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WO2012090971A1 - Élément de conversion photoélectrique et composition utilisée dans celui-ci - Google Patents

Élément de conversion photoélectrique et composition utilisée dans celui-ci Download PDF

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WO2012090971A1
WO2012090971A1 PCT/JP2011/080138 JP2011080138W WO2012090971A1 WO 2012090971 A1 WO2012090971 A1 WO 2012090971A1 JP 2011080138 W JP2011080138 W JP 2011080138W WO 2012090971 A1 WO2012090971 A1 WO 2012090971A1
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健一郎 大家
大西　敏博
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
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    • 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
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    • 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
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    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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    • 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
    • H10K85/141—Organic polymers or oligomers comprising aliphatic or olefinic chains, e.g. poly N-vinylcarbazol, PVC or PTFE
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    • 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
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    • 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
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1426—Side-chains containing oxygen containing carboxy groups (COOH) and/or -C(=O)O-moieties
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    • 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
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
    • C08G2261/342—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3424—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms non-conjugated, e.g. paracyclophanes or xylenes
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08G2261/36—Oligomers, i.e. comprising up to 10 repeat units
    • C08G2261/364—Oligomers, i.e. comprising up to 10 repeat units containing hetero atoms
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    • 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
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    • 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
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
    • H10K39/30—Devices controlled by radiation
    • H10K39/32—Organic image sensors
    • 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
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
    • 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
    • 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 photoelectric conversion element and a composition used therefor.
  • the ⁇ -conjugated polymer compound is attracting attention for its absorption of light in the visible light region and its conductive properties, and its application to a photoelectric conversion element is being studied.
  • an element having an organic layer containing a ⁇ -conjugated polymer compound can omit a high-temperature process and a vacuum process necessary for manufacturing an inorganic element such as a silicon-based semiconductor, and can reduce energy in manufacturing.
  • An element having an organic layer containing a ⁇ -conjugated polymer compound can be a flexible film-like element, and has attracted attention as a next-generation element.
  • a photoelectric conversion element having an organic layer containing a ⁇ -conjugated polymer compound for example, a photoelectric conversion element having an organic layer containing poly (3-hexylthiophene) has been proposed (Polymer Reviews, 48, 531-582 (2008)). ). However, the characteristics of the photoelectric conversion element are not sufficient, and a new photoelectric conversion element has been demanded.
  • the present invention first has a pair of electrodes and an active layer provided between the electrodes, and the active layer has the formula (I) (In the formula, R 1 and R 2 are the same or different and each represents a substituent. N and m are the same or different and each represents an integer of 0 to 3. When there are a plurality of R 1 , they are the same. However, when there are a plurality of R 2 , they may be the same or different.)
  • the photoelectric conversion element containing the high molecular compound containing the repeating unit represented by these is provided.
  • the present invention also provides a composition comprising a polymer compound containing a repeating unit represented by formula (I) and an electron-accepting compound or electron-donating polymer compound different from the polymer compound. .
  • the present invention provides a polymer compound containing a repeating unit represented by formula (I), wherein the weight average molecular weight is 10,000 or more.
  • Y ′ represents a divalent group.
  • R 1 and R 2 are the same or different and each represents a substituent.
  • N and m are the same or different and each represents an integer of 0 to 3.
  • R When there are a plurality of R 1 s, they may be the same or different. When there are a plurality of R 2 s , they may be the same or different.
  • the composition which is a high molecular compound containing the repeating unit represented by these is provided.
  • the present invention relates to a method for producing a photoelectric conversion element having a pair of electrodes and an active layer provided between the electrodes, the layer containing a polymer compound containing a repeating unit represented by the formula (III) Of a photoelectric conversion element having a step of forming an active layer containing a polymer compound containing a repeating unit represented by the formula (I) by performing a treatment for removing a divalent group represented by Y ′ A manufacturing method is also provided.
  • the photoelectric conversion element of the present invention has a pair of electrodes and an active layer provided between the electrodes, and the active layer contains a polymer compound containing a repeating unit represented by the formula (I).
  • R 1 And R 2 are the same or different and each represents a substituent.
  • the substituent is preferably a group having 1 to 30 carbon atoms.
  • substituents include alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, butyl, hexyl, octyl, dodecyl, methoxy, ethoxy, butoxy, hexyloxy, octyloxy Groups, alkoxy groups having 1 to 30 carbon atoms such as dodecyloxy group, heteroaryl groups such as thienyl group, and aryl groups having 1 to 30 carbon atoms such as phenyl group and naphthyl group.
  • n and m are the same or different and represent an integer of 0 to 3, and n and m are preferably 0.
  • the polymer compound containing the repeating unit represented by the formula (I) is further converted to the formula (II)
  • C ′ represents an optionally substituted arylene group, divalent heterocyclic group, divalent aromatic amine residue, alkenylene group or alkynylene group, provided that C ′ represents the formula (I) It is different from the group represented by It is preferable that the repeating unit represented by these is included.
  • the arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon.
  • the number of carbon atoms constituting the aromatic ring contained in the arylene group is usually 6 to 60, preferably 6 to 20.
  • Aromatic hydrocarbon includes a compound containing a benzene ring, a compound containing a condensed ring, a compound containing a structure in which two or more of the independent benzene rings or condensed rings are directly bonded, or a group such as vinylene. Also included are compounds containing such structures.
