WO2023238764A1 - Composition, film, organic photoelectric conversion element, and photodetection element - Google Patents

Composition, film, organic photoelectric conversion element, and photodetection element Download PDF

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WO2023238764A1
WO2023238764A1 PCT/JP2023/020440 JP2023020440W WO2023238764A1 WO 2023238764 A1 WO2023238764 A1 WO 2023238764A1 JP 2023020440 W JP2023020440 W JP 2023020440W WO 2023238764 A1 WO2023238764 A1 WO 2023238764A1
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group
substituent
type semiconductor
surfactant
photoelectric conversion
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French (fr)
Japanese (ja)
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史郎 片倉
裕 篠田
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住友化学株式会社
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/60—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation in which radiation controls flow of current through the devices, e.g. photoresistors
    • 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 composition, a film, an organic photoelectric conversion element, and a photodetection element.
  • Non-Patent Document 1 In recent years, organic photoelectric conversion elements containing organic compounds in their active layers have attracted attention. Attempts have also been made to improve the characteristics of photodetecting elements including such organic photoelectric conversion elements (see Non-Patent Document 1).
  • the photoelectric conversion element included in the photodetection element preferably has a small current flowing in a dark state (dark current). Therefore, a composition that can produce an active layer of a photoelectric conversion element with reduced dark current; a film that can function as an active layer of a photoelectric conversion element with reduced dark current; an organic photoelectric conversion element containing such a film; There is a need for a photodetection element with reduced dark current, including such an organic photoelectric conversion element.
  • the present inventors conducted intensive research to solve the above problems, and as a result, completed the present invention.
  • the present invention provides the following.
  • a composition containing a p-type semiconductor, an n-type semiconductor, a surfactant, and a solvent [2] The composition according to [1], wherein the p-type semiconductor is a polymer compound having a donor-acceptor structure. [3] The p-type semiconductor is a polymer compound containing one or more structural units selected from the group consisting of a structural unit represented by the following formula (I) and a structural unit represented by the following formula (II). The composition according to [1] or [2].
  • Ar 1 and Ar 2 each independently represent a trivalent aromatic heterocyclic group which may have a substituent
  • Z represents a group represented by any one of the following formulas (Z-1) to (Z-7).
  • R is hydrogen atom, halogen atom, an alkyl group that may have a substituent, cycloalkyl group which may have a substituent, Alkenyl group which may have a substituent, Cycloalkenyl group which may have a substituent, an alkynyl group which may have a substituent, cycloalkynyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, cycloalkylthio group which may have a substituent, Arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, imine residue which may have a substituent
  • the surfactant is a compound having an organopolysiloxane structure.
  • the surfactant is a fluorosurfactant.
  • An organic photoelectric conversion element comprising a first electrode, the film according to [11], and a second electrode in this order.
  • a photodetection element comprising the organic photoelectric conversion element according to [12].
  • a composition that can produce an active layer of a photoelectric conversion element with reduced dark current; a film that can function as an active layer of a photoelectric conversion element with reduced dark current; A photoelectric conversion element; a photodetection element with reduced dark current that includes such an organic photoelectric conversion element; can be provided.
  • FIG. 1 is a diagram schematically showing a configuration example of a photoelectric conversion element.
  • polymer compound refers to a polymer having a molecular weight distribution and a number average molecular weight in terms of polystyrene of 1 x 103 or more and 1 x 108 or less.
  • the total amount of structural units contained in the polymer compound is 100 mol%.
  • structural unit refers to one or more units present in a polymer compound.
  • “Monomeric unit” means a unit having a structure that can be obtained by polymerizing the monomer.
  • a “monomeric unit” is not limited by its manufacturing method.
  • a "hydrogen atom” may be a light hydrogen atom or a deuterium atom.
  • halogen atom examples include fluorine atom, chlorine atom, bromine atom, and iodine atom.
  • Embodiments that "may have a substituent” include cases where all hydrogen atoms constituting the compound or group are unsubstituted, and cases where one or more hydrogen atoms are partially or entirely substituted with a substituent. Both aspects are included.
  • substituents include halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, cycloalkynyl groups, alkyloxy groups, cycloalkyloxy groups, alkylthio groups, cycloalkylthio groups, aryl groups, Aryloxy group, arylthio group, monovalent heterocyclic group, hydroxy group, carboxy group, substituted amino group, acyl group, imine residue, amide group, acid imide group, substituted oxycarbonyl group, cyano group, alkylsulfonyl group, and a nitro group.
  • alkyl group may have a substituent.
  • the “alkyl group” may be either linear or branched unless otherwise specified.
  • the number of carbon atoms in the linear alkyl group, not including the number of carbon atoms in substituents, is usually 1 to 50, preferably 1 to 30, and more preferably 1 to 20.
  • the number of carbon atoms in the branched or cyclic alkyl group, not including the number of carbon atoms in substituents is usually 3 to 50, preferably 3 to 30, and more preferably 4 to 20.
  • alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isoamyl group, 2-ethylbutyl group, n- Hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, 3-n-propylheptyl group, n-decyl group, 3,7-dimethyloctyl group, 2-ethyloctyl group, 2-n-hexyl group - Unsubstituted alkyl groups such as decyl group, n-dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group; trifluoromethyl group, pentafluoride,
  • the "cycloalkyl group” may be a monocyclic group or a polycyclic group.
  • the cycloalkyl group may have a substituent.
  • the number of carbon atoms in the cycloalkyl group, not including the number of carbon atoms in substituents, is usually 3 to 30, preferably 3 to 20.
  • cycloalkyl groups include alkyl groups without substituents such as cyclopentyl group, cyclohexyl group, cycloheptyl group, and adamantyl group, and hydrogen atoms in these groups include alkyl groups, alkyloxy groups, and aryl groups. , a group substituted with a substituent such as a fluorine atom.
  • cycloalkyl group having a substituent examples include a methylcyclohexyl group and an ethylcyclohexyl group.
  • alkenyl group may be linear or branched.
  • the alkenyl group may have a substituent.
  • the number of carbon atoms in the alkenyl group, not including the number of carbon atoms in substituents, is usually 2 to 30, preferably 2 to 20.
  • alkenyl groups include vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, 3-butenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 5-hexenyl group, Examples include alkenyl groups having no substituent, such as a 7-octenyl group, and groups in which a hydrogen atom in these groups is substituted with a substituent such as an alkyloxy group, an aryl group, or a fluorine atom.
  • the "cycloalkenyl group” may be a monocyclic group or a polycyclic group.
  • the cycloalkenyl group may have a substituent.
  • the number of carbon atoms in the cycloalkenyl group, not including the number of carbon atoms in substituents, is usually 3 to 30, preferably 3 to 20.
  • cycloalkenyl groups include cycloalkenyl groups without substituents such as cyclohexenyl groups, and hydrogen atoms in these groups with substituents such as alkyl groups, alkyloxy groups, aryl groups, and fluorine atoms. Examples include substituted groups.
  • Examples of the cycloalkenyl group having a substituent include a methylcyclohexenyl group and an ethylcyclohexenyl group.
  • alkynyl group may be linear or branched.
  • the alkynyl group may have a substituent.
  • the number of carbon atoms in the alkynyl group, not including the number of carbon atoms in substituents, is usually 2 to 30, preferably 2 to 20.
  • alkynyl groups include ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group, 4-pentynyl group, 1-hexynyl group, 5-hexynyl group, etc.
  • alkynyl groups include ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group, 4-pentynyl group, 1-hexynyl group, 5-hexynyl group, etc.
  • the "cycloalkynyl group” may be a monocyclic group or a polycyclic group.
  • the cycloalkynyl group may have a substituent.
  • the number of carbon atoms in the cycloalkynyl group, not including the number of carbon atoms in substituents, is usually 4 to 30, preferably 4 to 20.
  • cycloalkynyl groups include cycloalkynyl groups without substituents such as cyclohexynyl groups, and hydrogen atoms in these groups substituted with substituents such as alkyl groups, alkyloxy groups, aryl groups, and fluorine atoms.
  • substituents such as alkyl groups, alkyloxy groups, aryl groups, and fluorine atoms. The following groups are mentioned.
  • Examples of the cycloalkynyl group having a substituent include a methylcyclohexynyl group and an ethylcyclohexynyl group.
  • alkyloxy group may be linear or branched.
  • the alkyloxy group may have a substituent.
  • the number of carbon atoms in the alkyloxy group, not including the number of carbon atoms in substituents, is usually 1 to 30, preferably 1 to 20.
  • alkyloxy groups include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, 3,7-dimethyloctyloxy group, 3-heptyldodecyloxy group, lauryloxy group, etc.
  • Examples thereof include an alkyloxy group having no substituent, and a group in which a hydrogen atom in these groups is substituted with a substituent such as an alkyloxy group, an aryl group, or a fluorine atom.
  • the cycloalkyl group possessed by the "cycloalkyloxy group” may be a monocyclic group or a polycyclic group.
  • the cycloalkyloxy group may have a substituent.
  • the number of carbon atoms in the cycloalkyloxy group, not including the number of carbon atoms in substituents, is usually 3 to 30, preferably 3 to 20.
  • cycloalkyloxy groups include cycloalkyloxy groups without substituents such as cyclopentyloxy, cyclohexyloxy, and cycloheptyloxy groups, and hydrogen atoms in these groups such as fluorine atoms, alkyl groups, etc. Examples include groups substituted with substituents.
  • alkylthio group may be linear or branched.
  • the alkylthio group may have a substituent.
  • the number of carbon atoms in the alkylthio group, not including the number of carbon atoms in substituents, is usually 1 to 30, preferably 1 to 20.
  • alkylthio groups that may have substituents include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, tert-butylthio group, n-pentylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, 2-ethylhexylthio group, n-nonylthio group, n-decylthio group, 3,7-dimethyloctylthio group, 3-heptyldodecylthio group, laurylthio group, and trifluoromethylthio group.
  • the cycloalkyl group possessed by the "cycloalkylthio group” may be a monocyclic group or a polycyclic group.
  • the cycloalkylthio group may have a substituent.
  • the number of carbon atoms in the cycloalkylthio group, not including the number of carbon atoms in substituents, is usually 3 to 30, preferably 3 to 20.
  • cycloalkylthio group which may have a substituent is a cyclohexylthio group.
  • P-valent aromatic carbocyclic group means an atomic group remaining after removing p hydrogen atoms directly bonded to carbon atoms constituting a ring from an aromatic hydrocarbon that may have a substituent. do.
  • Aromatic hydrocarbons also include compounds having fused rings, compounds in which two or more selected from the group consisting of independent benzene rings and fused rings are bonded directly or via a divalent group such as vinylene.
  • the p-valent aromatic carbocyclic group may further have a substituent.
  • Aryl group means a monovalent aromatic carbocyclic group.
  • the aryl group may have a substituent.
  • the number of carbon atoms in the aryl group, not including the number of carbon atoms in substituents, is usually 6 to 60, preferably 6 to 48.
  • aryl group examples include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, Aryl groups without substituents, such as 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 2-phenylphenyl group, 3-phenylphenyl group, 4-phenylphenyl group, and hydrogen atoms in these groups
  • examples thereof include groups substituted with substituents such as an alkyl group, an alkyloxy group, an aryl group, and a fluorine atom.
  • the "aryloxy group” may have a substituent.
  • the number of carbon atoms in the aryloxy group, not including the number of carbon atoms in substituents, is usually 6 to 60, preferably 6 to 48.
  • aryloxy groups include phenoxy groups, 1-naphthyloxy groups, 2-naphthyloxy groups, 1-anthracenyloxy groups, 9-anthracenyloxy groups, and 1-pyrenyloxy groups that have no substituents.
  • Examples include aryloxy groups and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyl groups, alkyloxy groups, and fluorine atoms.
  • the "arylthio group” may have a substituent.
  • the number of carbon atoms in the arylthio group, not including the number of carbon atoms in substituents, is usually 6 to 60, preferably 6 to 48.
  • Examples include thio group.
  • C1-C12 represents that the group immediately following it has 1 to 12 carbon atoms.
  • Cm to Cn indicates that the number of carbon atoms in the group immediately following it is m to n. The same applies below.
  • a "p-valent heterocyclic group” (p represents an integer of 1 or more) is a hydrogen bond directly bonded to a carbon atom or heteroatom constituting a ring of a heterocyclic compound that may have a substituent. It means the atomic group remaining after p hydrogen atoms are removed from the atoms.
  • the "p-valent heterocyclic group” includes "p-valent aromatic heterocyclic group.”
  • P-valent aromatic heterocyclic group means p of the hydrogen atoms directly bonded to the carbon atoms or hetero atoms constituting the ring from an aromatic heterocyclic compound which may have a substituent. It means the remaining atomic group after removing hydrogen atoms.
  • Aromatic heterocyclic compounds include compounds in which the heterocycle itself exhibits aromaticity, as well as compounds in which an aromatic ring is fused to the heterocycle, even if the heterocycle itself does not exhibit aromaticity. Ru.
  • aromatic heterocyclic compounds specific examples of compounds in which the heterocycle itself is aromatic include oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, and triazine. , pyridazine, quinoline, isoquinoline, carbazole, and dibenzophosphole.
  • aromatic heterocyclic compounds specific examples of compounds in which the heterocycle itself does not exhibit aromaticity and an aromatic ring is fused to the heterocycle include phenoxazine, phenothiazine, dibenzoborole, dibenzosilole, and benzopyran.
  • the p-valent heterocyclic group may have a substituent.
  • the number of carbon atoms in the p-valent heterocyclic group, not including the number of carbon atoms in substituents, is usually 2 to 60, preferably 2 to 20.
  • Examples of monovalent heterocyclic groups include monovalent aromatic heterocyclic groups (e.g., thienyl group, pyrrolyl group, furyl group, pyridyl group, quinolyl group, isoquinolyl group, pyrimidinyl group, triazinyl group), Examples include non-aromatic heterocyclic groups (eg, piperidyl group, piperazyl group), and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyl groups, alkyloxy groups, and fluorine atoms.
  • monovalent aromatic heterocyclic groups e.g., thienyl group, pyrrolyl group, furyl group, pyridyl group, quinolyl group, isoquinolyl group, pyrimidinyl group, triazinyl group
  • non-aromatic heterocyclic groups eg, piperidyl group, piperazyl group
  • groups in which hydrogen atoms in these groups are substituted with substituent
  • Substituted amino group means an amino group having a substituent.
  • Preferred substituents for the amino group include an alkyl group, a cycloalkyl group, an aryl group, and a monovalent heterocyclic group.
