WO2005121098A1 - Compose de squarylium, materiau de conversion photoelectrique utilisant ledit compose, convertisseur photoelectrique et cellule photoelectrochimique - Google Patents

Compose de squarylium, materiau de conversion photoelectrique utilisant ledit compose, convertisseur photoelectrique et cellule photoelectrochimique Download PDF

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WO2005121098A1
WO2005121098A1 PCT/JP2005/010570 JP2005010570W WO2005121098A1 WO 2005121098 A1 WO2005121098 A1 WO 2005121098A1 JP 2005010570 W JP2005010570 W JP 2005010570W WO 2005121098 A1 WO2005121098 A1 WO 2005121098A1
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group
ring
substituent
photoelectric conversion
compound
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PCT/JP2005/010570
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English (en)
Japanese (ja)
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Ikuo Shimizu
Masanori Ikuta
Shigeaki Kato
Yutaka Osedo
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Kyowa Hakko Chemical Co., Ltd.
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Priority to JP2006514556A priority Critical patent/JPWO2005121098A1/ja
Publication of WO2005121098A1 publication Critical patent/WO2005121098A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
    • 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
    • C09B57/007—Squaraine dyes
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/652—Cyanine dyes
    • 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
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • 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 squarylium compound that can be used for a photoelectric conversion element, a photoelectrochemical cell using the squarylium compound, and the like.
  • This battery is a wet solar battery using a ruthenium complex as a photosensitizer and a titanium dioxide porous thin film as a working electrode (see, for example, Patent Document 1 and Non-Patent Document 1).
  • a ruthenium complex of the sensitizing dye is expensive, development of a photoelectric conversion element that is sensitized by an inexpensive organic dye is desired.
  • Patent Document 1 U.S. Pat.No. 4,927,721
  • Patent Document 2 JP-A-11 86916
  • Patent Document 3 Specification of European Patent No. 911841
  • Patent Document 4 Japanese Patent Laid-Open No. 2001-76773
  • Non-Patent Document 1 “Nature”, 1991, No. 353, ⁇ ⁇ 737-740 Disclosure of Invention
  • An object of the present invention is to provide a squarylium compound that can be used for a photoelectric conversion element that is inexpensive and has high energy conversion efficiency, a photoelectrochemical cell using the same, etc. Means for Solving the Problems
  • the present invention provides the following [1] to [5].
  • R 1 and R 2 are the same or different and are each a hydrogen atom, an alkyl group optionally having a substituent, a substituent having a substituent, an atom group, an aryl group or Having a substituent, a force representing a radical aralkyl group, R 1 and R 2 together with the adjacent nitrogen atom form an optionally substituted heterocyclic ring;
  • R 3 , R 5 and R 6 are the same or different and represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, a hydroxy group, or a halogen atom, R 1 and R 3 , or R 2 and R 4 may be combined with adjacent N—C—C to form an optionally substituted heterocycle
  • R 7 is hydrogen An atom, an alkyl group which may have a substituent, a group having a substituent, a group having a substituent, an aralkyl group, a group having a substituent, a group having a substitu
  • a photoelectrochemical cell comprising the photoelectric conversion element according to [4].
  • squarylium compound represented by the general formula (I) may be expressed as squarylium compound (I). The same applies to the compounds of other formula numbers.
  • a squarylium compound that can be used in a photoelectric conversion element having low cost and high energy conversion efficiency, a photoelectrochemical cell using the squarylium compound, and the like are provided.
  • examples of the alkyl moiety in the alkyl group and the alkoxyl group include a linear or branched alkyl group having 1 to 6 carbon atoms or a cyclic group having 3 to 8 carbon atoms. Specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, 1-methylbutyl group.
  • aralkyl group examples include aralkyl groups having 7 to 15 carbon atoms, and specific examples thereof include a benzyl group, a phenethyl group, a phenylpropyl group, and a naphthylmethyl group.
  • aryl group examples include aryl groups having 6 to 14 carbon atoms, and specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, and an azulenyl group.
  • halogen atom examples include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.
  • heterocyclic ring in the heterocyclic group examples include, for example, a 5-membered or 6-membered monocyclic aromatic or aliphatic heterocyclic ring containing at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom, and 3 to 8 members.
  • heterocyclic ring in the heterocyclic group examples include condensed bicyclic or tricyclic condensed rings containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and specific examples thereof.