  • the divalent heterocyclic group refers to the remaining atomic group obtained by removing two hydrogen atoms from a heterocyclic compound. The number of carbon atoms constituting the ring contained in the divalent heterocyclic group is usually 3 to 60.
  • the heterocyclic compound refers to a compound that includes a carbon atom and hetero atoms such as oxygen, sulfur, nitrogen, phosphorus, boron, and arsenic as elements constituting a ring among organic compounds having a cyclic structure.
  • a heteroarylene group is preferable.
  • the arylene group which may be substituted include groups represented by Formulas 1 to 41 and Formulas 131 to 135.
  • Examples of the divalent heterocyclic group include Formulas 42 to 130, Examples include groups represented by formula 136 to formula 138.
  • R represents a hydrogen atom or a substituent. When there are a plurality of R, they may be the same or different.
  • R is a substituent
  • substituents include alkyl groups such as methyl group, ethyl group, butyl group, hexyl group, octyl group, dodecyl group, methoxy group, ethoxy group, butoxy group, hexyloxy group, Examples thereof include alkoxy groups such as octyloxy group and dodecyloxy group, aryl groups such as phenyl group and naphthyl group, and heteroaryl groups such as thienyl.
  • the substituent when the substituent is an alkyl group or an alkoxy group, the substituent preferably has 1 to 20 carbon atoms, more preferably 1 to 14 carbon atoms, and still more preferably 6 to 14 carbon atoms.
  • X 2 Represents ⁇ CH— or a nitrogen atom.
  • the divalent aromatic amine residue is a group obtained by removing one hydrogen atom on two different aromatic rings from an aromatic amine compound in which three aromatic groups are bonded to a nitrogen atom. Examples of the divalent aromatic amine residue include groups represented by Formula 139 and Formula 140.
  • the polymer compound containing the repeating unit represented by the formula (I) preferably contains a group represented by the formula 112 as a repeating unit.
  • the polymer compound in the present invention has a weight average molecular weight of 3 ⁇ 10. 3 It refers to the above compounds.
  • the weight average molecular weight of the polymer compound containing the repeating unit represented by the formula (I) is 3 ⁇ 10.
  • Weight average molecular weight 3 ⁇ 10 3 When it is as described above, the occurrence of defects in the film is suppressed during film formation during device fabrication.
  • Weight average molecular weight is 1 ⁇ 10 7 When it is below, solubility in a solvent and applicability at the time of device production are enhanced.
  • the weight average molecular weight is 8 ⁇ 10 3 ⁇ 5 ⁇ 10 6 More preferably, 1 ⁇ 10 4 ⁇ 1 ⁇ 10 6 It is particularly preferred that From the viewpoint of suppressing the occurrence of defects in the film during film formation during device fabrication, it is preferably 10,000 or more.
  • the number average molecular weight of the polymer compound containing the repeating unit represented by the formula (I) is 1 ⁇ 10 3 ⁇ 1 ⁇ 10 8
  • 2 ⁇ 10 3 ⁇ 1 ⁇ 10 7 It is more preferable that Number average molecular weight is 1 ⁇ 10 3
  • 1 ⁇ 10 8 In the following cases, the solubility of the polymer compound is high and the production of the thin film is easy.
  • the weight average molecular weight and number average molecular weight in this invention point out the polystyrene-reduced weight average molecular weight and polystyrene-reduced number average molecular weight which were calculated using the standard data of polystyrene using gel permeation chromatography (GPC).
  • the polymer compound containing the repeating unit represented by the formula (I) has an amount of the repeating unit represented by the formula (I) of 20 to 100 when the total amount of the repeating units of the polymer compound is 100. Preferably, it is preferably 30 to 70.
  • the polymer compound further includes a repeating unit represented by the formula (II)
  • the repeating unit represented by the formula (II) when the total amount of the repeating units possessed by the polymer compound is 100, the repeating unit represented by the formula (II) The amount is preferably 20 to 80, more preferably 30 to 70.
  • the polymer compound containing the repeating unit represented by formula (I) has a light absorption terminal wavelength of 600 nm or more from the viewpoint of conversion efficiency. Preferably, it is 650 nm or more, more preferably 700 nm or more, and particularly preferably 720 nm or more.
  • the characteristics of the photoelectric conversion element using the obtained polymer compound may be deteriorated when a group involved in polymerization remains at the molecular chain terminal. Therefore, the terminal is preferably protected with a stable group that does not participate in polymerization.
  • the stable group is preferably a group having a conjugated bond continuous with the conjugated structure of the molecular chain main chain.
  • substituents represented by the formula (6) are listed in columns 6 to 10 of USP 582002.
  • the photoelectric conversion element of the present invention has a pair of electrodes and an active layer provided between the electrodes, and the active layer contains a polymer compound containing a repeating unit represented by the formula (I).
  • the active layer may contain an electron-donating compound (p-type semiconductor) or an electron-accepting compound (n-type semiconductor) in addition to the polymer compound containing the repeating unit represented by the formula (I). Good.
  • at least one of the electrodes is preferably transparent or translucent.