  • the number of carbon atoms in the substituted amino group is usually 2 to 30, not including the number of carbon atoms in the substituents.
  • substituted amino groups include dialkylamino groups (e.g. dimethylamino group, diethylamino group), diarylamino groups (e.g. diphenylamino group, bis(4-methylphenyl)amino group, bis(4-tert-butylphenyl) ) amino group, bis(3,5-di-tert-butylphenyl)amino group).
  • dialkylamino groups e.g. dimethylamino group, diethylamino group
  • diarylamino groups e.g. diphenylamino group, bis(4-methylphenyl)amino group, bis(4-tert-butylphenyl) ) amino group, bis(3,5-di-tert-butylphenyl)amino group.
  • the "acyl group” may have a substituent.
  • the number of carbon atoms in the acyl group, not including the number of carbon atoms in substituents, is usually 2 to 20, preferably 2 to 18.
  • Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.
  • Imine residue means an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom or nitrogen atom constituting a carbon atom-nitrogen atom double bond from an imine compound.
  • Imine compound means an organic compound having a carbon atom-nitrogen atom double bond in the molecule.
  • imine compounds include aldimine, ketimine, and aldimine in which the hydrogen atom bonded to the nitrogen atom forming the carbon-nitrogen double bond is substituted with a substituent such as an alkyl group or a cycloalkyl group. Examples include compounds such as
  • the number of carbon atoms in the imine residue is usually 2 to 20, preferably 2 to 18.
  • Examples of imine residues include groups represented by the following structural formula.
  • Amide group means an atomic group remaining after removing one hydrogen atom bonded to a nitrogen atom from amide.
  • the number of carbon atoms in the amide group is usually about 1 to 20, preferably 1 to 18.
  • Specific examples of the amide group include formamide group, acetamide group, propioamide group, butyroamide group, benzamide group, trifluoroacetamide group, pentafluorobenzamide group, diformamide group, diacetamide group, dipropioamide group, dibutyroamide group, dibenzamide group. , ditrifluoroacetamide group, and dipentafluorobenzamide group.
  • Acid imide group means an atomic group remaining after removing one hydrogen atom bonded to a nitrogen atom from an acid imide.
  • the acid imide group usually has 4 to 20 carbon atoms. Specific examples of the acid imide group include the groups shown below.
  • R' represents an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group, and these groups may have a substituent.
  • the substituted oxycarbonyl group usually has 2 to 60 carbon atoms, preferably 2 to 48 carbon atoms.
  • substituted oxycarbonyl groups include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, tert-butoxycarbonyl group, pentyloxycarbonyl group, and hexyloxycarbonyl group.
  • Examples include fluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group, perfluorooctyloxycarbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group, and pyridyloxycarbonyl group.
  • alkylsulfonyl group may be linear or branched.
  • the alkylsulfonyl group may have a substituent.
  • the number of carbon atoms in the alkylsulfonyl group is usually 1 to 30, not including the number of carbon atoms in substituents.
  • Specific examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, and a dodecylsulfonyl group.
  • ⁇ -conjugated system means a system in which ⁇ electrons are delocalized across multiple bonds.
  • (Meth)acrylic includes acrylic, methacrylic, and combinations thereof.
  • (Meth)acrylate includes acrylate, methacrylate, and combinations thereof.
  • solvent can be a dispersion medium.
  • a composition according to one embodiment of the present invention includes a p-type semiconductor, an n-type semiconductor, a surfactant, and a solvent.
  • the composition may contain arbitrary components as necessary.
  • the composition may be a solution, or a dispersion such as a dispersion, an emulsion, or a suspension.
  • a photoelectric conversion element including a film obtained from the composition of this embodiment has reduced dark current.
  • surfactant is meant a substance that changes the properties of the interface upon addition. Surfactants usually have both a hydrophilic group and a hydrophobic group in one molecule.
  • the dark current of a photoelectric conversion element including a film obtained from the composition can be effectively reduced.
  • a composition is applied to a coating object such as an electrode or an intermediate layer to form a coating film, and the coating film is further dried to form a film (active layer).
  • a film active layer
  • the surfactant exists in the form of a film on the surface of the coating film, and when the coating film dries, the surfactant unevenly distributed on the surface of the coating film segregates as it is and solidifies.
  • a thin film of surfactant exists on the surface of the obtained film (active layer) and functions as an insulating layer, which is thought to reduce the dark current of the photoelectric conversion element.
  • phase separation structure formed by the p-type semiconductor and the n-type semiconductor changes due to the action of the surfactant, and this change is thought to reduce the dark current of the photoelectric conversion element.
  • a surfactant that can effectively reduce the dark current of a photoelectric conversion element including a film obtained from the composition according to the present embodiment it is necessary to appropriately select the types of hydrophilic groups and hydrophobic groups in the molecule.
  • a suitable surfactant can be selected.
  • a surfactant classified as nonionic When selecting the surfactant contained in the composition of the present embodiment based on the type of hydrophilic group, it is preferable to use a surfactant classified as nonionic.
  • a non-aqueous solvent such as an aromatic hydrocarbon solvent is used as the solvent contained in the composition of this embodiment.
  • Nonionic surfactants are preferred also because they have excellent solubility in solvents.
  • hydrophilic groups include groups having epoxy groups such as ethylene oxide and propylene oxide, amino groups, ketone groups, carboxyl groups, and sulfone groups.
  • the surfactant may have one or more groups selected from these as hydrophilic groups.
  • surfactants contained in the composition of the present embodiment based on the type of hydrophobic group, acrylic surfactants whose hydrophobic groups have a poly(meth)acrylate structure, silicone surfactants whose hydrophobic groups have a poly(meth)acrylate structure, and silicone surfactants whose hydrophobic groups have a poly(meth)acrylate structure and fluorine-based surfactants in which some or all of the hydrogen atoms of these groups are substituted with fluorine atoms.
  • the surfactant preferably has a poly(meth)acrylate structure.
  • the poly(meth)acrylate structure is a structure represented by the following formula (SF-1).
  • SF-1 formula 1
  • the surfactant may contain any structural unit in addition to the poly(meth)acrylate structure.
  • Surfactants having a poly(meth)acrylate structure can be oligomers or polymers.
  • R sf1 's each independently represent a hydrogen atom or a methyl group.
  • a plurality of R sf2 's each independently represent an organic group. Two or more of the plurality of R sf2 may be combined to form a crosslinking group.
  • R sf2 preferably each independently represents an alkyl group, a cycloalkyl group, an alkyloxyalkyl group, a group having a polyoxyalkylene group, an aryl group, an arylalkyl group, an aryloxyalkyl group, and these groups are It may have a substituent (for example, a fluorine atom).
  • alkyl group represented by R sf2 include fluorine atom-substituted alkyl groups in which some of the hydrogen atoms of the alkyl group are substituted with fluorine atoms (e.g., difluoromethyl group, 2,2-difluoroethyl group).
  • n number of repeating units is, for example, 2 or more, 3 or more, 4 or more, 5 or more, 10 or more, and, for example, 3000 or less.
  • surfactant having a poly(meth)acrylate structure Commercially available products can be used as the surfactant having a poly(meth)acrylate structure.
  • nonionic surfactants having a poly(meth)acrylate structure include "F-556,”"R-40,””MEGAFACEF-110,” and "Megaface F.
  • the surfactant preferably has an organopolysiloxane structure.
  • the organopolysiloxane structure is a structure represented by the following formula (SF-2).
  • SF-2 formula 2
  • the surfactant may contain any structural unit in addition to the organopolysiloxane structure.
  • Surfactants having an organopolysiloxane structure can be oligomers or polymers.
  • R sf3 's each independently represent an organic group.
  • Surfactants having an organopolysiloxane structure can have any terminal group.
  • Examples of terminal groups that a surfactant having an organopolysiloxane structure may have include an alkyl group, a cycloalkyl group, an alkyloxy group, a cycloalkyloxy group, a group having a polyoxyalkylene group, an aryl group, and an arylalkyl group.
  • a poly(meth)acryloyl group and these groups may have a substituent (eg, a fluorine atom).
  • n number of repeating units
  • n number of repeating units
  • the surfactant is preferably a fluorosurfactant.
  • the fluorine-based surfactant means a surfactant containing a fluorine atom in its molecule.
  • the dark current of the photoelectric conversion element can be effectively reduced.
  • fluorosurfactant Commercially available products can be used as the fluorosurfactant.
  • fluorosurfactants include "F-556", “R-40", Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (manufactured by DIC), Florado FC430, FC431, FC171, Novec FC4430, FC4432 (manufactured by 3M Japan), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by Asahi Glass Co., Ltd.), Examples include PF636, PF656, PF6320, PF6520, and
  • the surfactant is preferably liquid at 25° C. and 1 atm. Since the surfactant is liquid at 25° C. and 1 atm, it has good solubility in the composition.
  • the viscosity ⁇ of the surfactant is preferably 1 mPa ⁇ s or more, more preferably 10 mPa ⁇ s or more, even more preferably 100 mPa ⁇ s or more, and preferably 10,000 mPa ⁇ s or less, more preferably 5,000 mPa ⁇ s. It is as follows. When the viscosity ⁇ of the surfactant is within the above range, the dark current of the photoelectric conversion element can be effectively reduced.
  • the viscosity ⁇ is a value measured using a rheometer at a temperature of 25° C. and a shear rate of 100 (1/s).
  • the peak molecular weight Mp of the surfactant is preferably 100 or more, more preferably 1000 or more, and preferably 10,000 or less, more preferably 5,000 or less. When the peak molecular weight Mp of the surfactant is within the above range, the dark current of the photoelectric conversion element can be effectively reduced.
  • the peak molecular weight Mp of the surfactant is a value measured by gel permeation chromatography (GPC).
  • the peak molecular weight Mp may be the peak top value in a GPC chromatogram measured under the following measurement conditions.
  • O-dichlorobenzene is used as the mobile phase for GPC, and it is flowed at a flow rate of 1.0 mL/min.
  • Shodex KD-806M manufactured by Showa Denko Co., Ltd. is used, and as the guard column, Shodex KD-G manufactured by Showa Denko Co., Ltd. is used.
  • a UV-vis detector manufactured by Shimadzu Corporation, SPD-M20A
  • a differential refractive index detector manufactured by Shimadzu Corporation, RID-10A
  • the compound (polymer) to be measured is mixed in the solvent 1-chloronaphthalene to a concentration of 0.05% by mass, and stirred at 80°C for 2 hours to form a solution. .
  • the peak molecular weight (Mp) is measured by injecting 10 ⁇ L of the obtained solution into the above-mentioned measuring device (GPC) as a sample.
  • the fluorine content of the surfactant is preferably 1% by mass or more, based on the solid content excluding the solvent in the fluorosurfactant as 100% by mass, The content is more preferably 5% by mass or more, preferably 50% by mass or less, and even more preferably 30% by mass or less.
  • the fluorine content of the surfactant is within the above range, the dark current of the photoelectric conversion element can be effectively reduced.
  • the fluorine content of the surfactant is below the above upper limit, the water repellency of the film (active film) obtained from the composition decreases, and a water-based coating liquid can be easily applied onto the film.
  • the fluorine content in the surfactant can be measured by combustion ion chromatography or the like.
  • the content of the surfactant in the composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and preferably 1.0% by mass, based on the total mass of the solvent as 100% by mass.
  • the content is preferably 0.5% by mass or less.
  • the content of the surfactant in the composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, based on the total mass of the n-type semiconductor, p-type semiconductor, and surfactant as 100% by mass.
  • the content is more preferably 3% by mass or more.
  • the content of the surfactant in the composition is preferably 26% by mass or less, more preferably 24.5% by mass, based on the total mass of the n-type semiconductor, p-type semiconductor, and surfactant as 100% by mass.
  • the content is preferably 10% by mass or less, particularly preferably 5% by mass or less.
  • the dark current of the photoelectric conversion element can be effectively reduced.
  • the p-type semiconductor contained in the composition of this embodiment may be a single type or a combination of two or more types.
  • the p-type semiconductor may be a low-molecular compound or a high-molecular compound, preferably a high-molecular compound, and more preferably a ⁇ -conjugated high-molecular compound.
  • Examples of p-type semiconductors that are polymeric compounds include polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives containing an aromatic amine structure in the side chain or main chain, polyaniline and its derivatives, polythiophene and its derivatives, Examples include polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, and polyfluorene and its derivatives.
  • the p-type semiconductor is preferably a polymer compound having a donor-acceptor structure.
  • the donor-acceptor structure includes a donor building block and an acceptor building block.
  • a donor constitutional unit is a constitutional unit that is in excess of ⁇ electrons, and an acceptor constitutional unit is a constitutional unit that is deficient in ⁇ electrons.
  • the structural units that can constitute a polymer compound having a donor-acceptor structure include a structural unit in which a donor structural unit and an acceptor structural unit are directly bonded, and further a donor structural unit and an acceptor structural unit. Also included are structural units bonded via spacers (groups or structural units).
  • the p-type semiconductor has one or more configurations selected from the group consisting of the structural unit represented by the following formula (I) and the structural unit represented by the following formula (II).
  • a polymer compound containing units is preferable.
  • Ar 1 and Ar 2 each independently represent a trivalent aromatic heterocyclic group which may have a substituent, and Z represents the following formula (Z-1) to formula ( Represents a group represented by any one of Z-7).
  • R is hydrogen atom, halogen atom, an alkyl group that may have a substituent, cycloalkyl group which may have a substituent, Alkenyl group which may have a substituent, Cycloalkenyl group which may have a substituent, an alkynyl group which may have a substituent, cycloalkynyl group which may have a substituent, an aryl group which may have a substituent, an alkyloxy group which may have a substituent, cycloalkyloxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, cycloalkylthio group which may have a substituent, Arylthio group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituted amino group which may have a substituent, imine residue which may have a substituent,
  • R in formulas (Z-1) to (Z-7) is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, more preferably a hydrogen atom or an alkyl group, and even more preferably, A hydrogen atom or an alkyl group having 1 to 40 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, and particularly preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. . These groups may have a substituent. When a plurality of R's exist, the plurality of R's may be the same or different.
  • the structural unit represented by formula (I) is preferably a structural unit represented by formula (I-1) below.
  • Z represents the same meaning as above.
  • Examples of the structural unit represented by formula (I-1) include structural units represented by the following formulas (501) to (505).
  • R represents the same meaning as above.
  • the two R's may be the same or different.
  • the structural unit represented by formula (I) is preferably a group represented by formula (501) above.
  • Ar 3 represents a divalent aromatic heterocyclic group.
