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WO2012008556A1 - Elément de conversion photoélectrique - Google Patents

Elément de conversion photoélectrique Download PDF

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Publication number
WO2012008556A1
WO2012008556A1 PCT/JP2011/066168 JP2011066168W WO2012008556A1 WO 2012008556 A1 WO2012008556 A1 WO 2012008556A1 JP 2011066168 W JP2011066168 W JP 2011066168W WO 2012008556 A1 WO2012008556 A1 WO 2012008556A1
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formula
group
repeating unit
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compound
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健一郎 大家
吉村　研
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/124—Copolymers alternating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/141—Side-chains having aliphatic units
    • C08G2261/1412—Saturated aliphatic units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3246—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing nitrogen and sulfur as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/411—Suzuki reactions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C08G2261/91—Photovoltaic applications
    • 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
    • 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
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers
    • 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
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a photoelectric conversion element.
  • a high molecular compound having a ⁇ -conjugated structure absorbs light in a visible light region and a peripheral region of visible light and has a conductive property
  • application to a photoelectric conversion element has been studied.
  • a photoelectric conversion element provided with an organic layer containing a polymer compound having a ⁇ -conjugated structure a polymer compound having a repeating unit represented by the formula (A) and a repeating unit represented by the formula (B)
  • a photoelectric conversion element including an organic layer is known (WO2007 / 011739).
  • the photoelectric conversion element does not necessarily have high photoelectric conversion efficiency.
  • the present invention provides a photoelectric conversion element having high photoelectric conversion efficiency. That is, the present invention provides a photoelectric conversion element having a pair of electrodes and an organic layer containing a polymer compound having a repeating unit represented by the formula (I) between the electrodes.
  • Ar represents an arylene group.
  • R represents a fluorine atom or a monovalent organic group having a fluorine atom. Two R may be the same or different.
  • this invention provides the said photoelectric conversion element which has an organic layer containing the repeating unit represented by Formula (II) and Formula (III) other than the repeating unit represented by Formula (I).
  • X represents a sulfur atom or an oxygen atom.
  • Z represents ⁇ CH—, ⁇ C (R) —, or a nitrogen atom.
  • Two Z may be the same or different.
  • R represents the same meaning as described above.
  • E represents a sulfur atom, an oxygen atom, a selenium atom, -NH- or -N (R 1 ) ⁇ .
  • R 1 Represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a heteroaryl group. Multiple R 1 May be the same or different.
  • Y represents a divalent group.
  • R represents the same meaning as described above. Description of embodiment Hereinafter, the present invention will be described in detail.
  • the photoelectric conversion element of the present invention has a pair of electrodes and an organic layer containing a polymer compound having a repeating unit represented by the formula (I) between the electrodes.
  • Ar and R represent the same meaning as described above.
  • the arylene group represented by Ar is a group obtained by removing two hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent. Examples of the substituent include a bromine atom, a chlorine atom, an iodine atom, and an alkoxy group having 1 to 20 carbon atoms.
  • the carbon number of the arylene group is usually 6 to 60, preferably 6 to 16, and more preferably 6 to 10.
  • arylene group examples include a phenylene group, a naphthalenediyl group, an anthracenediyl group, a tetracenediyl group, a pentacenediyl group, and a pyrenediyl group.
  • R represents a fluorine atom or a monovalent organic group having a fluorine atom.
  • the monovalent organic group having a fluorine atom include an alkyl group substituted with a fluorine atom, an alkoxy group substituted with a fluorine atom, an aryl group substituted with a fluorine atom, and a heteroaryl group substituted with a fluorine atom. Is mentioned.
  • An alkyl group substituted with a fluorine atom, an alkoxy group substituted with a fluorine atom, an aryl group substituted with a fluorine atom, and a heteroaryl group substituted with a fluorine atom are further substituted with a substituent other than a fluorine atom.
  • substituents include a bromine atom, a chlorine atom, and an alkoxy group having 1 to 12 carbon atoms.
  • the alkyl group may be linear, branched, or cyclic.
  • the alkyl group usually has 1 to 30 carbon atoms.
  • alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl tomb, pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl.
  • hexyl group isohexyl group, 3-methylpentyl group, 21-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl And chain alkyl groups such as a group, tetradecyl group, hexadecyl tomb, octadecyl group and eicosyl group, and cyclic alkyl groups such as cyclopentyl group, cyclohexyl group and adamantyl group.
  • the alkyl part of the alkoxy group may be linear, branched or cyclic.
  • the carbon number of the alkoxy group is usually 1-20, and specific examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, Examples include hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, and lauryloxy.
  • Examples of the alkoxy group substituted with a substituent other than a fluorine atom include a methoxymethyloxy group and a 2-methoxyethyloxy group.
  • An aryl group is a group obtained by removing one hydrogen on an aromatic ring from an aromatic hydrocarbon compound.
  • the aryl group usually has 6 to 60 carbon atoms.
  • Specific examples of the aryl group include a phenyl group, a C1 to C12 alkylphenyl group (C1 to C12 represents 1 to 12 carbon atoms, and the same shall apply hereinafter), a 1-naphthyl group, and a 2-naphthyl group. Groups.
  • a heteroaryl group is a group obtained by removing one hydrogen on an aromatic ring from an aromatic heterocyclic compound.
  • the heteroaryl group usually has 2 to 60 carbon atoms.
  • Specific examples of the heteroaryl group include a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, and a triazinyl group.