  • the heterocycle formed by combining R 1 and R 2 with the adjacent nitrogen atom includes, for example, a 5-membered or 6-membered monocyclic heterocycle containing at least one nitrogen atom
  • a monocyclic heterocycle may contain other nitrogen, oxygen or sulfur atoms), a bicyclic or tricyclic condensed 3- to 8-membered ring and containing at least one nitrogen atom.
  • Cyclic heterocyclic rings (the condensed heterocyclic rings may contain other nitrogen, oxygen or sulfur atoms), and specific examples thereof include pyrrolidine ring, piperidine ring, piperidine ring, and the like.
  • the heterocyclic ring formed by combining R 1 and R 3 , or R 2 and R 4 together with adjacent N—C—C includes, for example, a 5-membered structure containing at least one nitrogen atom Or a 6-membered monocyclic heterocycle (this monocyclic heterocycle may contain other nitrogen, oxygen or sulfur atoms), a bicyclic or tricyclic condensed 3- to 8-membered ring Specific examples of the condensed heterocyclic ring containing at least one nitrogen atom (the condensed heterocyclic ring may contain other nitrogen atom, oxygen atom or sulfur atom).
  • a pyrroline ring 1, 2, 3, 4-tetrahydropyridine ring, 1, 2, 3, 4-tetrahydrovirazine ring, 2, 3-dihydronozole.
  • Examples include raoxazine ring, 2,3-dihydro-1,4_thiazine ring, tetrahydroazepine ring, tetrahydrazepine ring, tetrahydroquinoline ring, tetrahydroisoquinoline ring, pyrrole ring, imidazole ring, pyrazole ring, indole ring and the like.
  • an aralkyl group, an aryl group, a heterocyclic group, a heterocyclic ring formed by combining R 1 and R 2 with an adjacent nitrogen atom, and R 1 and, or R 2 and R 4 are adjacent to each other
  • substituent of the heterocyclic ring formed together with N—C—C include the same or different 1 to 5 substituents, specifically, hydroxyl group, carboxyl group, phosphono A group, a snorejo group, a halogen atom, an anolenoquinole group, an alkoxyl group, a nitro group, an alkyl-substituted or unsubstituted amino group, and the like.
  • a halogen atom, an alkyl group, and an alkoxy group are as defined above, and an alkyl portion of the alkyl-substituted amino group is as defined above.
  • Examples of the substituent of the alkyl group and alkoxyl group are the same or different:! To 3 substituents, specifically, a hydroxyl group, a carboxyl group, a phosphono group, a sulfo group, a halogen atom, an alkoxyl Group and the like.
  • the halogen atom and the alkoxyl group have the same meanings as described above.
  • An acidic group refers to a group having a hydrogen atom that can be dissociated, and examples thereof include a carboxyleno group, a hydroxyl group, a phosphono group, and a sulfo group. These groups may form salts with alkali metal ions, ammonium ions, organic ammonium ions, etc. Moreover, it may form an intramolecular complex salt. Examples of alkali metals in alkali metal ions include lithium, sodium, and potassium. Organic ammonium In organic ions, tetraptylammonium and the like can be mentioned.
  • the squarylium compound (I) is produced by a known method (WO01 / 44233 or the like) or a method equivalent thereto.
  • WO01 / 44233 or the like a known method
  • this invention is not limited to this.
  • R, R 2 , R 3 , A and X are each as defined above, W is a halogen atom such as chlorine or bromine, or OR 8 (wherein R 8 represents an alkyl group as defined above)]
  • Compound (IV) is obtained by reacting Compound (II) with 1 to 2 moles of Compound (III) in the presence of 1 to 2 moles of a base in a solvent at 0 to 40 ° C for 1 to 20 hours. Can be obtained.
  • Examples of the solvent include halogenated hydrocarbons such as chloroform, dichloromethane, 1,2-dichloroethane, ethers such as jetyl ether and tert-butyl methyl ether, and aromatics such as toluene and benzene.
  • halogenated hydrocarbons such as chloroform, dichloromethane, 1,2-dichloroethane
  • ethers such as jetyl ether and tert-butyl methyl ether
  • aromatics such as toluene and benzene.
  • hydrocarbons methanol, alcohols such as ethanol and propanol, tetrahydrofuran, ethyl acetate, dimethylformamide, and dimethylsulfoxide (DMSO).
  • DMSO dimethylsulfoxide
  • an organic base such as quinoline, triethylamine, pyridine or the like
  • an inorganic base such as potassium carbonate, potassium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, sodium hydroxide or the like
  • Compound (III) can be obtained, for example, as a commercial product.