  • Another preferred embodiment of the photoelectric conversion element of the present invention has a pair of electrodes, an active layer and an organic layer provided between the electrodes, and the repeating unit represented by the formula (I) in the active layer.
  • the photoelectric conversion element contains a polymer compound containing, and contains an electron-accepting compound or an electron-donating compound in the organic layer.
  • at least one of the electrodes is preferably transparent or translucent.
  • the organic layer contains an electron donating compound.
  • an electron-accepting compound is contained in the organic layer.
  • the electron donating compound may be a low molecular compound or a high molecular compound, but a high molecular compound is preferable.
  • the electron-donating compound examples include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, and aromatic groups in the side chain or main chain.
  • examples include polysiloxane derivatives having amine residues, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene and derivatives thereof, and poly-3,4-ethylenedioxythiophene. It is done.
  • the electron-accepting compound preferably has a work function of 3.0 eV or more, more preferably 3.2 eV or more, and particularly preferably 3.4 eV or more.
  • the work function indicates the absolute value of the lowest unoccupied orbital level (LUMO) energy when the vacuum level is 0 eV.
  • the electron-accepting compound may be an organic compound or an inorganic compound, but is preferably an organic compound from the viewpoint of solubility in an organic solvent.
  • the electron-accepting compound include carbon materials, metal oxides such as titanium oxide, oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetra Cyanoanthraquinodimethane 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, polyfluorene and derivatives thereof,
  • phenanthroline derivatives such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (bathocuproin), fullerenes, and fullerene derivatives, preferably titanium oxide, carbon Nanotubes, fullerene, a fullerene derivative, particularly preferably a 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 (1), a compound represented by the formula (2), a compound represented by the formula (3), and a compound represented by the formula (4).
  • R a Is a group having an alkyl group, an aryl group, a heteroaryl group or an ester structure. Multiple R a May be the same or different.
  • R b Represents an alkyl group or an aryl group.
  • R a And R b The alkyl group represented by may be linear or branched, and may be a cycloalkyl group.
  • 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, 2-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, nonyl group
  • chain alkyl groups such as decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl tomb, octadecyl group and eicosyl group, and cycloalkyl groups such as cyclopentyl group, cyclohexyl group and adamantyl group.
  • the aryl group represented by the formula has 6 to 60 carbon atoms and may have a substituent.
  • Specific examples of the aryl group which may have a substituent include a phenyl group and a C1-C12 alkyloxyphenyl group (C1-C12 alkyl is an alkyl having 1 to 12 carbon atoms. The same applies hereinafter. And a C1-C12 alkylphenyl group, a 1-naphthyl group, a 2-naphthyl group, and a pentafluorophenyl group.
  • R a Is usually 3 to 60 carbon atoms, and examples thereof include thienyl, pyrrolyl, furyl, pyridyl, quinolyl, and isoquinolyl groups.
  • R a The group having an ester structure represented by, for example, formula (5) (Wherein u1 represents an integer of 1 to 6, u2 represents an integer of 0 to 6, R c Represents an alkyl group, an aryl group or a heteroaryl group. ) The group represented by these is mentioned.
  • R c Definitions and specific examples of alkyl groups, aryl groups, and heteroaryl groups represented by a
  • Specific examples of the fullerene derivative are as follows.
  • C 70 Specific examples of the fullerene derivative are as follows.
  • 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-C61 Examples include butyric acid methyl ester ([6,6] -Thienyl C61 butyric acid methyl ester).
  • the ratio 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 thickness of the active layer is usually preferably 1 nm to 100 ⁇ m, more preferably 2 nm to 1000 nm, still more preferably 5 nm to 500 nm, more preferably 20 nm to 200 nm.
  • the photoelectric conversion element 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 material of the transparent or translucent electrode include a conductive metal oxide film and a translucent metal thin film.
  • Specific examples of the electrode material include indium oxide, zinc oxide, tin oxide, and conductive materials made of indium / tin / oxide (ITO), indium / zinc / oxide, etc., which are composites thereof. Film, NESA, gold, platinum, silver, copper.
  • transparent or translucent electrode materials 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. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an electrode material.
  • the material of one of the pair of electrodes is preferably a material having a low work function.
  • metals such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and two of them
  • One or more alloys, or one or more of them, and an alloy of one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite or graphite intercalation compounds are used. .
  • 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 and the organic layer may be used.
  • the material used for the intermediate layer include alkali metal or alkaline earth metal halides or oxides such as lithium fluoride.
  • the intermediate layer may be formed using fine particles of an inorganic semiconductor such as titanium oxide or PEDOT (poly-3,4-ethylenedioxythiophene).
  • the thickness of the intermediate layer is usually preferably 1 nm to 100 ⁇ m, more preferably 2 nm to 1000 nm, still more preferably 5 nm to 500 nm, more preferably 20 nm to 200 nm.
  • the photoelectric conversion device of the present invention includes two types of compounds, a polymer compound containing a repeating unit represented by formula (I) and an electron accepting compound or an electron donating compound. It is preferred to include the composition in the active layer.