  • R include a fluorine atom (formula (R-1)) and groups represented by formulas (R-2) to (R-11).
  • R is a fluorine atom, a group represented by formula (R-2), formula (R-5), formula (R-8), or formula (R-10).
  • R-2 is a fluorine atom, a group represented by formula (R-2), formula (R-5), formula (R-8), or formula (R-10).
  • a fluorine atom and a group represented by the formula (R-2) are more preferred, and a fluorine atom is particularly preferred.
  • the repeating unit represented by Formula (I) is preferably a repeating unit represented by Formula (A-1) to Formula (A-4).
  • R represents the same meaning as described above.
  • Examples of the repeating unit represented by formula (A-1) to formula (A-4) include the repeating units represented by formula (B-1) to formula (B-18).
  • R represents the same meaning as described above.
  • the formula (B-1), the formula (B-2), the formula ( B-3), Formula (B-4), Formula (B-5), Formula (B-8), Formula (B-10), Formula (B-11), Formula (B-12), Formula (B -13), the formula (B-15), the formula (B-16) and the repeating unit represented by the formula (B-18) are preferable, and the formula (B-1), the formula (B-4), the formula (B -5), the formula (B-11), the formula (B-12), and the repeating unit represented by the formula (B-15) are more preferable, the formula (B-1), the formula (B-5), the formula ( The repeating unit represented by B-12) and formula (B-15) is more preferred, and the repeating unit represented by formula (B-1) is particularly preferred.
  • the polymer compound used in the photoelectric conversion element of the present invention preferably has a repeating unit other than the repeating unit represented by the formula (I).
  • a repeating unit include an aromatic repeating unit different from the repeating unit represented by formula (I), and the repeating unit represented by formula (II) and the formula (III) described above. Are preferred.
  • the repeating unit represented by formula (II) include the repeating units represented by formula (C-1) to formula (C-12).
  • the alkyl group represented by may be linear, branched, or cyclic.
  • the alkyl group may have a substituent, and examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the alkyl group usually has 1 to 30 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl tomb, pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl.
  • hexyl group isohexyl group, 3-methylpentyl group, 21-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl And chain alkyl groups such as a group, tetradecyl group, hexadecyl tomb, octadecyl group and eicosyl group, and cyclic alkyl groups such as cyclopentyl group, cyclohexyl group and adamantyl group.
  • the alkyl part of the alkoxy group represented by may be linear, branched or cyclic.
  • the carbon number of the alkoxy group is usually 1-20.
  • the alkoxy group may have a substituent, and examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and an alkoxy group having 1 to 20 carbon atoms.
  • alkoxy group examples include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group Group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group and lauryloxy group.
  • alkoxy group substituted with a substituent examples include a methoxymethyloxy group and a 2-methoxyethyloxy group.
  • R 1 Is a group obtained by removing one hydrogen on an aromatic ring from an aromatic hydrocarbon compound.
  • the aryl group usually has 6 to 60 carbon atoms.
  • the aryl group may have a substituent, and examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and an alkoxy group having 1 to 20 carbon atoms.
  • Specific examples of the aryl group include a phenyl group, a C1 to C12 alkylphenyl group (C1 to C12 represents 1 to 12 carbon atoms, and the same shall apply hereinafter), a 1-naphthyl group, and a 2-naphthyl group. Groups.
  • aryl group substituted with a substituent examples include a C1-C12 alkoxyphenyl group.
  • R 1 Is a group obtained by removing one hydrogen on an aromatic ring from an aromatic heterocyclic compound.
  • the heteroaryl group usually has 2 to 60 carbon atoms.
  • the heteroaryl group may have a substituent. Examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms. And aryl groups having 6 to 60 carbon atoms.
  • heteroaryl group examples include a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, and a triazinyl group.
  • the repeating unit represented by the formula (III) examples include repeating units represented by the formulas (E-1) to (E-16). Where R 1 Represents the same meaning as described above.
  • the repeating units represented by (E-5), formula (E-9), formula (E-12) and formula (E-13) are preferred, and formula (E-1), formula (E-5) and formula are preferred.
  • the repeating unit represented by (E-9) is more preferable, and the repeating unit represented by Formula (E-1) and Formula (E-9) is particularly preferable.
  • the polymer compound having a repeating unit represented by formula (I) used in the present invention is used as a photoelectric conversion element, the polymer compound is based on the entire polymer compound from the viewpoint of photoelectric conversion efficiency.
  • the weight fraction of the repeating unit represented by the formula (I) is preferably 0.01 to 0.80, more preferably 0.03 to 0.50, and 0.05 to 0.20. It is particularly preferred.
  • the repeating unit represented by formula (I), formula (II), and formula (III) It is preferable from the viewpoint of photoelectric conversion efficiency.
  • the fraction of the repeating unit represented by the formula (I) is preferably 0.02 to 0.80, more preferably 0.05 to 0.50 from the viewpoint of photoelectric conversion efficiency. 0.10 to 0.30 is particularly preferable.
  • the polymer compound having a repeating unit represented by the formula (I) is preferably a polymer compound having a number average molecular weight of 3,000 or more, and a polymer compound having a number average molecular weight of 3,000 to 10,000,000. More preferably, a polymer compound having a number average molecular weight of 8,000 to 5,000,000 is more preferable, and a polymer compound having a number average molecular weight of 10,000 to 1,000,000 is particularly preferable. If the number average molecular weight is lower than 3,000, defects may occur in film formation during device fabrication, and if it exceeds 10,000,000, solubility in a solvent and applicability during device fabrication may be degraded. .
