solvents can be used. Examples of the organic solvent include alcohols such as methanol, ethanol, isopropyl alcohol, citronellol and terpineol, ketones such as acetone, esters such as ethyl acetate, dichloromethane, acetonitrile and the like.
  • a polymer such as polyethylene glycol, hydroxyethyl cellulose, carboxymethyl cellulose, a surfactant, an acid, or a chelating agent may be used in a small amount as a dispersion aid.
  • these dispersing aids are preferably removed by a filtration method, a method using a separation membrane, a centrifugal method or the like before the step of forming a film on a conductive support.
  • 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.
  • the solid content other than the solvent and the semiconductor fine particles can be 10% by mass or less of the entire semiconductor fine dispersion. It is preferable to consist essentially of semiconductor fine particles and a dispersion solvent.
  • the viscosity of the dispersion is preferably 10 to 300 N ⁇ s / m 2 at 25 ° C. More preferably, it is 50 to 200 N ⁇ s / m 2 at 25 ° C.
  • 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 1 is increased, and it becomes easy to apply the semiconductor fine particle dispersion. .
  • the preferred thickness of the entire semiconductor fine particle layer is 0.1 ⁇ m to 100 ⁇ m.
  • the thickness of the semiconductor fine particle layer is further preferably 1 ⁇ m to 30 ⁇ m, and more preferably 2 ⁇ m 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 g to 100 g.
  • the applied semiconductor fine particle layer is subjected to heat treatment in order 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 be used in addition to heat treatment.
  • the surface may be activated by applying light absorbed by the semiconductor fine particles 22 such as ultraviolet light, or only the surface of the semiconductor fine particles 22 is activated by laser light or the like.
  • the impurities adsorbed on the particle surfaces are decomposed by the activation of the particle surfaces, and can be brought into a preferable state for the above purpose.
  • the heating is preferably performed at 100 ° C. or higher and 250 ° C. or lower or preferably 100 ° C. or higher and 150 ° C.
  • the semiconductor fine particle dispersion may be applied to the conductive support 1 and subjected to other treatments other than heating and light irradiation. Examples of preferred methods include energization and chemical treatment.
  • the pressure may be applied after application, and examples of the method of applying pressure include 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-2002-353453.
  • Examples of the chemical treatment include JP-A-2001-357896.
  • the semiconductor fine particles 22 described in Japanese Patent No. 2664194 can be used in addition to the method of applying the semiconductor fine particle dispersion on the conductive support 1. It is possible to use a method such as a method in which the precursor is applied on the conductive support 1 and hydrolyzed with moisture in the air to obtain a semiconductor fine particle film.
  • Examples of 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 (such as an alkoxide) 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 to these slurries in a small amount, and examples of the binder include cellulose, fluoropolymer, crosslinked rubber, polybutyl titanate, carboxymethyl cellulose and the like.
  • Examples of the technology relating to the formation of the semiconductor fine particles 22 or the precursor layer thereof include a method of hydrophilizing by a physical method such as corona discharge, plasma, and UV, a chemical treatment with alkali, polyethylenedioxythiophene and polystyrenesulfonic acid, polyaniline, etc. Forming an intermediate film for bonding.
  • dry method examples include vapor deposition, sputtering, and aerosol deposition method. Further, electrophoresis or electrodeposition may be used.
  • a method of once forming a coating film on a heat-resistant substrate and then transferring it to a film such as plastic may be used.
  • a method of transferring via EVA described in JP-A No. 2002-184475, a semiconductor layer / conductive layer on a sacrificial substrate containing an inorganic salt that can be removed with ultraviolet rays and an aqueous solvent described in JP-A No. 2003-98977 And a method of removing the sacrificial substrate after transfer to an organic substrate.
  • the semiconductor fine particles 22 preferably have a large surface area so that a large amount of the sensitizing dye 21 can be adsorbed.
  • the surface area thereof is preferably 10 times or more, more preferably 100 times or more the projected area.
  • it is about 5000 times.
  • JP 2001-93591 A and the like can be mentioned.
  • the thickness of the semiconductor fine particle layer increases, so that the amount of the sensitizing dye 21 that can be carried per unit area increases, so that the light absorption efficiency increases.
  • the loss due to charge recombination increases because the diffusion distance of the generated electrons increases.
  • the preferred thickness of the semiconductor fine particle layer varies depending on the use of the device, but is typically 0.1 ⁇ m to 100 ⁇ m.
  • the thickness is preferably 1 ⁇ m to 50 ⁇ m, more preferably 3 ⁇ m to 30 ⁇ m.
  • the semiconductor fine particles may be heated at a temperature of 100 ° C. 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 ° C to 600 ° C.
  • the film forming method may be any one of (1) a wet method, (2) a dry method, and (3) an electrophoresis method (including an electrodeposition method), preferably (1) a wet method, or ( 2) A dry method, more preferably (1) a wet method.
  • the coating amount of the semiconductor fine particles 22 per 1 m 2 of the support is preferably 0.5 g to 500 g, more preferably 5 g to 100 g.