  • the number of carbon atoms in the divalent aromatic heterocyclic group represented by Ar 3 is usually 2 to 60, preferably 4 to 60, more preferably 4 to 20.
  • the divalent aromatic heterocyclic group represented by Ar 3 may have a substituent.
  • the structural unit represented by formula (II) is preferably a structural unit represented by any of the following formulas (II-1) to (II-8).
  • X 1 and X 2 each independently represent a sulfur atom or an oxygen atom
  • R is the same as defined in formulas (Z-1) to (Z-7).
  • a plurality of R's may be the same or different.
  • the two R's are preferably each independently a hydrogen atom, an alkyl group, or a halogen atom, more preferably a hydrogen atom or a halogen atom at the same time, and even more preferably, At the same time, it is a halogen atom.
  • X 1 and X 2 in formulas (II-1) to (II-8) are both sulfur atoms.
  • Examples of the divalent aromatic heterocyclic group represented by Ar 3 include groups represented by the following formulas (101) to (190). These groups may have a substituent.
  • R represents the same meaning as above.
  • the plurality of R's may be the same or different.
  • the p-type semiconductor may have an arylene group in addition to the structural unit represented by the formula (I) and/or the structural unit represented by the formula (II).
  • An arylene group means a divalent aromatic carbocyclic group.
  • the arylene group may have a substituent.
  • the number of carbon atoms in the arylene group excluding substituents is usually 6 to 60, preferably 6 to 20.
  • the number of carbon atoms in the arylene group including substituents is usually 6 to 100.
  • arylene group examples include a phenylene group, a naphthalene-diyl group, an anthracene-diyl group, a biphenyl-diyl group, a terphenyl-diyl group, a fluorene-diyl group, and a benzofluorene-diyl group.
  • the p-type semiconductor is a polymer compound containing the structural unit represented by formula (I) and/or the structural unit represented by formula (II), the structural unit represented by formula (I) and the structural unit represented by formula (I)
  • the total amount of the structural units represented by II) is usually 20 to 100 mol%, and is preferably 40 to 100 mol%, more preferably 50 to 100 mol%, since it improves charge transport properties as a p-type semiconductor. It is 100 mol%. However, the amount of all structural units contained in the polymer compound is 100 mol%.
  • Preferred specific examples of the p-type semiconductor include the following polymer compounds.
  • the content of the p-type semiconductor in the composition can be set to any suitable content depending on the required thickness of the functional layer (active layer), desired characteristics, and the like.
  • the content of the p-type semiconductor in the composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and preferably 20% by mass or less, more preferably It is 10% by mass or less.
  • n-type semiconductor contained in the composition of this embodiment may be a single type or a combination of two or more types.
  • the n-type semiconductor may be a low-molecular compound or a high-molecular compound.
  • n-type semiconductors include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, and diphenyl.
  • Dicyanoethylene and its derivatives diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, fullerenes such as C 60 fullerene and fullerene derivatives thereof (hereinafter sometimes referred to as fullerene compounds), bathocuproine, etc.
  • fullerene compounds such as C 60 fullerene and fullerene derivatives thereof (hereinafter sometimes referred to as fullerene compounds), bathocuproine, etc.
  • fullerene compounds such as C 60 fullerene and fullerene derivatives thereof (hereinafter sometimes referred to as fullerene compounds), bathocuproine, etc.
  • fullerene compounds such as C 60 fullerene and fullerene derivatives thereof (hereinafter sometimes referred to as fullerene compounds), bathocuproine, etc.
  • Examples include phenanthrene derivatives.
  • the n-type semiconductor may be fullerene such as C 60 fullerene and a fullerene derivative thereof, or may be a non-fullerene compound.
  • fullerene and fullerene derivatives may be referred to as fullerene compounds.
  • a non-fullerene compound means a compound other than fullerene and fullerene derivatives.
  • the n-type semiconductor contained in the composition is preferably one or more selected from fullerene and fullerene derivatives, and more preferably fullerene derivatives.
  • fullerenes include C 60 fullerene, C 70 fullerene, C 76 fullerene, C 78 fullerene, and C 84 fullerene.
  • fullerene derivatives include these fullerene derivatives.
  • Fullerene derivative means a compound in which at least a portion of fullerene is modified.
  • fullerene derivatives include compounds represented by the following formula.
  • R a represents an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, or a group having an ester structure, and these groups may have a substituent.
  • a plurality of R a 's may be the same or different.
  • R b represents an alkyl group, a cycloalkyl group, or an aryl group, and these groups may have a substituent.
  • a plurality of R b 's may be the same or different.
  • Examples of the group having an ester structure represented by R a include a group represented by the following formula.
  • u1 represents an integer from 1 to 6.
  • u2 represents an integer from 0 to 6.
  • R e represents an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent.
  • Examples of C 60 fullerene derivatives include the following compounds.
  • C70 fullerene derivatives include the following compounds.
  • 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 aci methyl ester), and [6,6 ]-Thienyl-C61 butyric acid methyl ester ([6,6]-Thienyl C61 butyric acid methyl ester).
  • the n-type semiconductor contained in the composition is preferably a non-fullerene compound.
  • a non-fullerene compound Various kinds of compounds are known as non-fullerene compounds, and any conventionally known suitable non-fullerene compounds can be used as the n-type semiconductor in this embodiment.
  • the n-type semiconductor contained in the composition is preferably a compound containing a perylenetetracarboxylic acid diimide structure.
  • compounds containing a perylenetetracarboxylic acid diimide structure that are non-fullerene compounds include compounds represented by the following formula.
  • R is as defined above.
  • a plurality of R's may be the same or different.
  • the n-type semiconductor is preferably a compound represented by the following formula (V).
  • the compound represented by the following formula (V) is a non-fullerene compound containing a perylenetetracarboxylic acid diimide structure.
  • R 1 is a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, or a cycloalkyl group that may have a substituent.
  • a good alkyloxy group, a cycloalkyloxy group that may have a substituent, an aryl group that may have a substituent, or a monovalent aromatic heterocyclic group that may have a substituent. represent.
  • a plurality of R 1 's may be the same or different.
  • each of the plurality of R 1 's independently represents an alkyl group which may have a substituent.
  • R2 is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkyloxy group, a substituent represents a cycloalkyloxy group which may have a substituent, an aryl group which may have a substituent, or a monovalent aromatic heterocyclic group which may have a substituent.
  • a plurality of R 2 may be the same or different.
  • the n-type semiconductor is preferably a compound represented by the following formula (VI).
  • a 1 and A 2 each independently represent an electron-withdrawing group, and B 10 represents a group containing a ⁇ -conjugated system.
  • T represents a carbocycle which may have a substituent or a heterocycle which may have a substituent.
  • Carbocycles and heterocycles may be monocyclic or fused rings. When these rings have multiple substituents, the multiple substituents may be the same or different.
  • Examples of the carbocycle which may have a substituent which is T include an aromatic carbocycle, and preferably an aromatic carbocycle.
  • Specific examples of the carbocyclic ring which may have a substituent which is T include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring, preferably a benzene ring, They are a naphthalene ring and a phenanthrene ring, more preferably a benzene ring and a naphthalene ring, and still more preferably a benzene ring. These rings may have a substituent.
  • heterocycle which may have a substituent which is T examples include an aromatic heterocycle, and preferably an aromatic heterocycle.
  • Specific examples of the heterocycle which may have a substituent which is T include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, and a thienothiophene ring, preferably a thiophene ring, a pyridine ring, a pyrazine ring, a thiazole ring, and a thienothiophene ring, and more preferably a thiophene ring. These rings may have a substituent.
  • substituents that the carbocyclic or heterocyclic ring T may have include a halogen atom, an alkyl group, an alkyloxy group, an aryl group, and a monovalent heterocyclic group, preferably a fluorine atom and/or or an alkyl group having 1 to 6 carbon atoms.
  • X 7 is a hydrogen atom, a halogen atom, a cyano group, an alkyl group that may have a substituent, an alkyloxy group that may have a substituent, an aryl group that may have a substituent, or Represents a monovalent heterocyclic group.
  • R a1 , R a2 , R a3 , R a4 , and R a5 each independently represent a hydrogen atom, an optionally substituted alkyl group, a halogen atom, and an optionally substituted alkyl group.
  • R a6 and R a7 are each independently a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, or a substituent.
  • the electron-withdrawing groups A 1 and A 2 include the following formulas (a-1-1) to (a-1-4), formula (a-6-1) and formula (a-7).
  • a group represented by any of formula (a-1-1) is preferred, and a group represented by formula (a-1-1) is more preferred.
  • each of the plural R a10 's independently represents a hydrogen atom or a substituent, and preferably represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent.
  • R a3 , R a4 , and R a5 each independently have the same meaning as above, and preferably each independently represents an alkyl group that may have a substituent or an aryl group that may have a substituent. represents a group.
  • An example of a group containing a ⁇ -conjugated system that is B 10 is a group represented by -(S 1 ) n1 -B 11 -(S 2 ) n2 - in a compound represented by formula (VII) described below. Can be mentioned.
  • the n-type semiconductor is preferably a compound represented by the following formula (VII).
  • a 1 and A 2 each independently represent an electron-withdrawing group. Examples and preferred examples of A 1 and A 2 are the same as those described for A 1 and A 2 in formula (VI) above.
  • the optionally substituted divalent carbocyclic group and the optionally substituted divalent heterocyclic group represented by S 1 and S 2 may be a fused ring.
  • the plurality of substituents may be the same or different.
  • n1 and n2 each independently represent an integer of 0 or more, preferably each independently represents 0 or 1, and more preferably represents 0 or 1 at the same time.
  • divalent carbocyclic groups include divalent aromatic carbocyclic groups.
  • divalent heterocyclic groups include divalent aromatic heterocyclic groups.
  • the divalent aromatic carbocyclic group or the divalent aromatic heterocyclic group is a condensed ring, all of the rings constituting the condensed ring may be aromatic, or only some of the rings may be aromatic. It may be a condensed ring having aromaticity.
  • S 1 and S 2 include groups represented by any of the formulas (101) to (190) listed as examples of the divalent aromatic heterocyclic group represented by Ar 3 as described above; and groups in which hydrogen atoms in these groups are substituted with substituents.
  • S 1 and S 2 preferably each independently represent a group represented by the following formula (s-1) or (s-2).
  • X 3 represents an oxygen atom or a sulfur atom.
  • R a10 is as defined above.
  • S 1 and S 2 are preferably each independently a group represented by formula (142), formula (148), or formula (184), or a group in which the hydrogen atom in these groups is substituted with a substituent. More preferably, one hydrogen atom in the group represented by formula (142) or formula (184) or the group represented by formula (184) is substituted with an alkyloxy group. .
  • B11 is a fused ring group having two or more structures selected from the group consisting of a carbocyclic structure and a heterocyclic structure, and is a fused ring group that does not contain an ortho-perifused structure, and has a substituent. represents a fused ring group that may be fused.
  • the fused ring group represented by B 11 may include a structure in which two or more mutually identical structures are condensed.
  • the fused ring group represented by B 11 has a plurality of substituents
  • the plurality of substituents may be the same or different.
  • Examples of carbocyclic structures that can constitute the fused ring group represented by B 11 include ring structures represented by the following formula (Cy1) or (Cy2).
  • B 11 is preferably a fused ring group having two or more structures selected from the group consisting of the structures represented by formulas (Cy1) to (Cy10), and is ortho-peripheral. It is a fused ring group that does not contain a fused structure and may have a substituent. B 11 may include a structure in which two or more of the same structures among the structures represented by formulas (Cy1) to (Cy10) are condensed.
  • B 11 is more preferably a fused ring group having two or more structures selected from the group consisting of structures represented by formulas (Cy1) to (Cy6) and formula (Cy8), and is an ortho-pericondensed ring group. It is a fused ring group that does not contain any structure and may have a substituent.
  • the substituent that the fused ring group B11 may have is preferably an alkyl group that may have a substituent, an aryl group that may have a substituent, or an aryl group that may have a substituent. an optionally substituted alkyloxy group, and a monovalent heterocyclic group optionally having a substituent.
  • the aryl group that the fused ring group represented by B 11 may have may be substituted with, for example, an alkyl group.
  • Examples of the fused ring group that is B 11 include groups represented by formulas (b-1) to (b-14) below, and hydrogen atoms in these groups that have a substituent (preferably a substituent).
  • An alkyl group that may have an optional substituent, an aryl group that may have a substituent, an alkyloxy group that may have a substituent, or a monovalent heterocyclic group that may have a substituent ) is included.
  • the fused ring group B11 is a group represented by the following formula (b-2) or (b-3), or a hydrogen atom in these groups has a substituent (preferably a substituent).
  • a substituent preferably a substituent.
  • an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, or an optionally substituted monovalent heterocyclic group A group represented by the following formula (b-2) or (b-3) is more preferable.
  • R a10 is as defined above.
  • each of the plurality of R a10s is preferably an alkyl group that may have a substituent, or an alkyl group that may have a substituent. It is an aryl group.
  • Examples of the compound represented by formula (VI) or formula (VII) include compounds represented by the following formula.
  • R is as defined above, and X represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent.
  • R is preferably a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkyloxy group. .
  • the composition may contain only a non-fullerene compound, only a fullerene compound, or a combination of a non-fullerene compound and a fullerene compound as an n-type semiconductor.
  • n-type semiconductor contained in the composition is a compound represented by the following formula.
  • the content of the n-type semiconductor in the composition can be set to any suitable content depending on the required thickness of the functional layer (active layer), desired characteristics, and the like.
  • the content of the n-type semiconductor in the composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and preferably 20% by mass or less, more preferably It is 10% by mass or less.
  • the mass ratio of the p-type semiconductor to the n-type semiconductor in the composition is preferably 1/9 or more, more preferably 1/5 or more, and even more preferably 1/3. or more, preferably 9/1 or less, more preferably 5/1 or less, still more preferably 3/1 or less.
  • the mass ratio is a ratio of the total mass of p-type semiconductors when the composition includes multiple types of p-type semiconductors, and a ratio of the total mass of the p-type semiconductors when the composition includes multiple types of n-type semiconductors. It is a ratio with respect to the total mass.
  • solvents contained in the composition of this embodiment may be used alone or in combination of two or more.
  • composition of this embodiment may contain an aromatic hydrocarbon as a solvent, and preferably contains an aromatic hydrocarbon.
  • the aromatic hydrocarbon may have a substituent.
  • the aromatic hydrocarbon is preferably a compound that can dissolve the p-type semiconductor described above.