  • the number average molecular weight refers to the number average molecular weight in terms of polystyrene calculated using a standard sample of polystyrene using gel permeation chromatography (GPC).
  • the polymer compound having a repeating unit represented by the formula (I) preferably has a high solubility in a solvent in order to facilitate the production of the device.
  • the polymer compound used in the photoelectric conversion element of the present invention preferably has a solubility capable of producing a solution containing 0.01 wt% or more of the polymer compound, and a solution containing 0.1 wt% or more is preferable.
  • the polymer compound of the present invention can exhibit high electron and / or hole transport properties, when a thin film containing the polymer compound is used for an element, electrons or holes injected from the electrode, or light absorption. The charge generated by can be transported. Taking advantage of these characteristics, it can be suitably used for various electronic devices such as a photoelectric conversion device, an organic thin film transistor, and an organic electroluminescence device. Hereinafter, these elements will be described individually.
  • the thickness of the thin film containing the polymer compound of the present invention is usually 1 nm to 100 ⁇ m, preferably 2 nm to 1000 nm, more preferably 5 nm to 500 nm, and further preferably 20 nm to 200 nm.
  • the photoelectric conversion element containing the polymer compound of the present invention has one or more active layers containing the polymer compound of the present invention between a pair of electrodes, at least one of which is transparent or translucent.
  • a preferable form of the photoelectric conversion element containing the polymer compound of the present invention is formed from a pair of electrodes, at least one of which is transparent or translucent, and an organic composition of a p-type organic semiconductor and an n-type organic semiconductor. Having an active layer.
  • the polymer compound of the present invention is preferably used as a p-type organic semiconductor.
  • the photoelectric conversion element manufactured using the polymer compound of the present invention is usually formed on a substrate.
  • the substrate may be any substrate that does not chemically change when the electrodes are formed and the organic layer is formed. Examples of the material for the substrate include glass, plastic, polymer film, and silicon.
  • the opposite electrode that is, the electrode far from the substrate is preferably transparent or translucent.
  • the first active layer containing the polymer compound of the present invention is interposed between a pair of electrodes, at least one of which is transparent or translucent, and the first A photoelectric conversion element including a second active layer containing an electron accepting compound such as a fullerene derivative adjacent to the active layer.
  • the transparent or translucent electrode material include a conductive metal oxide film and a translucent metal thin film.
  • indium oxide, zinc oxide, tin oxide, and their composite materials such as indium tin oxide (ITO), indium zinc oxide, etc., conductive materials, NESA, gold, platinum, silver, Copper is used, and ITO, indium / zinc / oxide, and tin oxide are preferable.
  • Examples of the method for producing the electrode include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like.
  • As the electrode material an organic transparent conductive film such as polyaniline and derivatives thereof, polythiophene and derivatives thereof may be used.
  • One electrode may not be transparent, and a metal, a conductive polymer, etc. can be used as an electrode material of the electrode.
  • the electrode material include metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like. And one or more alloys selected from the group consisting of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, and tin. Examples include alloys with metals, graphite, graphite intercalation compounds, polyaniline and derivatives thereof, and polythiophene and derivatives thereof.
  • the alloy examples include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy.
  • An additional intermediate layer other than the active layer may be used as a means for improving the photoelectric conversion efficiency.
  • the material used for the intermediate layer include alkali metals such as lithium fluoride, halides of alkaline earth metals, oxides such as titanium oxide, and PEDOT (poly-3,4-ethylenedioxythiophene).
  • the active layer may contain the polymer compound of the present invention alone or in combination of two or more.
  • compounds other than the polymer compound of the present invention can be mixed and used as the electron donating compound and / or the electron accepting compound in the active layer.
  • the electron-donating compound and the electron-accepting compound are relatively determined from the energy levels of these compounds.
  • the electron-donating compound in addition to the polymer compound of the present invention, for example, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, Examples thereof include polysiloxane derivatives having an aromatic amine residue in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof.
  • the electron-accepting compound in addition to the polymer compound of the present invention, for example, carbon materials, metal oxides such as titanium oxide, oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof Derivatives, anthraquinones and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof Derivatives, polyfluorenes and derivatives thereof, phenanthroline derivatives such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (basocproin), fullerenes and fullerene derivatives Details, titanium oxide, carbon nanotubes, fulleren
  • Fullerene and fullerene derivatives include C 60 , C 70 , C 76 , C 78 , C 84 And derivatives thereof.
  • the fullerene derivative represents a compound in which at least a part of fullerene is modified.
  • Examples of the fullerene derivative include a compound represented by the formula (15), a compound represented by the formula (16), a compound represented by the formula (17), and a compound represented by the formula (18).
  • R a Is a group having a substituted or unsubstituted alkyl group, aryl group, heteroaryl group or ester structure. Multiple R a May be the same or different.
  • R b Represents a substituted or unsubstituted alkyl group or aryl group.
  • R a and R b The definition and specific examples of the substituted or unsubstituted alkyl group and aryl group represented by are the same as the definition and specific examples of the substituted or unsubstituted alkyl group and aryl group represented by R.
  • R a Is a remaining atomic group obtained by removing two hydrogen atoms from an aromatic heterocyclic compound which may have a substituent. Examples of the heteroaryl group include thienyl group, pyrrolyl group, furyl group, pyridyl group, quinolyl group, isoquinolyl group and the like.