  • adsorb the sensitizing dye 21 to the semiconductor fine particles 22 it is preferable to immerse the well-dried semiconductor fine particles 22 in a dye adsorbing dye solution comprising the solution and the dye according to the present invention for a long time.
  • the solvent used for the dye solution for dye adsorption can be used without particular limitation as long as it can dissolve the sensitizing dye 21 according to the present invention.
  • Such a solvent that dissolves the metal complex dye composition in the present invention is an organic solvent, and includes a nonpolar solvent, a polar aprotic solvent, a polar protic solvent, an ionic liquid, and preferably a nonpolar solvent.
  • Solvents, polar aprotic solvents, polar protic solvents are mentioned as preferred targets, for example, ethanol, methanol, isopropanol, toluene, t-butanol, acetonitrile, acetone, n-butanol, N, N-dimethylformamide, N, N-dimethylacetamide and the like can be used. Among these, ethanol and toluene can be preferably used.
  • the solubility of the metal complex dye composition in the solvent is 25 ° C., preferably 100 mg / L or more, more preferably 105 mg / L or more, and particularly preferably 110 mg / L or more.
  • the dye solution for dye adsorption comprising the solvent and the dye of the present invention may be heated to 50 ° C. to 100 ° C. as necessary.
  • Adsorption of the sensitizing dye 21 may be performed before or after the application of the semiconductor fine particles 22.
  • the semiconductor fine particles 22 and the sensitizing dye 21 may be applied and adsorbed simultaneously. Unadsorbed sensitizing dye 21 is removed by washing.
  • the sensitizing dye 21 to be adsorbed may be one kind of the dye A1 described above, or may be mixed with another dye.
  • the dye to be mixed is selected so as to make the wavelength range of photoelectric conversion as wide as possible.
  • the total amount of the sensitizing dye 21 used is preferably 0.01 to 100 mmol, more preferably 0.1 to 50 mmol, particularly preferably 0.1 to 10 mmol per 1 m 2 of the support. .
  • the amount of the sensitizing dye 21 according to the present invention is preferably 5 mol% or more.
  • the adsorption amount of the sensitizing dye 21 to the semiconductor fine particles 22 is preferably 0.001 to 1 mmol, more preferably 0.1 to 0.5 mmol, with respect to 1 g of the semiconductor fine particles.
  • a sensitizing effect in a semiconductor can be sufficiently obtained.
  • the amount of the dye is small, the sensitizing effect is insufficient, and when the amount of the dye is too large, the dye not attached to the semiconductor floats and causes the sensitizing effect to be reduced.
  • a colorless compound may be co-adsorbed for the purpose of reducing the interaction between the dyes such as association.
  • hydrophobic compound to be co-adsorbed include steroid compounds having a carboxyl group (for example, cholic acid and pivaloyl acid).
  • the surface of the semiconductor fine particles 22 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 4 functions as a positive electrode of the photoelectrochemical cell.
  • the counter electrode 4 is generally synonymous with the conductive support 1 described above, but a support for the counter electrode is not necessarily required in a configuration in which the strength is sufficiently maintained. However, having a support is advantageous in terms of hermeticity.
  • the material of the counter electrode 4 include platinum, carbon, and conductive polymer. Preferable examples include platinum, carbon, and conductive polymer.
  • the structure of the counter electrode 4 is preferably a structure having a high current collecting effect.
  • Preferred examples include JP-A-10-505192.
  • the light receiving electrode 5 may be a composite electrode such as titanium oxide and tin oxide (TiO 2 / SnO 2 ).
  • a mixed electrode of titania include Japanese Patent Application Laid-Open No. 2000-1113913.
  • Examples of mixed electrodes other than titania include Japanese Patent Application Laid-Open Nos. 2001-185243 and 2003-282164.
  • the photoelectric conversion 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 in the case of being different, the absorption spectra are preferably different.
  • the light receiving electrode 5 may be a tandem type in order to increase the utilization rate of incident light.
  • Examples of preferred tandem type configurations include those described in JP-A Nos. 2000-90989 and 2002-90989.
  • a light management function for efficiently performing light scattering and reflection inside the layer of the light receiving electrode 5 may be provided.
  • Preferable examples include those described in JP-A-2002-93476.
  • a short-circuit prevention layer between the conductive support 1 and the porous semiconductor fine particle layer in order to prevent reverse current due to direct contact between the electrolyte and the electrode.
  • Preferable examples include Japanese Patent Application Laid-Open No. 06-507999.
  • a spacer or a separator In order to prevent contact between the light receiving electrode 5 and the counter electrode 4, it is preferable to use a spacer or a separator.
  • a preferable example is JP-A-2001-283941.
  • Cell and module sealing methods include polyisobutylene thermosetting resin, novolak resin, photo-curing (meth) acrylate resin, epoxy resin, ionomer resin, glass frit, method using aluminum alkoxide for alumina, low melting point glass paste It is preferable to use a laser melting method. When glass frit is used, powder glass mixed with acrylic resin as a binder may be used.