  • the weight average molecular weight of the polymer compound containing the repeating unit represented by the formula (I) contained in the composition is 3 ⁇ 10 3 ⁇ 1 ⁇ 10 7 Preferably 8 ⁇ 10 3 ⁇ 5 ⁇ 10 6 More preferably, 1 ⁇ 10 4 ⁇ 1 ⁇ 10 6 It is particularly preferred that From the viewpoint of suppressing the occurrence of defects in the film during film formation during device fabrication, it is preferably 10,000 or more. Moreover, it is preferable that the high molecular compound containing the repeating unit represented by Formula (I) further contains the repeating unit represented by Formula (II).
  • the composition preferably contains a polymer compound containing a repeating unit represented by formula (I) and an electron-accepting compound or an electron-donating polymer compound, and is represented by formula (I). It is more preferable to include a polymer compound containing a repeating unit and an electron accepting compound, and the electron accepting compound is more preferably a fullerene or a fullerene derivative.
  • the content of the polymer compound containing the repeating unit represented by the formula (I) in the composition is preferably 0.01 wt% to 99.9 wt%, more preferably 0.1 wt% to 50 wt%. %, More preferably 0.3 to 30% by weight, particularly preferably 0.5 to 10% by weight.
  • the content of the electron-accepting compound or the electron-donating compound in the composition is preferably 0.01% by weight to 99.9% by weight, more preferably 0.1% by weight to 50% by weight, and still more preferably 0%. .3% by weight to 30% by weight, particularly preferably 0.5% by weight to 10% by weight.
  • the composition may contain other compounds.
  • the content ratio between the content of the electron-accepting compound and the polymer compound containing the repeating unit represented by formula (I) is (content of electron-accepting compound) ) / (Content of polymer compound containing a repeating unit represented by formula (I)) is preferably 0.1 to 10, more preferably 0.2 to 5.
  • This composition can be manufactured from the raw material composition containing the high molecular compound containing the repeating unit represented by Formula (III), and an electron-accepting compound or an electron-donating compound.
  • the weight average molecular weight of the polymer compound containing the repeating unit represented by the formula (III) contained in the raw material composition is 3 ⁇ 10 3 ⁇ 1 ⁇ 10 7 Preferably 8 ⁇ 10 3 ⁇ 5 ⁇ 10 6 More preferably, 1 ⁇ 10 4 ⁇ 1 ⁇ 10 6 It is particularly preferred that From the viewpoint of suppressing the occurrence of defects in the film during film formation during device fabrication, it is preferably 10,000 or more.
  • the polymer compound containing the repeating unit represented by the formula (III) is further represented by the formula (IV)
  • C ′′ represents an optionally substituted arylene group, divalent heterocyclic group, divalent aromatic amine residue, alkenylene group or alkynylene group, provided that C ′′ represents the formula ( It is different from the group represented by III). It is preferable that the repeating unit represented by these is included.
  • the definition and specific examples of the optionally substituted arylene group, divalent heterocyclic group, divalent aromatic amine residue, alkenylene group and alkenylene group represented by C ′′ are represented by the aforementioned C ′.
  • the definitions and specific examples of the optionally substituted arylene group, divalent heterocyclic group, divalent aromatic amine residue, alkenylene group and alkenylene group are the same.
  • the polymer compound containing a repeating unit represented by the formula (III) has a repeating unit number represented by the formula (III) of 20 when the total amount of the repeating units of the polymer compound is 100. It is preferably from 100 to 100, more preferably from 30 to 70.
  • the polymer compound further contains a repeating unit represented by the formula (IV)
  • the number is preferably 20 to 80, and more preferably 30 to 70.
  • Y ′ represents a divalent group.
  • the divalent group is preferably a group that can be eliminated by applying energy such as heat or light to the compound represented by the formula (III).
  • Examples of the divalent group represented by Y ′ include the following groups.
  • R 3 ⁇ R 13 Are the same or different and each represents a hydrogen atom or a substituent. Among these, a hydrogen atom or a group having 1 to 30 carbon atoms is preferable.
  • R 3 ⁇ R 12 When is a substituent, examples of the substituent include an alkyl group having 1 to 30 carbon atoms such as a methyl group, an ethyl group, a butyl group, a hexyl group, an octyl group, and a dodecyl group, a methoxy group, an ethoxy group, and a butoxy group. Group, a hexyloxy group, an octyloxy group, a dodecyloxy group and the like, an alkoxy group having 1 to 30 carbon atoms, a phenyl group, an aryl group such as a naphthyl group and the like.
  • an alkyl group having 1 to 30 carbon atoms is preferable, an alkyl group having 1 to 20 carbon atoms is more preferable, an alkyl group having 1 to 12 carbon atoms is further preferable, and an alkyl group having 1 to 6 carbon atoms is particularly preferable.
  • R 13 When is a substituent, examples of the substituent include an alkyl group having 1 to 30 carbon atoms such as a methyl group, an ethyl group, a butyl group, a hexyl group, an octyl group, and a dodecyl group, a methoxy group, an ethoxy group, and a butoxy group.
  • X 1 Represents a halogen atom.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • a chlorine atom and a bromine atom are preferable, and a chlorine atom is more preferable.
  • R 1 And R 2 are the same or different and each represents a substituent.
  • the substituent is preferably a group having 1 to 30 carbon atoms.