  • R a Examples of the group having an ester structure represented by the formula (19) include a group represented by the formula (19).
  • R c Represents a substituted or unsubstituted alkyl group, aryl group or heteroaryl group.
  • C 60 Specific examples of fullerene derivatives include the following.
  • C 70 Specific examples of fullerene derivatives include the following.
  • fullerene derivatives include [6,6] phenyl-C61 butyric acid methyl ester (C60PCBM, [6,6] -phenyl C61 butyric acid methyl ester), [6,6] phenyl-C71 butyric acid methyl ester (C70PCBM). , [6,6] -Phenyl C71 butyric acid methyl ester), [6,6] phenyl-C85 butyric acid methyl ester (C84PCBM, [6,6] -Phenyl C85 butyric acid methyl ester), [6,6] thienyl- And C61 butyric acid methyl ester ([6,6] -Thienyl C61 butyric acid methyl ester).
  • the amount of the fullerene derivative is preferably 10 to 1000 parts by weight with respect to 100 parts by weight of the polymer compound of the present invention. More preferably, it is ⁇ 500 parts by weight.
  • the active layer is a thin film of a composition comprising the polymer compound of the present invention and an electron accepting compound, and the thickness is usually 1 nm to 100 ⁇ m, preferably 2 nm to 1000 nm, more preferably 5 nm to 500 nm. More preferably, it is 20 nm to 200 nm.
  • the method for producing the active layer may be produced by any method, and examples thereof include film formation from a solution containing a polymer compound and film formation by a vacuum deposition method.
  • a preferred method for producing a photoelectric conversion element is a method for producing an element having a first electrode and a second electrode, and having an active layer between the first electrode and the second electrode, Applying a solution (ink) containing the polymer compound of the present invention and a solvent on the first electrode by a coating method to form an active layer; and forming a second electrode on the active layer. It is a manufacturing method of the element which has.
  • the solvent used for film formation from a solution may be any one that dissolves the polymer compound of the present invention.
  • the solvent examples include hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, butylbenzene, sec-butylbenzene, tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, Examples thereof include halogenated hydrocarbon solvents such as bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, chlorobenzene, dichlorobenzene, and trichlorobenzene, and ether solvents such as tetrahydrofuran and tetrahydropyran.
  • hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, bicycl
  • the polymer compound of the present invention can usually be dissolved in the solvent in an amount of 0.1% by weight or more.
  • the surface tension of the solvent at 25 ° C. is preferably larger than 15 mN / m, more preferably larger than 15 mN / m and smaller than 100 mN / m, larger than 25 mN / m and larger than 60 mN / m. It is more preferable that the value is small.
  • the polymer compound of the present invention can also be used for organic thin film transistors.
  • the organic thin film transistor has a configuration including a source electrode and a drain electrode, an organic semiconductor layer (active layer) serving as a current path between these electrodes, and a gate electrode for controlling the amount of current passing through the current path.
  • the organic semiconductor layer is constituted by the organic thin film described above. Examples of such an organic thin film transistor include a field effect type and an electrostatic induction type.
  • a field effect organic thin film transistor includes a source electrode and a drain electrode, an organic semiconductor layer (active layer) serving as a current path between them, a gate electrode for controlling the amount of current passing through the current path, and an organic semiconductor layer and a gate electrode It is preferable to provide an insulating layer disposed between the two.
  • the source electrode and the drain electrode are preferably provided in contact with the organic semiconductor layer (active layer), and the gate electrode is preferably provided with an insulating layer in contact with the organic semiconductor layer interposed therebetween.
  • the organic semiconductor layer is constituted by an organic thin film containing the polymer compound of the present invention.
  • the static induction organic thin film transistor has a source electrode and a drain electrode, an organic semiconductor layer (active layer) serving as a current path between them, and a gate electrode that controls the amount of current passing through the current path. It is preferable to be provided in the organic semiconductor layer.
  • the source electrode, the drain electrode, and the gate electrode provided in the organic semiconductor layer are preferably provided in contact with the organic semiconductor layer.
  • the structure of the gate electrode may be a structure in which a current path flowing from the source electrode to the drain electrode is formed and the amount of current flowing through the current path can be controlled by a voltage applied to the gate electrode.
  • An electrode is mentioned.
  • the organic semiconductor layer is constituted by an organic thin film containing the polymer compound of the present invention.
  • the polymer compound of the present invention can also be used for an organic electroluminescence device (organic EL device).
  • An organic EL element has a light emitting layer between a pair of electrodes, at least one of which is transparent or translucent.
  • the organic EL element may include a hole transport layer and an electron transport layer in addition to the light emitting layer.
  • the polymer compound of the present invention is contained in any one of the light emitting layer, the hole transport layer, and the electron transport layer.
  • the light emitting layer may contain a charge transport material (which means a generic term for an electron transport material and a hole transport material).
  • a charge transport material which means a generic term for an electron transport material and a hole transport material.
  • an organic EL element an element having an anode, a light emitting layer, and a cathode, and an anode, a light emitting layer, and an electron having an electron transport layer containing an electron transport material adjacent to the light emitting layer between the cathode and the light emitting layer.
  • the photoelectric conversion element using the polymer compound of the present invention is operated as an organic thin film solar cell by generating photovoltaic power between the electrodes by irradiating light such as sunlight from a transparent or translucent electrode. Can do. It can also be used as an organic thin film solar cell module by integrating a plurality of organic thin film solar cells.