  • aromatic hydrocarbons that can be used as solvents include toluene, xylene (e.g. o-xylene, m-xylene, p-xylene), trimethylbenzene (e.g. mesitylene, 1,2,4-trimethylbenzene (pseudocumene), )), butylbenzene (e.g., n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalene (e.g., 1-methylnaphthalene), 1,2,3,4-tetrahydronaphthalene (tetralin), indan , 1-chloronaphthalene, chlorobenzene and dichlorobenzene (1,2-dichlorobenzene).
  • xylene e.g. o-xylene, m-xylene, p-xylene
  • trimethylbenzene e.g. mesitylene, 1,2,
  • the solvent may be composed of only one type of aromatic hydrocarbon, or may be composed of two or more types of aromatic hydrocarbons.
  • Aromatic hydrocarbons that can constitute the solvent are preferably toluene, o-xylene, m-xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert - One or more selected from the group consisting of butylbenzene, methylnaphthalene, tetralin, 1-chloronaphthalene, chlorobenzene, and dichlorobenzene (1,2-dichlorobenzene).
  • the content of the aromatic hydrocarbon solvent in the solvent is preferably 80% by mass or more, more preferably 90% by mass or more, and usually 100% by mass or less, based on the total mass of the solvent as 100% by mass.
  • composition of this embodiment may contain an alkyl halide as a solvent.
  • alkyl halide examples include chloroform.
  • composition of the present embodiment may be used in combination with an additional solvent selected from the viewpoint of particularly increasing the solubility of the n-type semiconductor.
  • examples of further solvents include aromatic carbonyl compounds, aromatic ester compounds, and nitrogen-containing heterocyclic compounds.
  • the composition of the present embodiment may contain, as a solvent, one or more compounds selected from the group consisting of aromatic carbonyl compounds, aromatic ester compounds, and nitrogen-containing heterocyclic compounds.
  • aromatic carbonyl compound examples include acetophenone, propiophenone, butyrophenone, cyclohexylphenyl ketone, and benzophenone, and these compounds may have a substituent.
  • aromatic ester compounds include methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isopropyl benzoate, benzyl benzoate, cyclohexyl benzoate, and phenyl benzoate. It may have a substituent.
  • nitrogen-containing heterocyclic compounds include pyridine, quinoline, quinoxaline, 1,2,3,4-tetrahydroquinoline, pyrimidine, pyrazine, and quinazoline, and these nitrogen-containing heterocyclic compounds have a substituent. may have.
  • the nitrogen-containing heterocyclic compound may have a substituent directly bonded to the ring structure.
  • substituents that the ring structure of the nitrogen-containing heterocyclic compound may have include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, and an alkylthio group. Can be mentioned.
  • the total mass of the solvent contained in the composition of this embodiment is preferably 90% by mass from the viewpoint of further improving the solubility of the p-type semiconductor and the n-type semiconductor, when the total mass of the composition is 100% by mass. % or more, more preferably 92% by mass or more, still more preferably 95% by mass or more, and the concentration of the p-type semiconductor and n-type semiconductor in the composition is increased to form a layer with a certain thickness or more. From the viewpoint of making it easier to form, the content is preferably 99.9% by mass or less.
  • composition according to the present embodiment may contain arbitrary components as long as the objects and effects of the present invention are not impaired.
  • optional ingredients include UV absorbers, antioxidants, sensitizers to enhance the ability of absorbed light to generate a charge, and photostabilizers to increase stability from UV radiation. It will be done.
  • the total content of optional components in the composition is preferably 10% by mass or less, more preferably 5% by mass or less, and usually 0% by mass or more, and may be 0% by mass.
  • the p-type semiconductor and the n-type semiconductor may be dissolved or dispersed. It is preferable that at least a portion of the p-type semiconductor and the n-type semiconductor be dissolved in the composition.
  • the total concentration of the p-type semiconductor and n-type semiconductor in the composition of this embodiment can be set to any suitable concentration depending on the required thickness of the functional layer (active layer), desired characteristics, etc. I can do it.
  • the total concentration of the p-type semiconductor and the n-type semiconductor is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, preferably 10% by mass or less, and more preferably 5% by mass. % or less, more preferably 0.01% by mass or more and 20% by mass or less, still more preferably 0.01% by mass or more and 10% by mass or less, even more preferably 0.01% by mass or more and 5% by mass or less.
  • the content is particularly preferably 0.1% by mass or more and 5% by mass or less.
  • composition can be manufactured by a conventionally known method.
  • the solvent, p-type semiconductor, n-type semiconductor, and surfactant may be mixed by heating to a temperature below the boiling point of the solvent.
  • the resulting mixture may be filtered using a filter, and the resulting filtrate may be used as a composition.
  • a filter for example, a filter made of a fluororesin such as polytetrafluoroethylene (PTFE) can be used.
  • PTFE polytetrafluoroethylene
  • composition can be suitably used as an ink for forming a film containing a p-type semiconductor, an n-type semiconductor, and a surfactant by a coating method.
  • ink means a liquid substance used in a coating method, and is not limited to a colored liquid.
  • coating method includes a method of forming a film (layer) using a liquid material. Examples of coating methods include slot die coating, slit coating, knife coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, and spray coating. method, screen printing method, gravure printing method, flexographic printing method, offset printing method, inkjet coating method, dispenser printing method, nozzle coating method, and capillary coating method.
  • a film according to an embodiment of the present invention includes a p-type semiconductor, an n-type semiconductor, and a surfactant.
  • the film can be suitably used as an active layer included in a photoelectric conversion element.
  • the examples and preferred examples of the p-type semiconductor, n-type semiconductor, and surfactant contained in the film are the examples and preferred examples of the p-type semiconductor, n-type semiconductor, and surfactant that may be contained in the composition, respectively. The same is true.
  • the content of the p-type semiconductor in the film of this embodiment can be set to any suitable content depending on desired characteristics and the like.
  • the content of the p-type semiconductor in the film is preferably 1% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and preferably 99% by mass or less, more preferably 90% by mass.
  • the content is preferably 80% by mass or less.
  • the content of the n-type semiconductor in the film of this embodiment can be set to any suitable content depending on desired characteristics and the like.
  • the content of the n-type semiconductor in the film is preferably 1% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and preferably 99% by mass or less, more preferably 90% by mass.
  • the content is preferably 80% by mass or less.
  • the mass ratio of the p-type semiconductor to the n-type semiconductor is usually the mass ratio of the p-type semiconductor to the n-type semiconductor in the composition for manufacturing the film. It's the same.
  • the content ratio of the surfactant in the film of this embodiment is preferably 0.1% by mass or more, more preferably 1% by mass, with the total mass of the n-type semiconductor, p-type semiconductor, and surfactant being 100% by mass. % or more, preferably 10% by mass or less, more preferably 5% by mass or less.
  • the membrane of this embodiment does not substantially contain a solvent.
  • the content of the solvent in the membrane of this embodiment is preferably 1% by mass or less, more preferably 0.1% by mass or less, and usually 0% by mass or more, and may be 0% by mass.
  • the membrane of this embodiment can be manufactured by any method.
  • the film of this embodiment is manufactured by a manufacturing method including a step (i) of applying the composition to a coating object to obtain a coating film, and a step (ii) of removing the solvent from the obtained coating film. sell.
  • step (i) any of the conventionally known coating methods described above can be used to apply the composition to the object to be coated.
  • the composition is applied to an arbitrary application target.
  • the composition can be applied to, for example, a functional layer that may be included in the photoelectric conversion element, such as an electrode (anode or cathode), an electron transport layer, or a hole transport layer.
  • any suitable method can be used to remove the solvent from the coating film of the composition formed in step (i).
  • methods for removing the solvent include drying methods such as hot air drying, infrared heat drying, flash lamp annealing drying, and reduced pressure drying.
  • the photoelectric conversion element according to this embodiment includes a first electrode, a second electrode, and an active layer provided between the first electrode and the second electrode, and the active layer is as described above. It is a membrane.
  • a configuration example of the photoelectric conversion element of this embodiment will be specifically described with reference to the drawings.
  • FIG. 1 is a diagram schematically showing a configuration example of a photoelectric conversion element.
  • the photoelectric conversion element 10 is provided on a support substrate 11.
  • the photoelectric conversion element 10 includes a first electrode 12 provided in contact with a support substrate 11, a first intermediate layer 13 provided in contact with the first electrode 12, and a first intermediate layer. 13, a second intermediate layer 15 provided in contact with the active layer 14, and a second intermediate layer 15 provided in contact with the second intermediate layer 15. and an electrode 16.
  • a sealing member 17 is further provided in contact with the second electrode 16.
  • both the first intermediate layer 13 and the second intermediate layer 15 are provided, but only one of the first intermediate layer 13 and the second intermediate layer 15 is provided. It's okay.
  • the first intermediate layer 13 may not be provided.
  • the second intermediate layer 15 may not be provided.
  • a photoelectric conversion element is usually formed on a substrate (supporting substrate).
  • the device is further sealed with a substrate (sealing substrate).
  • One of a pair of electrodes consisting of a first electrode and a second electrode is usually formed on the substrate.
  • the material of the substrate is not particularly limited as long as it is a material that does not chemically change when forming a layer containing an organic compound.
  • the material for the substrate examples include glass, plastic, polymer film, and silicon.
  • the electrode on the opposite side of the electrode provided on the opaque substrate in other words, the electrode on the side far from the opaque substrate
  • the photoelectric conversion element includes a pair of electrodes, a first electrode and a second electrode. At least one of the first electrode and the second electrode is preferably a transparent or semitransparent electrode in order to allow light to enter.
  • transparent or translucent electrode materials include conductive metal oxide films and translucent metal thin films. Specifically, indium oxide, zinc oxide, tin oxide, indium tin oxide (ITO) which is a composite thereof, indium zinc oxide (IZO), conductive materials such as NESA, gold, platinum, silver, Copper is an example. As the transparent or translucent electrode material, ITO, IZO, and tin oxide are preferable. Further, as the electrode, a transparent conductive film using an organic compound such as polyaniline and its derivatives, polythiophene and its derivatives as a material may be used. The transparent or translucent electrode may be the first electrode or the second electrode.
  • the other electrode may be an electrode with low light transmittance.
  • electrode materials with low optical transparency include metals and conductive polymers. Specific examples of electrode materials with low optical transparency include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, Metals such as terbium and ytterbium, alloys of two or more of these, or one or more of these metals and gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin Examples include alloys with one or more metals selected from the group consisting of, graphite, graphite intercalation compounds, polyaniline and its derivatives, polythiophene and its derivatives.
  • Examples of the alloy 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.
  • the photoelectric conversion element of this embodiment includes the above-described film as an active layer.
  • the active layer of this embodiment has a bulk heterojunction type structure.
  • the thickness of the active layer is not particularly limited.
  • the thickness of the active layer can be set to any suitable thickness, taking into consideration, for example, the balance between suppression of dark current and extraction of generated photocurrent.
  • the thickness of the active layer is preferably 100 nm or more, more preferably 150 nm or more, and still more preferably 200 nm or more, especially from the viewpoint of further reducing dark current. Further, the thickness of the active layer is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and still more preferably 1 ⁇ m or less.
  • the photoelectric conversion element of this embodiment includes, for example, charge transport layers (electron transport layer, hole transport layer, electron injection layer, It is preferable to include an intermediate layer (buffer layer) such as a hole injection layer).
  • Examples of materials used for the intermediate layer include metals such as calcium, inorganic oxide semiconductors such as molybdenum oxide and zinc oxide, and PEDOT (poly(3,4-ethylenedioxythiophene)) and PSS (poly( 4-styrene sulfonate)) (PEDOT:PSS).
  • metals such as calcium, inorganic oxide semiconductors such as molybdenum oxide and zinc oxide, and PEDOT (poly(3,4-ethylenedioxythiophene)) and PSS (poly( 4-styrene sulfonate)) (PEDOT:PSS).
  • the intermediate layer can be formed by any conventionally known suitable forming method.
  • the intermediate layer can be formed by a vacuum deposition method or a coating method similar to the method for forming the active layer.
  • the photoelectric conversion element of this embodiment preferably includes an electron transport layer as a first intermediate layer between the first electrode and the active layer.
  • the photoelectric conversion element of this embodiment may or may not include a hole transport layer as a second intermediate layer between the second electrode and the active layer.
  • the photoelectric conversion element preferably includes an electron transport layer as a second intermediate layer between the second electrode and the active layer.
  • the photoelectric conversion element may or may not include a hole transport layer as a first intermediate layer between the first electrode and the active layer.
  • the electron transport layer has the function of transporting electrons from the active layer to the electrode.
  • the hole transport layer has the function of transporting holes from the active layer to the electrode.
  • An electron transport layer provided in contact with an electrode is sometimes referred to as an electron injection layer.
  • the electron transport layer (electron injection layer) provided in contact with the electrode has a function of promoting injection of electrons into the electrode.
  • the electron transport layer (electron injection layer) may be in contact with the active layer.
  • the electron transport layer contains an electron transport material.
  • electron-transporting materials include polyalkyleneimine and its derivatives, polymer compounds containing a fluorene structure, metals such as calcium, and metal oxides.
  • polyalkyleneimines and derivatives thereof include alkyleneimines having 2 to 8 carbon atoms, especially those having 2 to 8 carbon atoms, such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, octyleneimine.
  • alkyleneimines having 2 to 8 carbon atoms such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, octyleneimine.
  • examples include polymers obtained by polymerizing one or more of 2 to 4 alkylene imines by a conventional method, and polymers chemically modified by reacting them with various compounds.
  • polyethyleneimine (PEI) and ethoxylated polyethyleneimine (PEIE) are preferred.
  • polymer compound containing a fluorene structure is poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-ortho-2,7-(9 , 9'-dioctylfluorene)] (PFN) and PFN-P2.
  • metal oxides examples include zinc oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, titanium oxide, and niobium oxide.
  • metal oxides containing zinc are preferred, and zinc oxide is particularly preferred.
  • Examples of other electron-transporting materials include poly(4-vinylphenol) and perylene diimide.
  • a hole transport layer provided in contact with an electrode is sometimes referred to as a hole injection layer.
  • the hole transport layer (hole injection layer) provided in contact with the electrode has a function of promoting injection of holes generated in the active layer into the electrode.
  • the hole transport layer contains a hole transport material.
  • hole-transporting materials include polythiophene and its derivatives, aromatic amine compounds, polymer compounds containing structural units having aromatic amine residues, CuSCN, CuI, NiO, tungsten oxide (WO 3 ), and molybdenum oxide. (MoO 3 ).
  • the photoelectric conversion element of this embodiment further includes a sealing member, and is a sealed body sealed with the sealing member.