  • Compound (V) is compound (IV) in 50-90% by volume aqueous acetic acid solution, 90-: 120 ° C. for 0.7: -7 hours, or 50-99% by weight trifluoroacetic acid aqueous solution, It can be obtained by treating at 45 to 50 ° C for 0.:! To 3 hours.
  • Compound (I) is compound (V):! ⁇ 2 times mole of compound (VI), optionally in the presence of 1 ⁇ 2 times mole of base, in solvent, 80 ⁇ : 120 ° C 1 to: obtained by reacting for 15 hours.
  • Examples of the solvent include only alcohol solvents having 2 to 8 carbon atoms such as ethanol, propanol, isopropyl alcohol, butanol, and octanol, or a mixed solvent (alcohol 40) of the alcohol solvent and benzene or toluene. Volume% or more) is used.
  • Examples of the base include organic bases such as quinoline, triethylamine, and pyridine, and inorganic bases such as potassium carbonate, potassium bicarbonate, and sodium bicarbonate.
  • Compound (VI) can be produced by a known method (WO01 / 4437 or the like) or according thereto.
  • the compound (I) is further purified by a method usually used in organic synthetic chemistry (column chromatography, recrystallization, washing with a solvent, etc.), if necessary, by evaporating or filtering the solvent. Thus, it can be isolated and purified.
  • the photoelectric conversion element of the present invention is composed of a conductive support, a semiconductor thin film electrode made of a semiconductor sensitized by the squaric compound (I) placed on the conductive support, a charge transfer layer, a counter electrode, and the like.
  • the photoelectrochemical cell according to the present invention is one in which this photoelectric conversion element can be used for a battery used for work in an external circuit. That is, the photoelectrochemical cell of the present invention is such that an external circuit connected to the conductive support and the counter electrode of the photoelectric conversion element of the present invention via a lead works.
  • the photoelectrochemical cell is preferably sealed on the side with a polymer, an adhesive or the like in order to prevent deterioration of the constituents and volatilization of the electrolyte used for the charge transfer layer.
  • the semiconductor used for the photoelectric conversion material is a so-called photoconductor, which absorbs light and separates charges to generate electrons and holes.
  • semiconductors sensitized by squarylium compound (I) light absorption and the generation of electrons and holes due to this are mainly due to squarylium compound (I).
  • the semiconductor is responsible for receiving and transmitting these electrons.
  • the semiconductor is not particularly limited, but for example, a simple substance such as titanium oxide, indium oxide, tin oxide, bismuth oxide, zirconium oxide, tantalum oxide, niobium oxide, tandasten oxide, iron oxide, gallium oxide, nickel oxide or the like.
  • Semiconductor thin films can be manufactured using the semiconductors listed above, which are preferably compound semiconductors having nanoporous structures composed of nanoparticles [Journal of American 'Ceramic' Society (Journal of American Ceramic Society) ", 1997, No. 80, No. 12, p. 3157].
  • the semiconductor thin film electrode used in the photoelectric conversion element of the present invention is prepared, for example, by preparing a transparent electrode as a conductive support, laminating a semiconductor thin film thereon, and forming the squarylium compound ( It can be produced by adsorbing I).
  • the transparent electrode is not particularly limited as long as it has conductivity.
  • a transparent or translucent glass substrate or plastic plate for example, fluorine or antimony-doped oxide oxide, tin-doped indium oxide, zinc oxide, etc.
  • Those coated with a conductive transparent oxide semiconductor thin film, preferably those coated with a fluorine-doped tin oxide thin film are used.
  • Examples of the method of placing the compound semiconductor on the conductive support include a method of applying a dispersion or colloidal solution of the compound semiconductor on the conductive support.
  • Examples of the application method include a roller method, a dip method, an air knife method, a blade method, a spin method, and a spray method.
  • Compound semiconductors are used to electronically contact semiconductor fine particles after being applied to a conductive support, and to improve coating film strength and adhesion to the support.
  • a preferable heat treatment temperature range is 100 to 600 ° C.
  • the heat treatment time is 10 minutes to 10 hours.
  • a method of irradiating a microwave of about 28 GHz after applying a dispersion or colloidal solution on a conductive support is used.
  • the film thickness of the semiconductor thin film is preferably 0.1 to 100 / im, more preferably 2 to 25 / im.
  • the adsorption of the squarylium compound (I) onto the semiconductor thin film is performed by immersing the semiconductor thin film coated on the support in the squarylium compound (I) solution, and at room temperature for 1 minute to 2 days, or under heating conditions. It can be performed by leaving it for 1 minute to 24 hours.