  • substituents include alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, butyl, hexyl, octyl, dodecyl, methoxy, ethoxy, butoxy, hexyloxy, octyloxy Groups, alkoxy groups having 1 to 30 carbon atoms such as dodecyloxy group, heteroaryl groups such as thienyl group, and aryl groups having 1 to 30 carbon atoms such as phenyl group and naphthyl group.
  • n and m are the same or different and represent an integer of 0 to 3.
  • n and m are preferably 0.
  • the method for producing the polymer compound containing the repeating unit represented by the formula (III) is not particularly limited, but a method using a Suzuki coupling reaction is preferable from the viewpoint of ease of synthesis of the polymer compound.
  • a method using the Suzuki coupling reaction for example, the formula (100): Q 1 -E 1 -Q 2 (100) [Where E 1 Represents a group represented by the formula (III-1). (Where Y ′, R 1 , R 2 , M and n represent the same meaning as described above. ) Q 1 And Q 2 Are the same or different and represent boronic acid residues or boric acid ester residues.
  • T 1 -E 2 -T 2 (200) [Where E 2 Represents an arylene group, a heteroarylene group or a divalent aromatic amine residue.
  • T 1 And T 2 are the same or different and each represents a halogen atom, an alkyl sulfonate group, an aryl sulfonate group or an arylalkyl sulfonate group.
  • the manufacturing method which has a process with which 1 or more types of compounds represented by these are made to react in presence of a palladium catalyst and a base is mentioned.
  • the total number of moles of one or more compounds represented by formula (200) used in the reaction is preferably excessive with respect to the total number of moles of one or more compounds represented by formula (100).
  • the total number of moles of one or more compounds represented by formula (200) used in the reaction is 1 mole
  • the total number of moles of one or more compounds represented by formula (100) is 0.6 to 0.00.
  • the amount is preferably 99 mol, more preferably 0.7 to 0.95 mol.
  • Examples of the halogen atom represented by the formula include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • a bromine atom and an iodine atom are preferable, and a bromine atom is more preferable.
  • T in equation (200) 1 And T 2 Examples of the alkyl sulfonate group represented by the formula include a methane sulfonate group, an ethane sulfonate group, and a trifluoromethane sulfonate group.
  • Examples of the aryl sulfonate group include a benzene sulfonate group and a p-toluene sulfonate group.
  • Examples of the aryl sulfonate group include a benzyl sulfonate group.
  • arylene group, heteroarylene group or divalent aromatic amine residue represented by the formula include groups represented by the formulas 1 to 140.
  • the palladium catalyst used in the Suzuki coupling reaction include a Pd (0) catalyst and a Pd (II) catalyst.
  • Specific examples of the palladium catalyst include palladium [tetrakis (triphenylphosphine)], palladium acetate, and dichlorobis (triphenylphosphine) palladium (II). Ease of reaction (polymerization) operation, reaction (polymerization) rate From this viewpoint, dichlorobis (triphenylphosphine) palladium (II) and palladium acetate are preferable.
  • the addition amount of the palladium catalyst is not particularly limited as long as it is an effective amount as a catalyst, but is usually 0.0001 mol to 0.5 mol with respect to 1 mol of the compound represented by the formula (100). The amount is preferably 0.0003 mol to 0.1 mol.
  • the base used for the Suzuki coupling reaction is an inorganic base, an organic base, an inorganic salt, or the like. Examples of the inorganic base include potassium carbonate, sodium carbonate, and barium hydroxide. Examples of the organic base include triethylamine and tributylamine. An example of the inorganic salt is cesium fluoride.
  • the amount of the base added is usually 0.5 mol to 100 mol, preferably 0.9 mol to 20 mol, more preferably 1 mol to 10 mol, relative to 1 mol of the compound represented by the formula (100). is there.
  • a phosphorus compound may be added as a ligand.
  • the phosphorus compound include triphenylphosphine, tri (o-tolyl) phosphine, and tri (o-methoxyphenyl) phosphine.
  • the addition amount is usually 0.5 to 100 mol, preferably 0.9 to 20 mol, more preferably 1 mol to 1 mol of the palladium catalyst. 10 moles.
  • the reaction is usually performed in a solvent.
  • the solvent include N, N-dimethylformamide, toluene, dimethoxyethane, and tetrahydrofuran. From the viewpoint of solubility of the polymer compound, toluene and tetrahydrofuran are preferred.
  • the base may be added to the reaction system as an aqueous solution, and the monomer may be reacted in a two-phase solvent of an aqueous phase and an organic phase.
  • an inorganic salt is used as the base, the monomer is usually reacted as an aqueous solution in the reaction system in a two-phase solvent.
  • a phase transfer catalyst such as a quaternary ammonium salt may be added to the reaction system as necessary.
  • the temperature of the Suzuki coupling reaction is usually about 50 to 160 ° C., although it depends on the solvent. From the viewpoint of increasing the molecular weight of the polymer compound, 60 to 120 ° C. is preferable. Alternatively, the temperature may be raised to near the boiling point of the solvent and refluxed.
  • the time (reaction time) for performing the Suzuki coupling reaction may be the end point when the target degree of polymerization is reached, but is usually about 0.1 to 200 hours, and preferably about 1 to 30 hours.
  • the Suzuki coupling reaction is performed in a reaction system in which the palladium catalyst is not deactivated under an inert atmosphere such as argon gas or nitrogen gas.