  • the organic thin film transistor can be used as a pixel driving element used for controlling the pixel of an electrophoretic display, a liquid crystal display, an organic electroluminescence display, etc., and controlling the uniformity of screen luminance and the screen rewriting speed.
  • the organic thin film solar cell can basically have the same module structure as a conventional solar cell module.
  • the solar cell module generally has a structure in which cells are formed on a support substrate such as metal or ceramic, and the cell is covered with a filling resin or protective glass, and light is taken in from the opposite side of the support substrate. It is also possible to use a transparent material such as tempered glass for the support substrate, configure a cell thereon, and take in light from the transparent support substrate side.
  • a module structure called a super straight type, a substrate type, and a potting type, a substrate integrated module structure used in an amorphous silicon solar cell, and the like are known.
  • the organic thin-film solar cell manufactured using the polymer compound of the present invention can also be appropriately selected from these module structures depending on the purpose of use, place of use and environment.
  • a typical super straight type or substrate type module cells are arranged at regular intervals between support substrates that are transparent on one or both sides and subjected to antireflection treatment, and adjacent cells are connected by metal leads or flexible wiring.
  • the current collector electrode is connected to the outer edge portion, and the generated power is taken out to the outside.
  • plastic materials such as ethylene vinyl acetate (EVA) may be used between the substrate and the cell in the form of a film or a filling resin depending on the purpose in order to protect the cell and improve the current collection efficiency.
  • EVA ethylene vinyl acetate
  • the surface protection layer is made of a transparent plastic film, or the protective function is achieved by curing the filling resin. It is possible to eliminate the supporting substrate on one side.
  • the periphery of the support substrate is fixed in a sandwich shape with a metal frame in order to ensure internal sealing and module rigidity, and the support substrate and the frame are hermetically sealed with a sealing material.
  • a flexible material is used for the cell itself, the support substrate, the filling material, and the sealing material, a solar cell can be formed on the curved surface.
  • a solar cell using a flexible support such as a polymer film
  • cells are sequentially formed while feeding out a roll-shaped support, cut to a desired size, and then the periphery is sealed with a flexible and moisture-proof material.
  • the battery body can be produced.
  • a module structure called “SCAF” described in Solar Energy Materials and Solar Cells, 48, p383-391 may be used.
  • a solar cell using a flexible support can be used by being bonded and fixed to a curved glass or the like.
  • Synthesis Example 1 Synthesis of Compound 2 In a four-necked flask, 2.674 g (15.00 mmol) of Compound 1, 6.083 g (31.50 mmol) of bromooctane, 62.25 mg (2.5 mol%) of potassium iodide, and 50 mL of dimethyl sulfoxide were added. Argon bubbling was performed at room temperature (25 ° C.) for 30 minutes. After cooling to 0 ° C. with an ice bath, 2.525 g (45.00 mmol) of potassium hydroxide was added and reacted for 6 days.
  • NBS N-bromosuccinimide
  • the toluene solution was passed through an alumina / silica gel column, and the resulting solution was poured into methanol to precipitate a polymer.
  • the polymer was filtered and dried to obtain 150 mg of polymer compound A.
  • the weight average molecular weight (Mw) was 8,000
  • the number average molecular weight (Mn) was 6,000.
  • Synthesis Example 5 Synthesis of Compound 8 In a 1000 mL four-necked flask in which the air in the flask was replaced with argon, 13.0 g (80.0 mmol) of 3-bromothiophene and 80 mL of diethyl ether were added to obtain a uniform solution. While maintaining the solution at ⁇ 78 ° C., 31 mL of a 2.6M n-butyllithium (n-BuLi) hexane solution (n-BuLi was 80.6 mmol) was added dropwise. After reacting at ⁇ 78 ° C.
  • reaction solution was cooled to ⁇ 25 ° C., and a solution in which 60 g (236 mmol) of iodine was dissolved in 1000 mL of diethyl ether was added dropwise over 30 minutes. After dropping, the mixture was stirred at room temperature (25 ° C.) for 2 hours, and 50 mL of 1N aqueous sodium thiosulfate solution was added to stop the reaction. After extracting the reaction product with diethyl ether, the reaction product was dried with magnesium sulfate, filtered, and the filtrate was concentrated to obtain 35 g of a crude product. The crude product was purified by recrystallization using chloroform to obtain 28 g of Compound 8.
  • Synthesis Example 6 Synthesis of Compound 9 10.5 g (23.4 mmol) of bisiodothienylmethanol (Compound 8) and 150 mL of methylene chloride were added to a 300 mL four-necked flask to obtain a uniform solution. To the solution, 7.50 g (34.8 mmol) of pyridinium chlorochromate was added and stirred at room temperature (25 ° C.) for 10 hours. The reaction solution was filtered to remove insolubles, and then the filtrate was concentrated to obtain 10.0 g (22.4 mmol) of Compound 9.
  • Synthesis Example 7 Synthesis of Compound 10 In a 300 mL flask in which the air in the flask was replaced with argon, 10.0 g (22.4 mmol) of compound 9 and 6.0 g (94.5 mmol) of copper powder, dehydrated N, N-dimethylformamide (hereinafter referred to as DMF). 120 mL) was added and stirred at 120 ° C. for 4 hours. After the reaction, the flask was cooled to room temperature (25 ° C.), and the reaction solution was passed through a silica gel column to remove insoluble components. Thereafter, 500 mL of water was added, and the reaction product was extracted with chloroform.