  • a sealing member Any suitable conventionally known member can be used as the sealing member.
  • An example of the sealing member is a combination of a glass substrate as a substrate (sealing substrate) and a sealing material (adhesive) such as a UV curable resin.
  • the sealing member may be a sealing layer having a layer structure of one or more layers.
  • layers constituting the sealing layer include a gas barrier layer and a gas barrier film.
  • the sealing layer is preferably formed of a material that has a property of blocking moisture (water vapor barrier property) or a property of blocking oxygen (oxygen barrier property).
  • materials suitable for the sealing layer include trifluoropolyethylene, polytrifluorochloride ethylene (PCTFE), polyimide, polycarbonate, polyethylene terephthalate, alicyclic polyolefin, and ethylene-vinyl alcohol copolymer.
  • examples include organic materials, and inorganic materials such as silicon oxide, silicon nitride, aluminum oxide, and diamond-like carbon.
  • the sealing member is usually made of a material that can withstand heat treatment that can be performed when the photoelectric conversion element is applied, for example, when it is incorporated into a device of an application example described below.
  • both or either of the first intermediate layer 13 and the second intermediate layer 15 may not be provided.
  • the photoelectric conversion element of this embodiment can be manufactured by any conventionally known suitable manufacturing method.
  • the photoelectric conversion element of this embodiment can be manufactured by combining suitable processes for the materials selected for forming the constituent elements.
  • a support substrate provided with a first electrode is prepared.
  • a substrate provided with a conductive thin film made of the electrode material already described from the market and patterning the conductive thin film as necessary to form the first electrode A support substrate provided with a first electrode can be provided.
  • the method for forming the first electrode when forming the first electrode on the support substrate is not particularly limited.
  • the first electrode is formed by using the previously described material by any conventionally known suitable method such as vacuum evaporation, sputtering, ion plating, plating, or coating. for example, a supporting substrate, an active layer, a hole transport layer).
  • the method for manufacturing a photoelectric conversion element may include a step of forming a hole transport layer (hole injection layer) provided between the active layer and the first electrode.
  • the method for forming the hole transport layer is not particularly limited. From the viewpoint of simplifying the step of forming the hole transport layer, it is preferable to form the hole transport layer by any suitable coating method known in the art.
  • the hole transport layer can be formed, for example, by a coating method using a coating liquid containing a material capable of forming the hole transport layer and a solvent as described above, or a vacuum evaporation method.
  • an active layer is formed on the hole transport layer.
  • the active layer can be formed by any suitable conventional formation process.
  • the active layer can be manufactured by the coating method using the composition described above.
  • the active layer can be formed in the same manner as the "film” described above.
  • the active layer can be formed by a process including a drying process.
  • the method for manufacturing a photoelectric conversion element of this embodiment may include a step of forming an electron transport layer (electron injection layer) provided in contact with the active layer.
  • the method for forming the electron transport layer is not particularly limited. From the viewpoint of simplifying the step of forming the electron transport layer, it is preferable to form the electron transport layer by any conventionally known suitable vacuum deposition method.
  • the method of forming the second electrode is not particularly limited.
  • the second electrode can be formed, for example, using the above-mentioned electrode material by any conventionally known suitable method such as a coating method, a vacuum evaporation method, a sputtering method, an ion plating method, or a plating method. Through the above steps, the photoelectric conversion element of this embodiment is manufactured.
  • any conventionally known suitable sealing material (adhesive) and substrate (sealing substrate) are used. Specifically, a sealing material such as a UV curable resin is applied onto the supporting substrate so as to surround the periphery of the manufactured photoelectric conversion element, and then the selected material is bonded together without any gaps using the sealing material.
  • a sealed body of the photoelectric conversion element can be obtained by sealing the photoelectric conversion element in the gap between the supporting substrate and the sealing substrate using a method such as UV light irradiation that is suitable for the sealed sealing material. can.
  • Photoelectric conversion elements Applications of the photoelectric conversion element of this embodiment include photodetection elements and solar cells.
  • the photoelectric conversion element of this embodiment can generate photovoltaic force between electrodes when irradiated with light, and can be operated as a solar cell.
  • a solar cell module can also be formed by integrating a plurality of photoelectric conversion elements.
  • the photoelectric conversion element of this embodiment can cause a photocurrent to flow by irradiating light from the transparent or semitransparent electrode side with a voltage (reverse bias voltage) applied between the electrodes, and the photodetection element (optical sensor). Furthermore, by integrating a plurality of photodetecting elements, it can also be used as an image sensor.
  • the photoelectric conversion element of this embodiment can be particularly suitably used as a photodetection element.
  • the photoelectric conversion element according to this embodiment is suitably applied as a photodetection element to detection units included in various electronic devices such as workstations, personal computers, personal digital assistants, room access control systems, digital cameras, and medical equipment. can do.
  • the photoelectric conversion element of this embodiment includes, for example, an image detection unit (for example, an image sensor such as an X-ray sensor) for a solid-state imaging device such as an X-ray imaging device and a CMOS image sensor, and a fingerprint A detection unit of a biometric information authentication device that detects a predetermined characteristic of a part of a living body, such as a detection unit, a face detection unit, a vein detection unit, and an iris detection unit (for example, a near-infrared sensor), and an optical biosensor such as a pulse oximeter. It can be suitably applied to a detection unit and the like.
  • an image detection unit for example, an image sensor such as an X-ray sensor
  • a solid-state imaging device such as an X-ray imaging device and a CMOS image sensor
  • a fingerprint A detection unit of a biometric information authentication device that detects a predetermined characteristic of a part of a living body, such as a detection unit, a face detection unit,
  • the photoelectric conversion element of this embodiment can also be suitably applied as an image detection unit for a solid-state imaging device, and further to a time-of-flight (TOF) type distance measuring device (TOF type distance measuring device).
  • TOF time-of-flight
  • a TOF distance measuring device measures distance by having a photoelectric conversion element receive reflected light emitted from a light source and reflected by an object to be measured. Specifically, the distance to the measurement target is determined by detecting the flight time of the irradiation light emitted from the light source until it is reflected by the measurement target and returns as reflected light.
  • the TOF type includes a direct TOF method and an indirect TOF method. In the direct TOF method, the difference between the time when the light is irradiated from the light source and the time when the reflected light is received by the photoelectric conversion element is directly measured, and the indirect TOF method converts the change in the amount of charge accumulation depending on the flight time into a time change. This is how you measure distance.
  • the distance measurement principle used in the indirect TOF method which obtains the flight time by charge accumulation, is a continuous wave (especially sine wave) modulation method that calculates the flight time from the phase of the emitted light from the light source and the reflected light reflected by the measurement target. and a pulse modulation method, and the photoelectric conversion element of this embodiment can be applied to a measuring device using any of these methods.
  • the photoelectric conversion element of this embodiment can have a photodetection function that can convert irradiated light into an electrical signal according to the amount of received light and output it to an external circuit via the electrode. Therefore, the photoelectric conversion element according to the embodiment of the present invention can be particularly suitably applied as a photodetection element having a photodetection function.
  • the photodetection element of this embodiment may be a photoelectric conversion element itself, or may further include a functional element for voltage control in addition to the photoelectric conversion element.
  • p-type semiconductor material P-1 a polymer compound synthesized with reference to the method described in International Publication No. 2013/051676 was used.
  • p-type semiconductor material P-2 a polymer compound synthesized with reference to the method described in International Publication No. 2011/052709 was used.
  • p-type semiconductor material P-3 a polymer compound manufactured by 1-Material, trade name: PM6 was used.
  • p-type semiconductor material P-4 a polymer compound manufactured by 1-Material Co., Ltd., trade name: PCE10 was used.
  • n-type semiconductor As the n-type semiconductor material N-1, Guard Surf NC-1010 manufactured by Harbes Co., Ltd. was used. As the n-type semiconductor material N-2, product name: E100 manufactured by Frontier Carbon Co., Ltd. was used. As the n-type semiconductor material N-3, product name: Y6 manufactured by 1-Material was used.
  • the surfactants used in the examples are as follows.
  • “F-556” Manufactured by DIC, nonionic, fluorine-based surfactant having a poly(meth)acrylate structure.
  • “R-40” Manufactured by DIC, nonionic, fluorine-based surfactant having a poly(meth)acrylate structure.
  • “KP-620” Manufactured by Shin-Etsu Chemical Co., Ltd., a nonionic surfactant having an organopolysiloxane structure.
  • “KP-323” Manufactured by Shin-Etsu Chemical Co., Ltd., a nonionic surfactant having an organopolysiloxane structure.
  • the viscosity ⁇ of the surfactant was measured by the following method and conditions.
  • the viscosity ⁇ was measured at a temperature of 25° C. and a shear rate of 100 (S ⁇ 1 ) using a modular compact rheometer MCR302 manufactured by Anton Paar.
  • the Mp (peak molecular weight) of the surfactant was measured by the following method and conditions. O-dichlorobenzene was used as the mobile phase for GPC at a flow rate of 1.0 mL/min. As the column, Shodex KD-806M manufactured by Showa Denko K.K. was used, and as the guard column, Shodex KD-G manufactured by Showa Denko K.K. was used.
  • a UV-vis detector manufactured by Shimadzu Corporation, SPD-M20A
  • a differential refractive index detector manufactured by Shimadzu Corporation, RID-10A
  • the compound (polymer) to be measured was mixed in 1-chloronaphthalene, a solvent, to a concentration of 0.05% by mass, and stirred at 80°C for 2 hours to create a solution. .
  • the peak molecular weight (Mp) was measured by injecting 10 ⁇ L of the obtained solution into the above-mentioned measuring device (GPC) as a sample.
  • Example 1 An ink solvent was prepared by mixing pseudocumene, tetralin, and butyl benzoate at mass ratios of 87%, 10%, and 3%, respectively.
  • a surfactant "F-556" manufactured by DIC was used. The ink solvent and the surfactant were mixed at a mass ratio of 99.9%:0.1% to obtain a mixture (a).
  • a mixture (b) was obtained by mixing a material P-1 as a p-type semiconductor and a material N-1 as an n-type semiconductor with respect to the mixture (a). The amount of the p-type semiconductor mixed was 1.5% by mass based on the entire ink composition (mixture (b)).
  • the amount of the n-type semiconductor mixed was 1.5% by mass based on the total mass of the ink composition (mixture (b)).
  • the resulting mixture (b) was stirred at 60° C. for 6 hours, and then filtered through a filter to obtain ink composition I-1.
  • the content of the surfactant is 0.097% by mass.
  • Example 2 The ink solvent and the surfactant were mixed at a mass ratio of 99.0%:1.0% to obtain a mixture (a).
  • Ink composition I-2 was obtained in the same manner as in Example 1 except for the above matters.
  • the content of the surfactant is 0.97% by mass.
  • Example 3 As a surfactant, "KP-620" manufactured by Shin-Etsu Chemical Co., Ltd. was used. Ink composition I-3 was obtained in the same manner as in Example 1 except for the above matters.
  • Example 4 An ink solvent was prepared by mixing pseudocumene and 1,2-dimethoxybenzene at a mass ratio of 97% and 3%, respectively. Ink composition I-4 was obtained in the same manner as in Example 1 except for the above matters.
  • Example 5 Material P-2 was used as the p-type semiconductor, and material N-2 was used as the n-type semiconductor. As a surfactant, "R-40" manufactured by DIC was used. Ink composition I-5 was obtained in the same manner as in Example 1 except for the above matters.
  • Example 6 Material P-2 was used as the p-type semiconductor, and material N-2 was used as the n-type semiconductor. Ink composition I-6 was obtained in the same manner as in Example 1 except for the above matters.
  • Example 7 Material P-3 was used as the p-type semiconductor, and material N-2 was used as the n-type semiconductor. O-dichlorobenzene was used as the ink solvent. Ink composition I-7 was obtained in the same manner as in Example 1 except for the above matters.
  • Example 8 Material P-4 was used as the p-type semiconductor, and material N-2 was used as the n-type semiconductor. O-dichlorobenzene was used as the ink solvent. Ink composition I-8 was obtained in the same manner as in Example 1 except for the above matters.
  • Example 9 Material P-1 was used as the p-type semiconductor, and material N-2 was used as the n-type semiconductor. Ink composition I-9 was obtained in the same manner as in Example 1 except for the above matters.
  • Example 10 Material P-1 was used as the p-type semiconductor, and material N-3 was used as the n-type semiconductor. Ink composition I-10 was obtained in the same manner as in Example 1 except for the above matters.
  • Example 11 Material P-3 was used as the p-type semiconductor, and material N-3 was used as the n-type semiconductor. Ink composition I-11 was obtained in the same manner as in Example 1 except for the above matters.
  • a glass substrate (hereinafter simply referred to as glass substrate) on which an ITO film as a first electrode was formed to a thickness of 100 nm by sputtering was prepared. Next, the glass substrate was subjected to surface treatment using ozone ultraviolet (UV) treatment.
  • UV ozone ultraviolet
  • the ink composition was applied onto an ITO film on a glass substrate by a spin coating method to form a coating film.
  • the glass substrate on which the coating film was formed was placed on a hot plate, and the coating film was dried in the atmosphere at 70° C. for 2 minutes. Subsequently, the glass substrate on which the coating film was formed was placed on a hot plate, and the coating film was further dried at 100° C. for 10 minutes in a nitrogen gas atmosphere. As a result, an active layer was formed on the ITO film.
  • the thickness of the formed active layer was about 250 nm.
  • an Ag film serving as an electrode was formed to a thickness of about 80 nm on the electron transport layer using a resistance heating evaporation apparatus.
  • a photoelectric conversion element A photodetection element A in which a glass substrate, a first electrode, an active layer, an electron transport layer, and a second electrode were provided in this order was obtained.
  • the dried glass substrate was washed with water, and the washed glass substrate was placed on a hot plate and dried in the atmosphere at 100° C. for 10 minutes. As a result, an electron transport layer was formed on the ITO film serving as the first electrode.
  • the ink composition was applied onto the electron transport layer formed on the ITO film by a slot die coating method to form a coating film.
  • vacuum drying treatment pressure 10 Pa, 70° C.
  • the glass substrate on which the dried coating film was formed was placed on a hot plate and dried at 100° C. for 12 minutes to form an active layer.
  • the thickness of the formed active layer was about 530 nm.
  • a photoelectric conversion element B photodetection element B in which a glass substrate, a first electrode, an electron transport layer, an active layer, and a second electrode were provided in this order was obtained.
  • the relative dark current (Jd) values for evaluations 1 to 4 are relative values when the dark current for evaluation 1 is taken as 100.