  • a crude purified product of metal complex is prepared by the following (1) method by external heating and (2) method by microwave heating. Purified.
  • (1) Preparation of crude product of metal complex dye by external heating (a) Preparation of crude product of metal complex dye D-20 Among the metal complex dyes of the general formula (1) shown in the specific examples, D- Twenty crude products were prepared by the method shown below.
  • Compound d-2-5 was prepared by the following method.
  • metal complex dye composition including metal complex dye of general formula (5) and / or metal complex dye of general formula (6) and metal complex dye (1)
  • metal complex dye composition by external heating (1) The crude product of the metal complex dye D-20 obtained in (a) is dissolved in a methanol solution together with TBAOH (tetrabutylammonium hydroxide), and then separated on a Sephadex LH-20 (trade name, manufactured by GE Healthcare) column. Purified. The main layer fraction was collected and concentrated, and then 0.2 M nitric acid was added to obtain a precipitate.
  • TBAOH tetrabutylammonium hydroxide
  • a metal complex dye composition comprising at least one of a metal complex dye of the general formula (5) and a metal complex dye of the general formula (6) having D-17 as a main component by washing with water and diethyl ether after filtration Got.
  • 50 g of the carrier is used for 200 mg of the crude product, and the number of column purification is changed from 1 to 4 times, whereby the metal complex dye of the general formula (5) and the general formula (6)
  • Metal complex dye compositions (Examples 1 to 4) containing at least one of the above metal complex dyes were obtained.
  • the crude product of the metal complex dye D-10 obtained in (1) (b) is purified, and the metal complex dye of the general formula (5) having D-11 as a main component and the general formula ( Metal complex dye compositions (Examples 5 to 8) containing at least one of the metal complex dyes of 6) were obtained. Further, the obtained metal complex dye composition is further dissolved in a methanol solution together with TBAOH (tetrabutylammonium hydroxide), and a 0.1N nitric acid methanol solution is dropped to pH 0 so that D-10 is a main component. Metal complex dye compositions (Examples 9 to 12) containing at least one of the metal complex dye of the formula (5) and the metal complex dye of the general formula (6) were obtained.
  • TBAOH tetrabutylammonium hydroxide
  • metal complex dye composition is further dissolved in a methanol solution together with TBAOH (tetrabutylammonium hydroxide), and a 0.1N nitric acid methanol solution is dropped to pH 0 so that D-10 is a main component.
  • Metal complex dye compositions (Comparative Examples 9 to 11) containing at least one of the metal complex dye of the formula (5) and the metal complex dye of the general formula (6) were obtained.
  • the obtained metal complex dye D-11 was dissolved in a methanol solution together with TBAOH (tetrabutylammonium hydroxide), and 0.1 N nitric acid methanol solution was dropped to pH 0 to obtain D-10 (Comparative Example 12).
  • water 63: 37 (0.1% trifluoroacetic acid)
  • spectral absorption measurement is performed using U-4100 spectrophotometer (manufactured by Hitachi).
  • the absorption maximum wavelength was 571 nm.
  • the metal complex dye of the general formula (5) and the metal complex dye of the general formula (6) contained in the metal complex dye composition containing D-17 as a main component were detected as the following structures.
  • the counter ion of the acidic group is detected as a proton because it contains trifluoroacetic acid in the eluent, but in the metal complex composition, the counter ion may be a proton or tetrabutylammonium.
  • Metal complex dye composition comprising D-11 as a main component and metal complex dye composition represented by general formula (5) and metal complex dye represented by general formula (6) contained in a metal complex dye composition comprising D-10 as a main component Both dyes were detected as the following structures.
  • the counter ion of the acidic group contains trifluoroacetic acid in the eluent, it is detected as a proton. In the metal complex composition, the counter ion is proton or tetrabutylammonium.
  • This dispersion was applied to a transparent conductive film and heated at 500 ° C. to produce a semiconductor fine particle 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 body was formed was immersed in an ethanol solution having the metal complex dye composition shown in Table 1 for 12 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 .
  • This dispersion was applied to a transparent conductive film and heated at 500 ° C. to produce a semiconductor fine particle 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, 4. The glass substrate on which the insulating porous material was formed was immersed in the dye solution shown in Table 1 prepared in step 12 for 12 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 .
  • the semiconductor fine particle electrode was disposed opposite to the platinum sputtered FTO substrate through a 50 ⁇ m thick thermoplastic polyolefin resin sheet, and the resin sheet portion was melted by heat to fix the bipolar plate.
  • the electrolyte solution was injected from the injection port of the electrolyte solution previously opened in the platinum sputter
  • 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 photoelectric conversion element.
  • a methoxypropionitrile solution of dimethylpropylimidazolium iodide (0.5 mol / L) and iodine (0.1 mol / L) was used as the electrolytic solution.
  • the conversion efficiency of the photoelectrochemical cell thus determined is 9.0% or more as A, 8.0% or more and less than 9.0% as B, 7.0% or more as less than 8.0% as C, 7.0. Less than% was D, and A and B were acceptable.

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