  • DMF dehydrated N, N-dimethylformamide
  • the toluene solution was passed through an alumina / silica gel column, and the resulting solution was poured into methanol to precipitate a polymer.
  • the polymer was filtered and dried to obtain 291 mg of polymer compound B.
  • the weight average molecular weight (Mw) was 32,000, and the number average molecular weight (Mn) was 16,000.
  • Synthesis Example 14 Synthesis of Compound 18 In a 200 mL flask in which the air in the flask was replaced with argon, 1.78 g (10.0 mmol) of compound 17, 5.83 g (25.0 mmol) of 2-ethylhexyl bromide, and 41.5 mg (0.25 mmol) of potassium iodide. ), 1.68 g (30.0 mmol) of potassium hydroxide was dissolved in 35 mL of dimethyl sulfoxide and stirred at room temperature (25 ° C.) for 24 hours.
  • 2-yl) -2,1,3-benzothiadiazole (manufactured by Sigma-Aldrich) 388.1 mg (1.00 mmol), methyltrialkylammonium chloride (trade name Aliquat 336 (registered trademark), manufactured by Sigma-Aldrich) was dissolved in 20 ml of toluene, and the resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 2.25 mg of palladium acetate, 12.3 mg of tris (2-methoxyphenyl) phosphine (12.3 mg) and 6.5 mL of 16.7 wt% aqueous sodium carbonate solution were added, and the mixture was added at 100 ° C. for 5 hours. Stirring was performed.
  • polymer compound C As for the molecular weight (polystyrene conversion) of the high molecular compound C measured by GPC, Mw was 30,000 and Mn was 14,000.
  • Mw As for the molecular weight (polystyrene conversion) of the high molecular compound C measured by GPC, Mw was 30,000 and Mn was 14,000.
  • the polymer compound B and fullerene C60PCBM (phenyl C61-butyric acid methyl ester, manufactured by Frontier Carbon Co.) have a ratio of the weight of C60PCBM to the weight of the polymer compound B of 3.
  • Ink 1 was produced by dissolving in orthodichlorobenzene as described above.
  • the total weight of the polymer compound B and the C60PCBM was 2.0% by weight with respect to the weight of the ink 1.
  • the ink 1 was applied on a glass substrate by spin coating to prepare an organic film containing the polymer compound B.
  • the film thickness was about 100 nm.
  • the light absorption edge wavelength of the organic film thus produced was 750 nm.
  • lithium fluoride was vapor-deposited with a thickness of 2 nm on the organic film by a vacuum vapor deposition machine, and then Al was vapor-deposited with a thickness of 100 nm to produce an organic thin film solar cell.
  • the shape of the obtained organic thin film solar cell was a square of 2 mm ⁇ 2 mm.
  • a solar simulator (trade name OTENTO-SUNII: AM1.5G filter, irradiance 100 mW / cm, manufactured by Spectrometer Co., Ltd.) was applied to the obtained organic thin film solar cell. 2 ) was irradiated with constant light, and the generated current and voltage were measured to determine photoelectric conversion efficiency, short-circuit current density, open-circuit voltage, and fill factor.
  • Jsc (short circuit current density) is 9.63 mA / cm 2 Voc (open end voltage) was 0.67 V
  • ff (fill factor (curve factor)) was 0.62
  • photoelectric conversion efficiency ( ⁇ ) was 4.03%.
  • Table 1 An ink and an organic thin film solar cell were prepared and evaluated in the same manner as in Example 3 except that the polymer compound A was used instead of the polymer compound B.
  • Jsc (short circuit current density) is 9.90 mA / cm 2 Voc (open end voltage) was 0.61 V
  • ff (fill factor) was 0.44
  • the photoelectric conversion efficiency ( ⁇ ) was 2.62%.
  • Table 1 The results are shown in Table 1.
  • Comparative Example 1 An ink and an organic thin film solar cell were prepared and evaluated in the same manner as in Example 3 except that the polymer compound C was used instead of the polymer compound B. Jsc (short circuit current density) is 4.61 mA / cm. 2 Voc (open end voltage) was 0.60 V, ff (fill factor (curve factor)) was 0.33, and photoelectric conversion efficiency ( ⁇ ) was 0.91%. The results are shown in Table 1.
  • Synthesis Example 17 Synthesis of Compound 21
  • a 500 ml flask 10.2 g (70.8 mmol) of 4,5-difluoro-1,2-diaminobenzene (Compound 20) (manufactured by Tokyo Chemical Industry Co., Ltd.) and 150 mL of pyridine were added to obtain a homogeneous solution.
  • 16.0 g (134 mmol) of thionyl chloride was dropped into the flask. After dropping, the flask was warmed to 25 ° C. and reacted for 6 hours. Thereafter, 250 ml of water was added to the reaction solution, and chloroform was further added to extract the reaction product.
  • the flask was cooled to room temperature (25 ° C.) and diluted with 100 mL of chloroform.
  • the obtained solution was poured into 300 mL of 5 wt% aqueous sodium sulfite solution and stirred for 1 hour.
  • the organic layer of the obtained mixture was separated with a separatory funnel, and the aqueous layer was extracted with chloroform three times.
  • the obtained extract was mixed with the organic layer, and the mixed solution was dried over sodium sulfate. After filtration, the filtrate was concentrated with an evaporator and the solvent was distilled off.
  • the obtained yellow solid was dissolved in 90 mL of methanol heated to 55 ° C., and then cooled to 25 ° C.