  • the Jd relative values of evaluations 5 to 6 are relative values when the dark current of evaluation 5 is set to 100.
  • the Jd relative values of evaluations 7 to 9 are relative values when the dark current of evaluation 7 is set to 100.
  • the Jd relative values of evaluations 10 to 11, evaluations 12 to 13, evaluations 14 to 15, evaluations 16 to 17, and evaluations 18 to 19 are the dark currents of evaluations 10, 12, 14, 16, and 18, respectively. This is the relative value when .
  • “Element A” represents photoelectric conversion element A manufactured by manufacturing method A
  • “Element B” represents photoelectric conversion element B manufactured by manufacturing method B.
  • a photoelectric conversion element with an active layer manufactured from a composition containing a surfactant has a higher dark It can be seen that the current decreases. Further, it can be seen that a photoelectric conversion element including an active layer manufactured from a composition containing a surfactant has a reduced dark current regardless of the structure of photoelectric conversion element A or photoelectric conversion element B.
  • Photoelectric conversion element 11 Support substrate 12 First electrode 13 First intermediate layer 14 Active layer 15 Second intermediate layer 16 Second electrode 17 Sealing member

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Abstract

The present invention addresses the problem of providing a composition capable of producing an active layer of a photoelectric conversion element exhibiting a reduced dark current.　The present invention pertains to a composition containing a p-type semiconductor, an n-type semiconductor, a surfactant, and a solvent. The present invention pertains to a film containing a p-type semiconductor, an n-type semiconductor, and a surfactant. The present invention pertains to an organic photoelectric conversion element comprising a first electrode, said film, and a second electrode in this order. The present invention pertains to a photodetection element comprising said organic photoelectric conversion element.

Description

組成物、膜、有機光電変換素子、及び光検出素子Composition, film, organic photoelectric conversion element, and photodetection element
　本発明は、組成物、膜、有機光電変換素子、及び光検出素子に関する。 The present invention relates to a composition, a film, an organic photoelectric conversion element, and a photodetection element.
　近年、活性層に有機化合物を含む有機光電変換素子が注目されている。かかる有機光電変換素子を含む光検出素子の特性を向上させる試みも行われている（非特許文献１参照）。 In recent years, organic photoelectric conversion elements containing organic compounds in their active layers have attracted attention. Attempts have also been made to improve the characteristics of photodetecting elements including such organic photoelectric conversion elements (see Non-Patent Document 1).
　光検出素子に含まれる光電変換素子は、暗状態で流れる電流（暗電流）が、小さいことが好ましい。したがって、暗電流が低減された光電変換素子の活性層を製造しうる、組成物；暗電流が低減された光電変換素子の活性層として機能しうる膜；かかる膜を含む、有機光電変換素子；かかる有機光電変換素子を含む、暗電流が低減された光検出素子；が求められる。 The photoelectric conversion element included in the photodetection element preferably has a small current flowing in a dark state (dark current). Therefore, a composition that can produce an active layer of a photoelectric conversion element with reduced dark current; a film that can function as an active layer of a photoelectric conversion element with reduced dark current; an organic photoelectric conversion element containing such a film; There is a need for a photodetection element with reduced dark current, including such an organic photoelectric conversion element.
　本発明者らは、前記課題を解決すべく鋭意研究を進めたところ、本発明を完成するに至った。
　本発明は、以下を提供する。 The present inventors conducted intensive research to solve the above problems, and as a result, completed the present invention.
The present invention provides the following.
　［１］　ｐ型半導体、ｎ型半導体、界面活性剤、及び溶媒を含む、組成物。
　［２］　前記ｐ型半導体が、ドナー・アクセプター構造を有する高分子化合物である、［１］に記載の組成物。
　［３］　前記ｐ型半導体が、下記式（Ｉ）で表される構成単位及び下記式（ＩＩ）で表される構成単位からなる群より選択される一種以上の構成単位を含む高分子化合物である、［１］又は［２］に記載の組成物。
Figure JPOXMLDOC01-appb-C000004
 　（式（Ｉ）中、
　Ａｒ１及びＡｒ２は、それぞれ独立して、置換基を有していてもよい３価の芳香族複素環基を表し、
　Ｚは下記式（Ｚ－１）～式（Ｚ－７）のいずれか１つで表される基を表す。
Figure JPOXMLDOC01-appb-C000005
 　（式（Ｚ－１）～（Ｚ－７）中、Ｒは、
　水素原子、
　ハロゲン原子、
　置換基を有していてもよいアルキル基、
　置換基を有していてもよいシクロアルキル基、
　置換基を有していてもよいアルケニル基、
　置換基を有していてもよいシクロアルケニル基、
　置換基を有していてもよいアルキニル基、
　置換基を有していてもよいシクロアルキニル基、
　置換基を有していてもよいアリール基、
　置換基を有していてもよいアルキルオキシ基、
　置換基を有していてもよいシクロアルキルオキシ基、
　置換基を有していてもよいアリールオキシ基、
　置換基を有していてもよいアルキルチオ基、
　置換基を有していてもよいシクロアルキルチオ基、
　置換基を有していてもよいアリールチオ基、
　置換基を有していてもよい１価の複素環基、
　置換基を有していてもよい置換アミノ基、
　置換基を有していてもよいイミン残基、
　置換基を有していてもよいアミド基、
　置換基を有していてもよい酸イミド基、
　置換基を有していてもよい置換オキシカルボニル基、
　シアノ基、
　ニトロ基、
　－Ｃ（＝Ｏ）－Ｒｃで表される基、又は
　－ＳＯ２－Ｒｄで表される基を表し、
　Ｒｃ及びＲｄは、それぞれ独立して、
　水素原子、
　置換基を有していてもよいアルキル基、
　置換基を有していてもよいシクロアルキル基、
　置換基を有していてもよいアリール基、
　置換基を有していてもよいアルキルオキシ基、
　置換基を有していてもよいシクロアルキルオキシ基、
　置換基を有していてもよいアリールオキシ基、又は
　置換基を有していてもよい１価の複素環基を表す。
　式（Ｚ－１）～式（Ｚ－７）中、Ｒが２つある場合、２つあるＲは同一であっても異なっていてもよい。））
Figure JPOXMLDOC01-appb-C000006
 　（式（ＩＩ）中、Ａｒ３は２価の芳香族複素環基を表す。）
　［４］　前記ｎ型半導体が、フラーレン誘導体である、［１］～［３］のいずれか一項に記載の組成物。
　［５］　前記ｎ型半導体が、非フラーレン化合物である、［１］～［３］のいずれか一項に記載の組成物。
　［６］　前記溶媒が、芳香族炭化水素溶媒を含む、［１］～［５］のいずれか一項に記載の組成物。
　［７］　前記界面活性剤が、ノニオン性界面活性剤である、［１］～［６］のいずれか一項に記載の組成物。
　［８］　前記界面活性剤が、ポリ（メタ）アクリレート構造を有する化合物である、［１］～［７］のいずれか一項に記載の組成物。
　［９］　前記界面活性剤が、オルガノポリシロキサン構造を有する化合物である、［１］～［８］のいずれか一項に記載の組成物。
　［１０］　前記界面活性剤が、フッ素系界面活性剤である、［１］～［９］のいずれか一項に記載の組成物。
　［１１］　ｐ型半導体、ｎ型半導体、及び界面活性剤を含む膜。
　［１２］　第１の電極と、［１１］に記載の膜と、第２の電極とをこの順で含む、有機光電変換素子。
　［１３］　［１２］に記載の有機光電変換素子を含む、光検出素子。 [1] A composition containing a p-type semiconductor, an n-type semiconductor, a surfactant, and a solvent.
[2] The composition according to [1], wherein the p-type semiconductor is a polymer compound having a donor-acceptor structure.
[3] The p-type semiconductor is a polymer compound containing one or more structural units selected from the group consisting of a structural unit represented by the following formula (I) and a structural unit represented by the following formula (II). The composition according to [1] or [2].
Figure JPOXMLDOC01-appb-C000004
 (In formula (I),
Ar 1 and Ar 2 each independently represent a trivalent aromatic heterocyclic group which may have a substituent,
Z represents a group represented by any one of the following formulas (Z-1) to (Z-7).
Figure JPOXMLDOC01-appb-C000005
 (In formulas (Z-1) to (Z-7), R is
hydrogen atom,
halogen atom,
an alkyl group that may have a substituent,
cycloalkyl group which may have a substituent,
Alkenyl group which may have a substituent,
Cycloalkenyl group which may have a substituent,
an alkynyl group which may have a substituent,
cycloalkynyl group which may have a substituent,
an aryl group which may have a substituent,
an alkyloxy group which may have a substituent,
cycloalkyloxy group which may have a substituent,
an aryloxy group which may have a substituent,
an alkylthio group which may have a substituent,
cycloalkylthio group which may have a substituent,
Arylthio group which may have a substituent,
a monovalent heterocyclic group which may have a substituent,
a substituted amino group which may have a substituent,
imine residue which may have a substituent,
An amide group which may have a substituent,
acid imide group which may have a substituent,
a substituted oxycarbonyl group which may have a substituent,
cyano group,
nitro group,
-C(=O)-R represents a group represented by c , or -SO 2 represents a group represented by R d ,
R c and R d are each independently,
hydrogen atom,
an alkyl group that may have a substituent,
cycloalkyl group which may have a substituent,
an aryl group which may have a substituent,
an alkyloxy group which may have a substituent,
cycloalkyloxy group which may have a substituent,
Represents an aryloxy group which may have a substituent or a monovalent heterocyclic group which may have a substituent.
In formulas (Z-1) to (Z-7), when there are two R's, the two R's may be the same or different. ))
Figure JPOXMLDOC01-appb-C000006
 (In formula (II), Ar 3 represents a divalent aromatic heterocyclic group.)
[4] The composition according to any one of [1] to [3], wherein the n-type semiconductor is a fullerene derivative.
[5] The composition according to any one of [1] to [3], wherein the n-type semiconductor is a non-fullerene compound.
[6] The composition according to any one of [1] to [5], wherein the solvent contains an aromatic hydrocarbon solvent.
[7] The composition according to any one of [1] to [6], wherein the surfactant is a nonionic surfactant.
[8] The composition according to any one of [1] to [7], wherein the surfactant is a compound having a poly(meth)acrylate structure.
[9] The composition according to any one of [1] to [8], wherein the surfactant is a compound having an organopolysiloxane structure.
[10] The composition according to any one of [1] to [9], wherein the surfactant is a fluorosurfactant.
[11] A film containing a p-type semiconductor, an n-type semiconductor, and a surfactant.
[12] An organic photoelectric conversion element comprising a first electrode, the film according to [11], and a second electrode in this order.
[13] A photodetection element comprising the organic photoelectric conversion element according to [12].
　本発明によれば、暗電流が低減された光電変換素子の活性層を製造しうる、組成物；暗電流が低減された光電変換素子の活性層として機能しうる膜；かかる膜を含む、有機光電変換素子；かかる有機光電変換素子を含む、暗電流が低減された光検出素子；が提供されうる。 According to the present invention, a composition that can produce an active layer of a photoelectric conversion element with reduced dark current; a film that can function as an active layer of a photoelectric conversion element with reduced dark current; A photoelectric conversion element; a photodetection element with reduced dark current that includes such an organic photoelectric conversion element; can be provided.
図１は、光電変換素子の構成例を模式的に示す図である。FIG. 1 is a diagram schematically showing a configuration example of a photoelectric conversion element.
　以下、図面を参照して、本発明の実施形態について説明する。なお、図面は、発明が理解できる程度に、構成要素の形状、大きさ及び配置が概略的に示されているに過ぎない。本発明は以下の記述によって限定されるものではなく、各構成要素は本発明の要旨を逸脱しない範囲において適宜変更可能である。以下の説明に用いる図面において、同様の構成要素については同一の符号を付して示し、重複する説明については省略する場合がある。また、本発明の実施形態にかかる構成は、必ずしも図示例の配置で使用されるとは限らない。以下に示す実施形態の構成要素は、適宜組み合わせうる。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. Note that the drawings merely show the shapes, sizes, and arrangements of the components schematically to the extent that the invention can be understood. The present invention is not limited to the following description, and each component can be modified as appropriate without departing from the gist of the present invention. In the drawings used in the following description, similar components are designated by the same reference numerals, and overlapping descriptions may be omitted. Further, the configuration according to the embodiment of the present invention is not necessarily used in the arrangement shown in the illustrated example. The components of the embodiments shown below can be combined as appropriate.
［１．共通する用語の説明］
　本明細書において、「高分子化合物」とは、分子量分布を有し、ポリスチレン換算の数平均分子量が、１×１０３以上１×１０８以下である重合体を意味する。高分子化合物に含まれる構成単位は、合計１００モル％である。 [1. Explanation of common terms]
As used herein, the term "polymer compound" refers to a polymer having a molecular weight distribution and a number average molecular weight in terms of polystyrene of 1 x 103 or more and 1 x 108 or less. The total amount of structural units contained in the polymer compound is 100 mol%.
　本明細書において、「構成単位」とは、高分子化合物中に１個以上存在する単位を意味する。「単量体単位」とは、当該単量体（モノマー）を重合することにより得られうる構造を有する単位を意味する。「単量体単位」は、その製造方法により限定されない。 As used herein, the term "structural unit" refers to one or more units present in a polymer compound. "Monomeric unit" means a unit having a structure that can be obtained by polymerizing the monomer. A "monomeric unit" is not limited by its manufacturing method.
　本明細書において、「水素原子」は、軽水素原子であっても、重水素原子であってもよい。 In this specification, a "hydrogen atom" may be a light hydrogen atom or a deuterium atom.
　本明細書において、「ハロゲン原子」の例としては、フッ素原子、塩素原子、臭素原子、及びヨウ素原子が挙げられる。 In this specification, examples of "halogen atom" include fluorine atom, chlorine atom, bromine atom, and iodine atom.
　「置換基を有していてもよい」態様には、化合物又は基を構成するすべての水素原子が無置換の場合、及び１個以上の水素原子の一部又は全部が置換基によって置換されている場合の両方の態様が含まれる。 Embodiments that "may have a substituent" include cases where all hydrogen atoms constituting the compound or group are unsubstituted, and cases where one or more hydrogen atoms are partially or entirely substituted with a substituent. Both aspects are included.