  • the solvent used when the squarylium compound (I) is adsorbed on the semiconductor thin film is not particularly limited as long as it is a solvent that dissolves the squarylium compound (I).
  • alcohol solvents such as methanol and ethanol, benzene and the like
  • Hydrocarbon solvents organic solvents such as tetrahydrofuran and acetonitrile, and the like, and mixed solvents thereof are preferable.
  • the concentration of the squarylium compound (I) solution is preferably not less than 0.1 Olmmol / 1, and 0.1 to 1.0 mmolZl. More preferred.
  • the squarylium compound (I) and known dyes such as ruthenium complex dyes, other organic dyes (for example, a polymethine dye) may be used in combination.
  • a steroid compound having a carboxynole group for example, chenodeoxycholic acid
  • a steroid compound having a carboxynole group for example, chenodeoxycholic acid
  • the charge transfer layer is a layer having a function of replenishing electrons to the oxidant of the squarylium compound (I).
  • squarylium compound (I) that absorbs light emits electrons by sensitization, Converted to oxidant.
  • Examples of the charge transfer layer used in the photoelectric conversion element of the present invention include a liquid (electrolytic solution) obtained by dissolving a redoxion pair in an organic solvent, a gel electrolyte obtained by impregnating a polymer in a liquid obtained by dissolving a redox ion pair in an organic solvent, Examples thereof include a molten salt containing a redox ion pair, a solid electrolyte, an inorganic compound semiconductor, and an organic hole transport material.
  • the redox ion pair includes, for example, iodine redox, bromine redox, iron redox, tin redox, chromium redox, vanadium redox, sulfide ion redox, anthraquinone redox, and the like.
  • iodine redox includes imidazolium iodide derivatives, lithium iodide, potassium iodide, tetraalkylammonium iodide and iodine mixtures
  • bromine redox includes imidazolium bromide derivatives.
  • the organic solvent that dissolves the redox ion pair is not limited as long as it is a stable solvent that dissolves the redox ion pair.
  • organic solvents such as carbonate, propylene carbonate, dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, and nitromethane. It is preferable to use a mixed solvent thereof.
  • Etc The concentration of the redox ion pair in the electrolytic solution is preferably 0.01 to 5. Omol / 1, more preferably 0.05 to 1. Omol / 1.
  • the electrolytic solution may contain a basic compound such as tert-butylpyridine, 2_picoline, 2,6-lutidine.
  • concentration of the basic compound is preferably 0.01 to 5. Omol / 1 More preferably, 0 ⁇ 1 to: ⁇ ⁇ Omol / 1.
  • Examples of the polymer used for the gel electrolyte include polyacrylonitrile and polyvinylidene fluoride.
  • Examples of the molten salt include 1_butyl_3_methylpyridinum-mouldide, 1_butyl_3-methylimidazolium mouldide, lithium iodide, lithium acetate, and lithium perchlorate.
  • Examples thereof include thium salts, and the fluidity at room temperature may be improved by mixing a polymer such as polyethylene oxide with these.
  • solid electrolyte examples include polymers such as polyethylene oxide derivatives.
  • Examples of the inorganic compound semiconductor include copper iodide, copper bromide, and copper thiocyanide.
  • the inorganic compound semiconductor may contain a molten salt such as triethyl ammonium thiocyanate.
  • organic hole transport material examples include polythiophene derivatives and polypyrrole derivatives.
  • a titanium dioxide thin film may be applied as an undercoat layer (short-circuit prevention layer) using a technique such as spray pyrolysis to prevent a short circuit.
  • charge transfer layer There are two methods for forming the charge transfer layer, and one is that a counter electrode is first bonded to a semiconductor thin film electrode on which a dye is adsorbed, and a liquid charge transfer layer is injected into the gap. It is a method to do. The other is a method in which a charge transfer layer is directly applied to a semiconductor thin film electrode, and a counter electrode is subsequently applied.
  • a normal pressure process utilizing capillary action and a vacuum process in which the gas phase is replaced with a liquid phase at a pressure lower than normal pressure can be used.
  • a counter electrode is provided without being dried, and measures for preventing liquid leakage at the edge are also taken.
  • a gel electrolyte there is a method of applying it wet and immobilizing it by a method such as polymerization. In that case, the electrode can be applied after drying and immobilization.