  • the solution was kept at ⁇ 78 ° C., and 4.37 mL (11.4 mmol) of 2.6M butyllithium (n-BuLi) in hexane was added dropwise to the solution over 10 minutes. After dropping, the mixture was stirred at ⁇ 78 ° C. for 30 minutes, and then stirred at room temperature (25 ° C.) for 2 hours. Thereafter, the flask was cooled to ⁇ 78 ° C., and 4.07 g (12.5 mmol) of tributyltin chloride was added. After the addition, the mixture was stirred at -78 ° C for 30 minutes, and then stirred at room temperature (25 ° C) for 3 hours.
  • Example 5 Synthesis of polymer compound D In a 100 mL flask in which the air in the flask was replaced with argon, 500 mg (0.475 mmol) of compound 23, 123 mg (0.373 mmol) of compound 22, 24 mg (0.088 mmol) of compound 24, and 32 ml of toluene were uniformly mixed. It was. The resulting toluene solution was bubbled with argon for 30 minutes. Thereafter, 6.33 mg (0.007 mmol) of tris (dibenzylideneacetone) dipalladium and 12.6 mg of tris (2-toluyl) phosphine were added to the toluene solution, and the mixture was stirred at 100 ° C. for 6 hours.
  • the organic layer is washed twice with 50 ml of water, then twice with 50 mL of 3 wt% aqueous acetic acid, then twice with 50 mL of water and then twice with 50 mL of water.
  • the resulting solution was poured into methanol to precipitate a polymer.
  • the polymer was filtered and dried, and the resulting polymer was dissolved again in 30 mL of o-dichlorobenzene and passed through an alumina / silica gel column.
  • the obtained solution was poured into methanol to precipitate a polymer, and the polymer was filtered and then dried to obtain 40 mg of a purified polymer.
  • polymer compound D this polymer is referred to as polymer compound D.
  • Example 6 Preparation and evaluation of ink and organic thin-film solar cell An ink and an organic thin film solar cell were prepared and evaluated in the same manner as in Example 3 except that the polymer compound D was used instead of the polymer compound B. Jsc (short circuit current density) is 12.64 mA / cm 2 Voc (open end voltage) was 0.75 V, ff (fill factor (curve factor)) was 0.61, and photoelectric conversion efficiency ( ⁇ ) was 5.74%. The results are shown in Table 2.
  • Synthesis Example 20 Synthesis of Compound 25 To a four-necked flask, 10.00 g (48.02 mmol) of Compound 11 and 400 mL of tetrahydrofuran were added, and argon bubbling was performed at room temperature (25 ° C.) for 30 minutes. After cooling the reaction solution to ⁇ 40 ° C., 144 mL of diethyl ether solution containing 1.0 mol / L of dodecylmagnesium bromide was added and stirred while raising the temperature to 0 ° C. After 3 hours, disappearance of the raw material was confirmed by liquid chromatography.
  • Synthesis Example 21 Synthesis of Compound 26 To the four-necked flask, a total amount of the mixed oil containing Compound 25 and 200 mL of toluene were added, and argon bubbling was performed at room temperature (25 ° C.) for 30 minutes. Next, 1000 mg of para-toluenesulfonic acid monohydrate was added to the reaction solution, and then the mixture was heated to 120 ° C. and stirred. After 1 hour, disappearance of the raw materials was confirmed by liquid chromatography.
  • the solution was kept at ⁇ 78 ° C., and 9.04 mL (23.5 mmol) of 2.6M butyllithium (n-BuLi) in hexane was added dropwise to the solution over 10 minutes. After dropping, the mixture was stirred at ⁇ 78 ° C. for 30 minutes, and then stirred at room temperature (25 ° C.) for 2 hours. Thereafter, the flask was cooled to ⁇ 78 ° C., and 8.43 g (25.9 mmol) of tributyltin chloride was added. After the addition, the mixture was stirred at -78 ° C for 30 minutes, and then stirred at room temperature (25 ° C) for 3 hours.
  • Example 7 Synthesis of polymer compound E In a 100 mL flask in which the air in the flask was replaced with argon, 200 mg (0.190 mmol) of compound 23, 211 mg (0.190 mmol) of compound 27, 96 mg (0.291 mmol) of compound 22, and 20 mg (0. 074 mmol) and 32 ml of toluene to make a uniform solution. The resulting toluene solution was bubbled with argon for 30 minutes.
  • the precipitated polymer was collected by filtration, and the obtained polymer was put into a cylindrical filter paper and extracted with methanol, acetone and hexane for 5 hours each using a Soxhlet extractor.
  • the polymer remaining in the cylindrical filter paper was dissolved in 100 mL of o-dichlorobenzene, 2 g of sodium diethyldithiocarbamate and 40 mL of water were added, and the mixture was stirred under reflux for 8 hours. After removing the aqueous layer, the organic layer is washed twice with 50 ml of water, then twice with 50 mL of a 3 wt% aqueous acetic acid solution, then twice with 50 mL of water and then twice with 50 mL of water.
  • Example 8 Production and evaluation of ink and organic thin film solar cell An ink and an organic thin film solar cell were prepared and evaluated in the same manner as in Example 3 except that the polymer compound E was used instead of the polymer compound B.
  • the present invention is useful because it provides a photoelectric conversion element with high photoelectric conversion efficiency.