  • an inert atmosphere such as argon gas or nitrogen gas.
  • it is performed in a system sufficiently deaerated with argon gas or nitrogen gas.
  • reaction vessel After the inside of the reaction vessel (reaction system) is sufficiently substituted with nitrogen gas and degassed, a compound represented by the formula (100), a compound represented by the formula (200), Dichlorobis (triphenylphosphine) palladium (II) is charged, the reaction vessel is sufficiently replaced with nitrogen gas, degassed, and then degassed by bubbling with nitrogen gas in advance, for example, degassed toluene
  • a base degassed by bubbling with nitrogen gas in advance for example, a degassed sodium carbonate aqueous solution
  • heated and heated for example, at reflux temperature for 8 hours. Polymerize while maintaining an active atmosphere.
  • the terminal is protected with a stable group that does not participate in polymerization.
  • the stable group is preferably a group having a conjugated bond continuous with the conjugated structure of the molecular chain main chain.
  • substituents represented by the formula (6) are listed in columns 6 to 10 of USP 582002.
  • the electron donating compound is preferably an electron donating compound which is a polymer compound, and the electron accepting compound is preferably fullerene or a fullerene derivative.
  • the content of the polymer compound containing the repeating unit represented by the formula (I) in the raw material composition is preferably 0.01 wt% to 99.9 wt%, more preferably 0.1 wt% to 50 wt%.
  • the content of the electron donating compound or the electron accepting compound in the composition is preferably 0.01% by weight to 99.9% by weight, more preferably 0.1% by weight to 50% by weight, and still more preferably 0.8%. It is 3 to 30% by weight, particularly preferably 0.5 to 10% by weight.
  • the content ratio between the content of the electron-accepting compound and the polymer compound containing the repeating unit represented by the formula (I) is (content of electron-accepting compound) ) / (Content of polymer compound containing a repeating unit represented by formula (I)) is preferably 0.1 to 10, more preferably 0.2 to 5.
  • the raw material composition may contain other compounds.
  • the solution of the present invention includes a raw material composition and a solvent.
  • the solvent include carbons such as aromatic hydrocarbons (eg, toluene, xylene, mesitylene, tetralin, butylbenzene, sec-butylbenzene, tert-butylbenzene) and aliphatic hydrocarbons (eg, decalin, bicyclohexyl).
  • Hydrogen solvent aromatic halogenated hydrocarbons (eg chlorobenzene, dichlorobenzene, trichlorobenzene), aliphatic halogenated hydrocarbons (eg carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, And halogenated hydrocarbon solvents such as chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane) and ether solvents such as tetrahydrofuran and tetrahydropyran.
  • aromatic halogenated hydrocarbons eg chlorobenzene, dichlorobenzene, trichlorobenzene
  • aliphatic halogenated hydrocarbons eg carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane,
  • an aromatic hydrocarbon solvent and an aromatic halogenated hydrocarbon solvent are preferable, dichlorobenzene is more preferable, and orthodichlorobenzene is more preferable.
  • a solvent having a surface tension at 25 ° C. of 15 mN / m or more is preferable, and a solvent having a surface tension of 15 mN / m to 100 mN / m is more preferable. Specific examples of the solvent having a surface tension at 25 ° C.
  • 15 mN / m to 100 mN / m include toluene (27.9 mN / m), benzonitrile (34.5 mN / m), 1,3-benzodioxole ( 28.8 mN / m), ortho-xylene (29.8 mN / m), meta-xylene (28.5 mN / m), para-xylene (28.0 mN / m), cyclohexanone (34.6 mN / m), chlorobenzene (33.
  • Numerical values in parentheses represent surface tension at 25 ° C.
  • the surface tension is described in “Lange's Handbook of Chemistry 13th edition”, John. A. Dean, McGaw-Hill, published in 1972, pp.
  • the values described in 10 / 103-10 / 116 are shown.
  • an aromatic compound having a substituent is preferable as the solvent from the viewpoint of solubility of the conjugated polymer compound, and chlorobenzene, orthodichlorobenzene, metadichlorobenzene, paradichlorobenzene.
  • Orthoxylene, metaxylene, paraxylene, and toluene are more preferable.
  • the weight of the solvent contained in the solution is preferably 50 to 99.9% by weight with respect to the total weight of the solution.
  • the composition containing two types of compounds of the present invention, the polymer compound containing the repeating unit represented by formula (I), and the electron-accepting compound or the electron-donating compound uses a raw material composition, (Iii) by removing the divalent group represented by Y ′ of the polymer compound containing the repeating unit represented by formula (III) and leading to a compound containing the repeating unit represented by formula (I). it can.
  • the polymer compound containing the repeating unit represented by the formula (III) can generate an anthracene skeleton by eliminating a divalent group represented by Y ′ by applying energy such as heat and light. .
  • any temperature can be set as long as it is not lower than the temperature at which the divalent group represented by Y ′ is eliminated and not higher than the temperature at which the polymer compound is decomposed. Usually, it is 150 to 400 ° C, preferably 200 to 350 ° C.
  • the heat treatment time can be selected within an industrial range, but is usually 1 minute to 50 hours, and preferably 10 minutes to 24 hours.