  • the method for applying the electrolyte, wet organic hole transport material or gel electrolyte is the same as that for applying the semiconductor thin film electrode and the dye, dipping method, roller method, dipping method, air knife method, blade method, spin method. Law, spray method, etc. it can.
  • a solid electrolyte, an inorganic compound semiconductor, or a solid organic hole transport material a solution obtained by dissolving them in a solvent or the like is dropped onto a heated semiconductor thin film electrode and dried by vaporizing the solvent on the semiconductor thin film electrode.
  • a counter electrode can be applied after the charge transfer layer is formed by forming a solidified charge transfer layer, or by forming a charge transfer layer by a dry film forming process such as a vacuum deposition method or a CVD method (chemical vapor deposition method).
  • Examples of the counter electrode used in the photoelectric conversion element of the present invention include platinum, rhodium, ruthenium, carbon, oxide semiconductor electrode and the like coated in a thin film on a conductive substrate. Platinum, carbon electrodes and the like coated in a thin film on a conductive substrate are preferred.
  • the photoelectric conversion element of the present invention there is no limitation as long as it prevents contact between the semiconductor thin film electrode and the counter electrode, which may use a spacer, but for example, a polymer film such as polyethylene is used. .
  • the squarylium compound (I) used in the present invention is inexpensive.
  • Titanium dioxide paste manufactured by Solaronix, SA
  • transparent conductive glass manufactured by Nippon Sheet Glass, surface resistance is about 15 ⁇ / cm 2
  • Ti-Nanoxide T was applied using a glass rod, dried at room temperature for 30 minutes, and then baked in an electric furnace at 450 ° C for 30 minutes. The thickness of titanium dioxide was 10 ⁇ . After removing the glass and cooling, it was added to the acetonitrile solution (compound (1) 0.1 mmol / l, chenodeoxycholic acid 10 mmol / l) mixed with compound (1) and chenodeoxycholic acid at 75 ° C. Soaked for 30 minutes. The glass adsorbed with the dye was washed with acetonitrile and allowed to air dry.
  • the titanium dioxide electrode substrate (lcm X 3cm) prepared as described above was superposed on a platinum-deposited glass of the same size.
  • an electrolyte solution iodine 0.05 mol / l, lithium iodide 0.1 mol / 1, dimethylpropylimidazolyl iodine 0.62 molZl and tert-butyl pyridine 0.5 mol / l acetonitrile solution
  • a photoelectrochemical cell was obtained by impregnating with a titanium dioxide electrode and introducing it between the titanium dioxide electrode and the counter electrode.
  • This photoelectrochemical cell was irradiated with 100 mW / cm 2 of artificial sunlight using a 500 W xenon short arc lamp (manufactured by Usio Electric), and its characteristics were evaluated with an IV curve tracer (manufactured by Eihiro Seiki).
  • the characteristics of the obtained photoelectrochemical cell were as follows: short-circuit current density 6.7 mA / cm 2 , open-circuit voltage 0.66 V, form factor (fill factor) 0.59, and energy conversion efficiency 2.5%. .
  • a squarylium compound that can be used in a photoelectric conversion element having low cost and high energy conversion efficiency, a photoelectrochemical cell using the squarylium compound, and the like are provided.

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Abstract

Il est prévu un composé de squarylium représenté par la formule générale suivante (I) (où R1 et R2 peuvent être identiques ou différents et représentent respectivement un atome d’hydrogène, un groupe alkyle substitué en option, un groupe aryle substitué en option ou similaire; R3, R4, R5 et R6 peuvent être identiques ou différents et représentent respectivement un atome d’hydrogène, un groupe alkyle substitué en option, un groupe alcoxyle substitué en option ou similaire; X représente un atome d’azote ou un atome d’oxygène; et A représente un groupe acide). Il est également prévu un matériau de conversion photoélectrique ou similaire contenant un tel composé de squarilium et un semi-conducteur.
PCT/JP2005/010570 2004-06-09 2005-06-09 Compose de squarylium, materiau de conversion photoelectrique utilisant ledit compose, convertisseur photoelectrique et cellule photoelectrochimique WO2005121098A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008090757A1 (fr) * 2007-01-22 2008-07-31 Konica Minolta Holdings, Inc. Composé de squarylium, composition contenant un composé de squarylium, filtre optique et filtre frontal pour écran d'affichage
JP2018510845A (ja) * 2015-01-27 2018-04-19 ソニー株式会社 有機フォトダイオード中の有機光電変換層の材料としてのスクアラインおよびチオフェン系分子

Citations (8)

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