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Abstract

La présente invention se rapporte à un élément de conversion photoélectrique qui comprend une paire d'électrodes et une couche organique qui est agencée entre les électrodes, et contient un composé polymère qui présente un motif répété représenté par la formule (I). L'élément de conversion photoélectrique présente une efficacité de conversion photoélectrique élevée. Dans la formule, Ar représente un groupe arylène ; R représente un atome de fluor ou un groupe organique monovalent ayant un atome de fluor ; et les deux fractions de R peuvent être identiques ou différentes.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013220994A (ja) * 2012-04-13 2013-10-28 Sumitomo Chemical Co Ltd 化合物及びそれを用いた電子素子
US20150034161A1 (en) * 2012-02-17 2015-02-05 Next Energy Technologies, Inc. Organic semiconducting compounds for use in organic electronic devices
US10770665B2 (en) 2015-03-26 2020-09-08 Next Energy Technology, Inc. Fluorinated dye compounds for organic solar cells
WO2021105706A1 (fr) 2019-11-29 2021-06-03 Sumitomo Chemical Co., Ltd Composition photoactive
US11127907B2 (en) 2012-02-14 2021-09-21 Next Energy Technologies, Inc. Electronic devices using organic small molecule semiconducting compounds

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103249799B (zh) * 2010-09-02 2016-07-06 默克专利股份有限公司 含新型光活性聚合物的光伏电池
JP2013095813A (ja) * 2011-10-31 2013-05-20 Sumitomo Chemical Co Ltd 高分子化合物及びそれを用いた光電変換素子
US10644241B2 (en) * 2014-12-19 2020-05-05 Lg Chem, Ltd. Polymer and organic solar cell comprising same
KR102250385B1 (ko) * 2017-10-18 2021-05-11 주식회사 엘지화학 유기 광 다이오드 및 이를 포함하는 유기 이미지 센서
KR102441144B1 (ko) 2018-05-17 2022-09-06 주식회사 엘지화학 헤테로환 화합물 및 이를 포함하는 유기 전자 소자

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002138132A (ja) * 2000-11-01 2002-05-14 Toppan Printing Co Ltd フッ素を含有する共役ポリマー及びそれを用いたエレクトロルミネセンス素子
JP2002317033A (ja) * 2001-04-19 2002-10-31 Fuji Photo Film Co Ltd 新規重合体、それを利用した発光素子材料および発光素子
JP2006511659A (ja) * 2002-12-19 2006-04-06 ダウ グローバル テクノロジーズ インコーポレイティド 三環アリールアミンモノマー及びポリマー及びそのデバイス
JP2007505958A (ja) * 2003-09-20 2007-03-15 メルク パテント ゲーエムベーハー 共役ポリマー、その調製と使用
WO2010117449A2 (fr) * 2009-04-06 2010-10-14 University Of Kentucky Research Foundation Composés semi-conducteurs et dispositifs intégrant ceux-ci

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7074886B2 (en) * 2001-05-07 2006-07-11 E. I. Du Pont De Memours And Company Electroactive fluorene polymers having perfluoroalkyl groups, process for preparing such polymers and devices made with such polymers
KR101314931B1 (ko) * 2006-10-30 2013-10-04 삼성전자주식회사 유기 고분자 반도체, 이의 제조방법 및 이를 이용한 양극성 유기 박막 트랜지스터

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002138132A (ja) * 2000-11-01 2002-05-14 Toppan Printing Co Ltd フッ素を含有する共役ポリマー及びそれを用いたエレクトロルミネセンス素子
JP2002317033A (ja) * 2001-04-19 2002-10-31 Fuji Photo Film Co Ltd 新規重合体、それを利用した発光素子材料および発光素子
JP2006511659A (ja) * 2002-12-19 2006-04-06 ダウ グローバル テクノロジーズ インコーポレイティド 三環アリールアミンモノマー及びポリマー及びそのデバイス
JP2007505958A (ja) * 2003-09-20 2007-03-15 メルク パテント ゲーエムベーハー 共役ポリマー、その調製と使用
WO2010117449A2 (fr) * 2009-04-06 2010-10-14 University Of Kentucky Research Foundation Composés semi-conducteurs et dispositifs intégrant ceux-ci

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHENGGUO ZHU ET AL.: "Panchromatic Conjugated Polymers Containing Alternating Donor/Acceptor Units for Photovoltaic Applications", MACROMOLECULES, vol. 40, 17 February 2007 (2007-02-17), pages 1981 - 1986, XP008111329, DOI: doi:10.1021/ma062376o *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11127907B2 (en) 2012-02-14 2021-09-21 Next Energy Technologies, Inc. Electronic devices using organic small molecule semiconducting compounds
US11309499B2 (en) 2012-02-14 2022-04-19 Next Energy Technologies, Inc. Electronic devices using organic small molecule semiconducting compounds
US20150034161A1 (en) * 2012-02-17 2015-02-05 Next Energy Technologies, Inc. Organic semiconducting compounds for use in organic electronic devices
US9865821B2 (en) * 2012-02-17 2018-01-09 Next Energy Technologies, Inc. Organic semiconducting compounds for use in organic electronic devices
JP2013220994A (ja) * 2012-04-13 2013-10-28 Sumitomo Chemical Co Ltd 化合物及びそれを用いた電子素子
US10770665B2 (en) 2015-03-26 2020-09-08 Next Energy Technology, Inc. Fluorinated dye compounds for organic solar cells
WO2021105706A1 (fr) 2019-11-29 2021-06-03 Sumitomo Chemical Co., Ltd Composition photoactive

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