  • the atmosphere for the heat treatment is preferably an inert atmosphere, and examples of the inert atmosphere include a nitrogen gas atmosphere, an argon gas atmosphere, and a vacuum. When oxygen is contained in the inert atmosphere, the oxygen concentration is preferably 100 ppm or less, and more preferably 10 ppm or less.
  • the oxygen partial pressure is preferably 200 Pa or less, more preferably 50 Pa.
  • a method for removing the divalent group represented by Y ′ by light include a method of irradiating ultraviolet rays having a wavelength of 400 nm or less.
  • the light intensity is not particularly limited as long as the divalent group represented by Y ′ can be eliminated.
  • the atmosphere in the case of irradiation with light is also preferably an inert atmosphere, and the range exemplified above can be suitably used.
  • the compound generated from the divalent group represented by Y ′ thus eliminated may be contained in the first composition as an electron donating compound or an electron accepting compound, or may be removed by purification. .
  • the process for producing a photoelectric conversion element of the present invention comprises a polymer compound having a pair of electrodes and an active layer provided between the electrodes, wherein the active layer contains a repeating unit represented by the formula (I).
  • a process for producing a photoelectric conversion element comprising the step of removing a divalent group represented by Y ′ on a layer containing a polymer compound containing a repeating unit represented by formula (III) Forming a layer.
  • a thin film is formed by applying a solution containing a polymer compound containing a repeating unit represented by formula (III), an electron accepting compound, and a solvent on one electrode.
  • a polymer compound containing a repeating unit represented by the formula (I) by applying energy such as heat and light to the thin film to remove a divalent group represented by Y ′ and an electron accepting compound; Can be manufactured from the step of forming an active layer containing the other electrode on the active layer.
  • Application methods such as printing method, offset printing method, inkjet printing method, dispenser printing method, nozzle coating method, capillary coating method can be used, spin coating method, flexographic printing method, gravure printing method, inkjet printing method, dispenser printing The method is preferred.
  • the thin film may be formed by a vacuum evaporation method.
  • the photoelectric conversion element of the present invention is manufactured by applying a solution containing the first composition and a solvent on one electrode to form an active layer, and forming the other electrode on the active layer. May be.
  • the photoelectric conversion element of the present invention can be operated as an organic thin film solar cell by irradiating light such as sunlight from a transparent or translucent electrode to generate a photovoltaic force between the electrodes. 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 solar cell of the present invention 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 module structure of the organic thin film solar cell of the present invention can be appropriately selected depending on the purpose of use, the place of use and the 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.
  • Various types of 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 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.
  • the polymer compound to be measured was dissolved in tetrahydrofuran to a concentration of about 0.5% by weight, and 30 ⁇ L was injected into GPC. Tetrahydrofuran was used as the mobile phase of GPC, and flowed at a flow rate of 0.6 mL / min.
  • Tetrahydrofuran was used as the mobile phase of GPC, and flowed at a flow rate of 0.6 mL / min.
  • two TSKgel SuperHM-H manufactured by Tosoh
  • TSKgel SuperH2000 manufactured by Tosoh
  • a differential refractive index detector (manufactured by Shimadzu Corporation, trade name: RID-10A) was used as the detector.
  • a spectrophotometer for example, JASCO-V670, made by JASCO Corporation
  • the measurable wavelength range was 200 to 1500 nm, and thus measurement was performed in this wavelength range.
  • the absorption spectrum of the substrate used for measurement was measured.
  • a quartz substrate, a glass substrate, or the like was used as the substrate.
  • a solution containing a polymer compound was applied onto the substrate and dried to form a thin film containing the polymer compound. Then, the absorption spectrum of the laminated body of a thin film and a board
  • the compound (C-1) was insoluble in toluene and was not uniform in the reaction system.
  • the oil bath temperature was set to 120 ° C. and the reaction solution was refluxed for 3.5 hours, whereby the Diels-Alder reaction proceeded and the reaction system became a homogeneous solution.
  • 20 mL of methanol was added to the reaction solution 5 times every 30 minutes (total 100 mL), and the mixture was heated to reflux for 3 hours to obtain a monoester body in which the anhydride was opened.
  • 1 g of concentrated sulfuric acid was added to the reaction solution twice every 3 hours and heated to reflux for 6 hours.
  • the organic layer was washed twice with 20 ml of water, twice with 20 mL of a 3 wt% aqueous acetic acid solution and twice with 20 mL of water, and the obtained solution was poured into methanol to precipitate a polymer.
  • the polymer is filtered and dried.
  • the obtained polymer is redissolved in 30 mL of o-dichlorobenzene, passed through an alumina / silica gel column, the obtained solution is poured into methanol to precipitate the polymer, and the polymer is filtered and dried. As a result, 60 mg of the purified polymer compound 1 was obtained.
  • the weight average molecular weight (Mw) was 13,000, and the number average molecular weight (Mn) was 4,000.
  • Reference Example 4 Synthesis of polymer compound 2 Polymerization was conducted in the same manner as in Example 2 except that the compound (D-2) was used instead of the compound (D-1) to obtain a polymer compound 2.
  • the molecular weight in terms of polystyrene of the polymer compound 2 measured by GPC was Mw of 94,000 and Mn of 60,000.