　置換基の例としては、ハロゲン原子、アルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アルキニル基、シクロアルキニル基、アルキルオキシ基、シクロアルキルオキシ基、アルキルチオ基、シクロアルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、１価の複素環基、ヒドロキシ基、カルボキシ基、置換アミノ基、アシル基、イミン残基、アミド基、酸イミド基、置換オキシカルボニル基、シアノ基、アルキルスルホニル基、及びニトロ基が挙げられる。 Examples of substituents include halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, cycloalkynyl groups, alkyloxy groups, cycloalkyloxy groups, alkylthio groups, cycloalkylthio groups, aryl groups, Aryloxy group, arylthio group, monovalent heterocyclic group, hydroxy group, carboxy group, substituted amino group, acyl group, imine residue, amide group, acid imide group, substituted oxycarbonyl group, cyano group, alkylsulfonyl group, and a nitro group.
　本明細書において、「アルキル基」は置換基を有していてもよい。「アルキル基」は、特に断らない限り、直鎖状及び分岐状のいずれであってもよい。直鎖状のアルキル基の炭素原子数は、置換基の炭素原子数を含めないで、通常１～５０であり、好ましくは１～３０であり、より好ましくは１～２０である。分岐状又は環状であるアルキル基の炭素原子数は、置換基の炭素原子数を含めないで、通常３～５０であり、好ましくは３～３０であり、より好ましくは４～２０である。 In this specification, the "alkyl group" may have a substituent. The "alkyl group" may be either linear or branched unless otherwise specified. The number of carbon atoms in the linear alkyl group, not including the number of carbon atoms in substituents, is usually 1 to 50, preferably 1 to 30, and more preferably 1 to 20. The number of carbon atoms in the branched or cyclic alkyl group, not including the number of carbon atoms in substituents, is usually 3 to 50, preferably 3 to 30, and more preferably 4 to 20.
　アルキル基の具体例としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソアミル基、２－エチルブチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、２－エチルヘキシル基、３－ｎ－プロピルヘプチル基、ｎ－デシル基、３，７－ジメチルオクチル基、２－エチルオクチル基、２－ｎ－ヘキシル－デシル基、ｎ－ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、エイコシル基等の非置換アルキル基；トリフルオロメチル基、ペンタフルオロエチル基、パーフルオロブチル基、パーフルオロヘキシル基、パーフルオロオクチル基、３－フェニルプロピル基、３－（４－メチルフェニル）プロピル基、３－（３，５－ジ－ｎ－ヘキシルフェニル）プロピル基、６－エチルオキシヘキシル基、シクロヘキシルメチル基、シクロヘキシルエチル基等の置換アルキル基が挙げられる。 Specific examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isoamyl group, 2-ethylbutyl group, n- Hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, 3-n-propylheptyl group, n-decyl group, 3,7-dimethyloctyl group, 2-ethyloctyl group, 2-n-hexyl group - Unsubstituted alkyl groups such as decyl group, n-dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group; trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group group, 3-phenylpropyl group, 3-(4-methylphenyl)propyl group, 3-(3,5-di-n-hexylphenyl)propyl group, 6-ethyloxyhexyl group, cyclohexylmethyl group, cyclohexylethyl group Substituted alkyl groups such as
　「シクロアルキル基」は、単環の基であってもよく、多環の基であってもよい。シクロアルキル基は、置換基を有していてもよい。シクロアルキル基の炭素原子数は、置換基の炭素原子数を含めないで、通常３～３０であり、好ましくは３～２０である。 The "cycloalkyl group" may be a monocyclic group or a polycyclic group. The cycloalkyl group may have a substituent. The number of carbon atoms in the cycloalkyl group, not including the number of carbon atoms in substituents, is usually 3 to 30, preferably 3 to 20.
　シクロアルキル基の例としては、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、アダマンチル基などの、置換基を有さないアルキル基、及びこれらの基における水素原子が、アルキル基、アルキルオキシ基、アリール基、フッ素原子などの置換基で置換された基が挙げられる。 Examples of cycloalkyl groups include alkyl groups without substituents such as cyclopentyl group, cyclohexyl group, cycloheptyl group, and adamantyl group, and hydrogen atoms in these groups include alkyl groups, alkyloxy groups, and aryl groups. , a group substituted with a substituent such as a fluorine atom.
　置換基を有するシクロアルキル基の具体例としては、メチルシクロヘキシル基、エチルシクロヘキシル基が挙げられる。 Specific examples of the cycloalkyl group having a substituent include a methylcyclohexyl group and an ethylcyclohexyl group.
　「アルケニル基」は、直鎖状でもあってもよく、分岐状であってもよい。アルケニル基は、置換基を有していてもよい。アルケニル基の炭素原子数は、置換基の炭素原子数を含めないで、通常２～３０であり、好ましくは２～２０である。 The "alkenyl group" may be linear or branched. The alkenyl group may have a substituent. The number of carbon atoms in the alkenyl group, not including the number of carbon atoms in substituents, is usually 2 to 30, preferably 2 to 20.
　アルケニル基の例としては、ビニル基、１－プロペニル基、２－プロペニル基、２－ブテニル基、３－ブテニル基、３－ペンテニル基、４－ペンテニル基、１－ヘキセニル基、５－ヘキセニル基、７－オクテニル基などの、置換基を有しないアルケニル基、及びこれらの基における水素原子が、アルキルオキシ基、アリール基、フッ素原子などの置換基で置換された基が挙げられる。 Examples of alkenyl groups include vinyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, 3-butenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 5-hexenyl group, Examples include alkenyl groups having no substituent, such as a 7-octenyl group, and groups in which a hydrogen atom in these groups is substituted with a substituent such as an alkyloxy group, an aryl group, or a fluorine atom.
　「シクロアルケニル基」は、単環の基であってもよく、多環の基であってもよい。シクロアルケニル基は、置換基を有していてもよい。シクロアルケニル基の炭素原子数は、置換基の炭素原子数を含めないで、通常３～３０であり、好ましくは３～２０である。 The "cycloalkenyl group" may be a monocyclic group or a polycyclic group. The cycloalkenyl group may have a substituent. The number of carbon atoms in the cycloalkenyl group, not including the number of carbon atoms in substituents, is usually 3 to 30, preferably 3 to 20.
　シクロアルケニル基の例としては、シクロヘキセニル基などの、置換基を有さないシクロアルケニル基、及びこれらの基における水素原子が、アルキル基、アルキルオキシ基、アリール基、フッ素原子などの置換基で置換された基が挙げられる。 Examples of cycloalkenyl groups include cycloalkenyl groups without substituents such as cyclohexenyl groups, and hydrogen atoms in these groups with substituents such as alkyl groups, alkyloxy groups, aryl groups, and fluorine atoms. Examples include substituted groups.
　置換基を有するシクロアルケニル基の例としては、メチルシクロヘキセニル基、及びエチルシクロヘキセニル基が挙げられる。 Examples of the cycloalkenyl group having a substituent include a methylcyclohexenyl group and an ethylcyclohexenyl group.
　「アルキニル基」は、直鎖状であってもよく、分岐状であってもよい。アルキニル基は、置換基を有していてもよい。アルキニル基の炭素原子数は、置換基の炭素原子数を含めないで、通常２～３０であり、好ましくは２～２０である。 The "alkynyl group" may be linear or branched. The alkynyl group may have a substituent. The number of carbon atoms in the alkynyl group, not including the number of carbon atoms in substituents, is usually 2 to 30, preferably 2 to 20.
　アルキニル基の例としては、エチニル基、１－プロピニル基、２－プロピニル基、２－ブチニル基、３－ブチニル基、３－ペンチニル基、４－ペンチニル基、１－ヘキシニル基、５－ヘキシニル基などの、置換基を有しないアルキニル基、及びこれらの基における水素原子が、アルキルオキシ基、アリール基、フッ素原子などの置換基で置換された基が挙げられる。 Examples of alkynyl groups include ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 3-pentynyl group, 4-pentynyl group, 1-hexynyl group, 5-hexynyl group, etc. Examples include an alkynyl group having no substituent, and a group in which a hydrogen atom in these groups is substituted with a substituent such as an alkyloxy group, an aryl group, or a fluorine atom.
　「シクロアルキニル基」は、単環の基であってもよく、多環の基であってもよい。シクロアルキニル基は、置換基を有していてもよい。シクロアルキニル基の炭素原子数は、置換基の炭素原子数を含めないで、通常４～３０であり、好ましくは４～２０である。 The "cycloalkynyl group" may be a monocyclic group or a polycyclic group. The cycloalkynyl group may have a substituent. The number of carbon atoms in the cycloalkynyl group, not including the number of carbon atoms in substituents, is usually 4 to 30, preferably 4 to 20.
　シクロアルキニル基の例としては、シクロヘキシニル基などの、置換基を有しないシクロアルキニル基、及びこれらの基における水素原子が、アルキル基、アルキルオキシ基、アリール基、フッ素原子などの置換基で置換された基が挙げられる。 Examples of cycloalkynyl groups include cycloalkynyl groups without substituents such as cyclohexynyl groups, and hydrogen atoms in these groups substituted with substituents such as alkyl groups, alkyloxy groups, aryl groups, and fluorine atoms. The following groups are mentioned.
　置換基を有するシクロアルキニル基の例としては、メチルシクロヘキシニル基、及びエチルシクロヘキシニル基が挙げられる。 Examples of the cycloalkynyl group having a substituent include a methylcyclohexynyl group and an ethylcyclohexynyl group.
　「アルキルオキシ基」は、直鎖状であってもよく、分岐状であってもよい。アルキルオキシ基は、置換基を有していてもよい。アルキルオキシ基の炭素原子数は、置換基の炭素原子数を含めないで、通常１～３０であり、好ましくは１～２０である。 The "alkyloxy group" may be linear or branched. The alkyloxy group may have a substituent. The number of carbon atoms in the alkyloxy group, not including the number of carbon atoms in substituents, is usually 1 to 30, preferably 1 to 20.
　アルキルオキシ基の例としては、メトキシ基、エトキシ基、ｎ－プロピルオキシ基、イソプロピルオキシ基、ｎ－ブチルオキシ基、イソブチルオキシ基、ｔｅｒｔ－ブチルオキシ基、ｎ－ペンチルオキシ基、ｎ－ヘキシルオキシ基、ｎ－ヘプチルオキシ基、ｎ－オクチルオキシ基、２－エチルヘキシルオキシ基、ｎ－ノニルオキシ基、ｎ－デシルオキシ基、３，７－ジメチルオクチルオキシ基、３－ヘプチルドデシルオキシ基、ラウリルオキシ基などの、置換基を有しないアルキルオキシ基、及びこれらの基における水素原子が、アルキルオキシ基、アリール基、フッ素原子等の置換基で置換された基が挙げられる。 Examples of alkyloxy groups include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, 3,7-dimethyloctyloxy group, 3-heptyldodecyloxy group, lauryloxy group, etc. Examples thereof include an alkyloxy group having no substituent, and a group in which a hydrogen atom in these groups is substituted with a substituent such as an alkyloxy group, an aryl group, or a fluorine atom.
　「シクロアルキルオキシ基」が有するシクロアルキル基は、単環の基であってもよく、多環の基であってもよい。シクロアルキルオキシ基は、置換基を有していてもよい。シクロアルキルオキシ基の炭素原子数は、置換基の炭素原子数を含めないで、通常３～３０であり、好ましくは３～２０である。 The cycloalkyl group possessed by the "cycloalkyloxy group" may be a monocyclic group or a polycyclic group. The cycloalkyloxy group may have a substituent. The number of carbon atoms in the cycloalkyloxy group, not including the number of carbon atoms in substituents, is usually 3 to 30, preferably 3 to 20.
　シクロアルキルオキシ基の例としては、シクロペンチルオキシ基、シクロヘキシルオキシ基、シクロヘプチルオキシ基などの、置換基を有しないシクロアルキルオキシ基、及びこれらの基における水素原子が、フッ素原子、アルキル基などの置換基で置換された基が挙げられる。 Examples of cycloalkyloxy groups include cycloalkyloxy groups without substituents such as cyclopentyloxy, cyclohexyloxy, and cycloheptyloxy groups, and hydrogen atoms in these groups such as fluorine atoms, alkyl groups, etc. Examples include groups substituted with substituents.
　「アルキルチオ基」は、直鎖状であってもよく、分岐状であってもよい。アルキルチオ基は、置換基を有していてもよい。アルキルチオ基の炭素原子数は、置換基の炭素原子数を含めないで、通常１～３０であり、好ましくは１～２０である。 The "alkylthio group" may be linear or branched. The alkylthio group may have a substituent. The number of carbon atoms in the alkylthio group, not including the number of carbon atoms in substituents, is usually 1 to 30, preferably 1 to 20.
　置換基を有していてもよいアルキルチオ基の例としては、メチルチオ基、エチルチオ基、ｎ－プロピルチオ基、イソプロピルチオ基、ｎ－ブチルチオ基、イソブチルチオ基、ｔｅｒｔ－ブチルチオ基、ｎ－ペンチルチオ基、ｎ－ヘキシルチオ基、ｎ－ヘプチルチオ基、ｎ－オクチルチオ基、２－エチルヘキシルチオ基、ｎ－ノニルチオ基、ｎ－デシルチオ基、３，７－ジメチルオクチルチオ基、３－ヘプチルドデシルチオ基、ラウリルチオ基、及びトリフルオロメチルチオ基が挙げられる。 Examples of alkylthio groups that may have substituents include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, tert-butylthio group, n-pentylthio group, n-hexylthio group, n-heptylthio group, n-octylthio group, 2-ethylhexylthio group, n-nonylthio group, n-decylthio group, 3,7-dimethyloctylthio group, 3-heptyldodecylthio group, laurylthio group, and trifluoromethylthio group.
　「シクロアルキルチオ基」が有するシクロアルキル基は、単環の基であってもよく、多環の基であってもよい。シクロアルキルチオ基は、置換基を有していてもよい。シクロアルキルチオ基の炭素原子数は、置換基の炭素原子数を含めないで、通常３～３０であり、好ましくは３～２０である。 The cycloalkyl group possessed by the "cycloalkylthio group" may be a monocyclic group or a polycyclic group. The cycloalkylthio group may have a substituent. The number of carbon atoms in the cycloalkylthio group, not including the number of carbon atoms in substituents, is usually 3 to 30, preferably 3 to 20.
　置換基を有していてもよいシクロアルキルチオ基の例としては、シクロヘキシルチオ基が挙げられる。 An example of the cycloalkylthio group which may have a substituent is a cyclohexylthio group.