  • Reference Example 5 Synthesis of Polymer Compound 3 Polymerization was carried out in the same manner as in Example 2 except that the compound (D-3) was used instead of the compound (D-1) to obtain a polymer compound 3.
  • Reference Example 6 Measurement of absorption wavelength
  • the polymer compound 1 was dissolved in orthodichlorobenzene at a concentration of 2% by weight to prepare a solution. The solution was applied on a glass plate to form a thin film having a thickness of 50 to 100 nm, and the absorption wavelength of the thin film was measured.
  • the glass plate on which the thin film was formed was heat-treated at 250 to 300 ° C. for 1 hour in a nitrogen atmosphere.
  • the absorption spectrum of the thin film on the glass plate after the heat treatment was measured.
  • the spectrum of the absorption wavelength of the polymer compound 1 before the heat treatment had a maximum value at 530 nm
  • the spectrum of the absorption wavelength of the polymer compound 1 after the heat treatment had a maximum value at 580 nm.
  • Reference Example 7 Measurement of absorption wavelength
  • the absorption wavelength of the polymer compound was measured in the same manner as in Reference Example 2, except that polymer compound 2 was used instead of polymer compound 1.
  • the absorption wavelength spectrum of the polymer compound 2 before the heat treatment had a maximum value at 525 nm, and the absorption wavelength spectrum of the polymer compound 2 after the heat treatment had a maximum value at 550 nm.
  • Reference Example 8 Measurement of absorption wavelength
  • the absorption wavelength of the polymer compound was measured in the same manner as in Reference Example 2, except that polymer compound 3 was used instead of polymer compound 1.
  • the absorption wavelength spectrum of the polymer compound 3 before the heat treatment had a maximum value at 440 nm, and the absorption wavelength spectrum of the polymer compound 3 after the heat treatment had a maximum value at 570 nm.
  • Example 1 (Production and Evaluation of Organic Thin Film Solar Cell) A glass substrate provided with an ITO film with a thickness of 150 nm by a sputtering method was subjected to surface treatment by ozone UV treatment. Next, when the polymer compound 1 and fullerene C60PCBM (phenyl C61-butyric acid methyl ester) (phenyl C61-butyric acid methyl ester, manufactured by Frontier Carbon Co., Ltd.), the ratio of the weight of C60PCBM to the weight of the polymer compound 1 is 3. Ink 1 was produced by dissolving in orthodichlorobenzene as described above. The total weight of polymer compound 1 and C60PCBM was 2.0% by weight with respect to the weight of ink 1.
  • C60PCBM phenyl C61-butyric acid methyl ester
  • the ink 1 was applied on a glass substrate by spin coating to produce an organic film containing the polymer compound 1.
  • the film thickness was about 100 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.
  • the obtained organic thin-film solar cell is irradiated with a constant light using a solar simulator (trade name OTENTO-SUN II: AM1.5G filter, irradiance 100 mW / cm 2 , manufactured by Spectrometer Co., Ltd.), and the generated current and voltage are The photoelectric conversion efficiency, short-circuit current density, open-circuit voltage, and fill factor were determined by measurement. Jsc (short circuit current density) is 0.30 mA / cm 2 , Voc (open circuit voltage) is 0.96 V, ff (fill factor) is 0.30, and photoelectric conversion efficiency ( ⁇ ) Was 0.086%. The results are shown in Table 1.
  • Example 2 (Production and Evaluation of Organic Thin Film Solar Cell) An organic thin film solar cell was prepared and evaluated in the same manner as in Example 1 except that the polymer compound 2 was used instead of the polymer compound 1. Jsc (short circuit current density) is 0.39 mA / cm 2 , Voc (open end voltage) is 0.73 V, ff (fill factor) is 0.24, and photoelectric conversion efficiency ( ⁇ ) was 0.068%. The results are shown in Table 1.
  • Example 3 (Production and Evaluation of 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 1 except that the polymer compound 3 was used instead of the polymer compound 1.
  • the present invention is useful for providing a photoelectric conversion element.

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  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
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Abstract

L'invention concerne un élément de conversion photoélectrique présentant d'excellentes caractéristiques, qui possède une paire d'électrodes et une couche active disposée entre les électrodes, et qui, dans la couche active, contient un polymère contenant une unité de répétition représentée par la formule (I). Dans ladite formule: R1 et R2 sont identiques ou différents et représentent un groupe substituant; n et m sont identiques ou différents et représentent un nombre entier compris entre 0 et 3; R1, lorsqu'il en existe plusieurs qui sont identiques, peuvent être identiques ou différents; et R2, lorsqu'il en existe plusieurs qui sont identiques, peuvent être identiques ou différents.
PCT/JP2011/080138 2010-12-27 2011-12-20 Élément de conversion photoélectrique et composition utilisée dans celui-ci Ceased WO2012090971A1 (fr)

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CN108137498A (zh) * 2015-10-06 2018-06-08 大金工业株式会社 富勒烯衍生物和n型半导体材料
CN112661939A (zh) * 2020-12-17 2021-04-16 广东聚华印刷显示技术有限公司 聚合物及其制备方法和应用

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CN112661939B (zh) * 2020-12-17 2024-05-31 广东聚华印刷显示技术有限公司 聚合物及其制备方法和应用

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