　「ｐ価の芳香族炭素環基」とは、置換基を有していてもよい芳香族炭化水素から環を構成する炭素原子に直接結合する水素原子ｐ個を除いた残りの原子団を意味する。芳香族炭化水素には、縮合環を有する化合物、独立したベンゼン環及び縮合環からなる群から選ばれる２つ以上が、直接又はビニレン等の２価の基を介して結合した化合物も含まれる。ｐ価の芳香族炭素環基は、置換基をさらに有していてもよい。 "P-valent aromatic carbocyclic group" means an atomic group remaining after removing p hydrogen atoms directly bonded to carbon atoms constituting a ring from an aromatic hydrocarbon that may have a substituent. do. Aromatic hydrocarbons also include compounds having fused rings, compounds in which two or more selected from the group consisting of independent benzene rings and fused rings are bonded directly or via a divalent group such as vinylene. The p-valent aromatic carbocyclic group may further have a substituent.
　「アリール基」は、１価の芳香族炭素環基を意味する。アリール基は置換基を有していてもよい。アリール基の炭素原子数は、置換基の炭素原子数を含まないで、通常６～６０であり、好ましくは６～４８である。 "Aryl group" means a monovalent aromatic carbocyclic group. The aryl group may have a substituent. The number of carbon atoms in the aryl group, not including the number of carbon atoms in substituents, is usually 6 to 60, preferably 6 to 48.
　アリール基の例としては、フェニル基、１－ナフチル基、２－ナフチル基、１－アントラセニル基、２－アントラセニル基、９－アントラセニル基、１－ピレニル基、２－ピレニル基、４－ピレニル基、２－フルオレニル基、３－フルオレニル基、４－フルオレニル基、２－フェニルフェニル基、３－フェニルフェニル基、４－フェニルフェニル基などの、置換基を有しないアリール基、及びこれらの基における水素原子が、アルキル基、アルキルオキシ基、アリール基、フッ素原子などの置換基で置換された基が挙げられる。 Examples of the aryl group include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, Aryl groups without substituents, such as 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 2-phenylphenyl group, 3-phenylphenyl group, 4-phenylphenyl group, and hydrogen atoms in these groups However, examples thereof include groups substituted with substituents such as an alkyl group, an alkyloxy group, an aryl group, and a fluorine atom.
　「アリールオキシ基」は、置換基を有していてもよい。アリールオキシ基の炭素原子数は、置換基の炭素原子数を含めないで、通常６～６０であり、好ましくは６～４８である。 The "aryloxy group" may have a substituent. The number of carbon atoms in the aryloxy group, not including the number of carbon atoms in substituents, is usually 6 to 60, preferably 6 to 48.
　アリールオキシ基の例としては、フェノキシ基、１－ナフチルオキシ基、２－ナフチルオキシ基、１－アントラセニルオキシ基、９－アントラセニルオキシ基、１－ピレニルオキシ基などの置換基を有しないアリールオキシ基、及びこれらの基における水素原子が、アルキル基、アルキルオキシ基、フッ素原子などの置換基で置換された基が挙げられる。 Examples of aryloxy groups include phenoxy groups, 1-naphthyloxy groups, 2-naphthyloxy groups, 1-anthracenyloxy groups, 9-anthracenyloxy groups, and 1-pyrenyloxy groups that have no substituents. Examples include aryloxy groups and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyl groups, alkyloxy groups, and fluorine atoms.
　「アリールチオ基」は、置換基を有していてもよい。アリールチオ基の炭素原子数は、置換基の炭素原子数を含めないで、通常６～６０であり、好ましくは６～４８である。 The "arylthio group" may have a substituent. The number of carbon atoms in the arylthio group, not including the number of carbon atoms in substituents, is usually 6 to 60, preferably 6 to 48.
　置換基を有していてもよいアリールチオ基の例としては、フェニルチオ基、Ｃ１～Ｃ１２アルキルオキシフェニルチオ基、Ｃ１～Ｃ１２アルキルフェニルチオ基、１－ナフチルチオ基、２－ナフチルチオ基、及びペンタフルオロフェニルチオ基が挙げられる。「Ｃ１～Ｃ１２」は、その直後に記載された基の炭素原子数が１～１２であることを表す。さらに、「Ｃｍ～Ｃｎ」は、その直後に記載された基の炭素原子数がｍ～ｎであることを表す。以下同様である。 Examples of the arylthio group which may have a substituent include phenylthio group, C1-C12 alkyloxyphenylthio group, C1-C12 alkylphenylthio group, 1-naphthylthio group, 2-naphthylthio group, and pentafluorophenyl group. Examples include thio group. "C1-C12" represents that the group immediately following it has 1 to 12 carbon atoms. Furthermore, "Cm to Cn" indicates that the number of carbon atoms in the group immediately following it is m to n. The same applies below.
　「ｐ価の複素環基」（ｐは、１以上の整数を表す。）は、置換基を有していてもよい複素環式化合物から環を構成する炭素原子又はヘテロ原子に直接結合する水素原子のうちのｐ個の水素原子を除いた残りの原子団を意味する。「ｐ価の複素環基」には、「ｐ価の芳香族複素環基」が含まれる。「ｐ価の芳香族複素環基」は、置換基を有していてもよい芳香族複素環式化合物から、環を構成する炭素原子又はヘテロ原子に直接結合している水素原子のうちのｐ個の水素原子を除いた残りの原子団を意味する。 A "p-valent heterocyclic group" (p represents an integer of 1 or more) is a hydrogen bond directly bonded to a carbon atom or heteroatom constituting a ring of a heterocyclic compound that may have a substituent. It means the atomic group remaining after p hydrogen atoms are removed from the atoms. The "p-valent heterocyclic group" includes "p-valent aromatic heterocyclic group." "P-valent aromatic heterocyclic group" means p of the hydrogen atoms directly bonded to the carbon atoms or hetero atoms constituting the ring from an aromatic heterocyclic compound which may have a substituent. It means the remaining atomic group after removing hydrogen atoms.
　芳香族複素環式化合物には、複素環自体が芳香族性を示す化合物に加えて、複素環自体は芳香族性を示さなくとも、複素環に芳香環が縮環している化合物が包含される。 Aromatic heterocyclic compounds include compounds in which the heterocycle itself exhibits aromaticity, as well as compounds in which an aromatic ring is fused to the heterocycle, even if the heterocycle itself does not exhibit aromaticity. Ru.
　芳香族複素環式化合物のうち、複素環自体が芳香族性を示す化合物の具体例としては、オキサジアゾール、チアジアゾール、チアゾール、オキサゾール、チオフェン、ピロール、ホスホール、フラン、ピリジン、ピラジン、ピリミジン、トリアジン、ピリダジン、キノリン、イソキノリン、カルバゾール、及びジベンゾホスホールが挙げられる。 Among aromatic heterocyclic compounds, specific examples of compounds in which the heterocycle itself is aromatic include oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, and triazine. , pyridazine, quinoline, isoquinoline, carbazole, and dibenzophosphole.
　芳香族複素環式化合物のうち、複素環自体が芳香族性を示さず、複素環に芳香環が縮環している化合物の具体例としては、フェノキサジン、フェノチアジン、ジベンゾボロール、ジベンゾシロール、及びベンゾピランが挙げられる。 Among aromatic heterocyclic compounds, specific examples of compounds in which the heterocycle itself does not exhibit aromaticity and an aromatic ring is fused to the heterocycle include phenoxazine, phenothiazine, dibenzoborole, dibenzosilole, and benzopyran.
　ｐ価の複素環基は、置換基を有していてもよい。ｐ価の複素環基の炭素原子数は、置換基の炭素原子数を含めないで、通常２～６０であり、好ましくは２～２０である。 The p-valent heterocyclic group may have a substituent. The number of carbon atoms in the p-valent heterocyclic group, not including the number of carbon atoms in substituents, is usually 2 to 60, preferably 2 to 20.
　１価の複素環基の例としては、１価の芳香族複素環基（例、チエニル基、ピロリル基、フリル基、ピリジル基、キノリル基、イソキノリル基、ピリミジニル基、トリアジニル基）、１価の非芳香族複素環基（例、ピペリジル基、ピペラジル基）、及びこれらの基における水素原子が、アルキル基、アルキルオキシ基、フッ素原子などの置換基で置換された基が挙げられる。 Examples of monovalent heterocyclic groups include monovalent aromatic heterocyclic groups (e.g., thienyl group, pyrrolyl group, furyl group, pyridyl group, quinolyl group, isoquinolyl group, pyrimidinyl group, triazinyl group), Examples include non-aromatic heterocyclic groups (eg, piperidyl group, piperazyl group), and groups in which hydrogen atoms in these groups are substituted with substituents such as alkyl groups, alkyloxy groups, and fluorine atoms.
　「置換アミノ基」は、置換基を有するアミノ基を意味する。アミノ基が有する置換基としては、アルキル基、シクロアルキル基、アリール基、及び１価の複素環基が好ましい。置換アミノ基の炭素原子数は、置換基の炭素原子数を含めないで、通常２～３０である。 "Substituted amino group" means an amino group having a substituent. Preferred substituents for the amino group include an alkyl group, a cycloalkyl group, an aryl group, and a monovalent heterocyclic group. The number of carbon atoms in the substituted amino group is usually 2 to 30, not including the number of carbon atoms in the substituents.
　置換アミノ基の例としては、ジアルキルアミノ基（例、ジメチルアミノ基、ジエチルアミノ基）、ジアリールアミノ基（例、ジフェニルアミノ基、ビス（４－メチルフェニル）アミノ基、ビス（４－ｔｅｒｔ－ブチルフェニル）アミノ基、ビス（３，５－ジ－ｔｅｒｔ－ブチルフェニル）アミノ基）が挙げられる。 Examples of substituted amino groups include dialkylamino groups (e.g. dimethylamino group, diethylamino group), diarylamino groups (e.g. diphenylamino group, bis(4-methylphenyl)amino group, bis(4-tert-butylphenyl) ) amino group, bis(3,5-di-tert-butylphenyl)amino group).
　「アシル基」は、置換基を有していてもよい。アシル基の炭素原子数は、置換基の炭素原子数を含めないで、通常２～２０であり、好ましくは２～１８である。アシル基の具体例としては、アセチル基、プロピオニル基、ブチリル基、イソブチリル基、ピバロイル基、ベンゾイル基、トリフルオロアセチル基、及びペンタフルオロベンゾイル基が挙げられる。 The "acyl group" may have a substituent. The number of carbon atoms in the acyl group, not including the number of carbon atoms in substituents, is usually 2 to 20, preferably 2 to 18. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.
　「イミン残基」とは、イミン化合物から、炭素原子－窒素原子二重結合を構成する炭素原子又は窒素原子に直接結合する水素原子を１個除いた残りの原子団を意味する。「イミン化合物」とは、分子内に、炭素原子－窒素原子二重結合を有する有機化合物を意味する。イミン化合物の例としては、アルジミン、ケチミン、及びアルジミン中の炭素原子－窒素原子二重結合を構成する窒素原子に結合している水素原子が、アルキル基、シクロアルキル基などの置換基で置換された化合物が挙げられる。 "Imine residue" means an atomic group remaining after removing one hydrogen atom directly bonded to a carbon atom or nitrogen atom constituting a carbon atom-nitrogen atom double bond from an imine compound. "Imine compound" means an organic compound having a carbon atom-nitrogen atom double bond in the molecule. Examples of imine compounds include aldimine, ketimine, and aldimine in which the hydrogen atom bonded to the nitrogen atom forming the carbon-nitrogen double bond is substituted with a substituent such as an alkyl group or a cycloalkyl group. Examples include compounds such as
　イミン残基の炭素原子数は、通常２～２０であり、好ましくは２～１８である。イミン残基の例としては、下記の構造式で表される基が挙げられる。 The number of carbon atoms in the imine residue is usually 2 to 20, preferably 2 to 18. Examples of imine residues include groups represented by the following structural formula.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　「アミド基」とは、アミドから窒素原子に結合した水素原子１つを除いた残りの原子団を意味する。アミド基の炭素原子数は、通常１～２０程度であり、好ましくは１～１８である。アミド基の具体例としては、ホルムアミド基、アセトアミド基、プロピオアミド基、ブチロアミド基、ベンズアミド基、トリフルオロアセトアミド基、ペンタフルオロベンズアミド基、ジホルムアミド基、ジアセトアミド基、ジプロピオアミド基、ジブチロアミド基、ジベンズアミド基、ジトリフルオロアセトアミド基、及びジペンタフルオロベンズアミド基が挙げられる。 "Amide group" means an atomic group remaining after removing one hydrogen atom bonded to a nitrogen atom from amide. The number of carbon atoms in the amide group is usually about 1 to 20, preferably 1 to 18. Specific examples of the amide group include formamide group, acetamide group, propioamide group, butyroamide group, benzamide group, trifluoroacetamide group, pentafluorobenzamide group, diformamide group, diacetamide group, dipropioamide group, dibutyroamide group, dibenzamide group. , ditrifluoroacetamide group, and dipentafluorobenzamide group.
　「酸イミド基」とは、酸イミドから窒素原子に結合した水素原子１つを除いた残りの原子団を意味する。酸イミド基の炭素原子数は、通常４～２０である。酸イミド基の具体例としては、以下に示す基が挙げられる。 "Acid imide group" means an atomic group remaining after removing one hydrogen atom bonded to a nitrogen atom from an acid imide. The acid imide group usually has 4 to 20 carbon atoms. Specific examples of the acid imide group include the groups shown below.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　「置換オキシカルボニル基」とは、Ｒ’－Ｏ－（Ｃ＝Ｏ）－で表される基を意味する。ここで、Ｒ’は、アルキル基、シクロアルキル基、アリール基、アリールアルキル基、又は１価の複素環基を表し、これらの基は置換基を有していてもよい。
　置換オキシカルボニル基は、炭素原子数が通常２～６０であり、好ましくは炭素原子数が２～４８である。 "Substituted oxycarbonyl group" means a group represented by R'-O-(C=O)-. Here, R' represents an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group, and these groups may have a substituent.
The substituted oxycarbonyl group usually has 2 to 60 carbon atoms, preferably 2 to 48 carbon atoms.
　置換オキシカルボニル基の具体例としては、メトキシカルボニル基、エトキシカルボニル基、プロポキシカルボニル基、イソプロポキシカルボニル基、ブトキシカルボニル基、イソブトキシカルボニル基、ｔｅｒｔ－ブトキシカルボニル基、ペンチルオキシカルボニル基、ヘキシルオキシカルボニル基、シクロヘキシルオキシカルボニル基、ヘプチルオキシカルボニル基、オクチルオキシカルボニル基、２－エチルヘキシルオキシカルボニル基、ノニルオキシカルボニル基、デシルオキシカルボニル基、３，７－ジメチルオクチルオキシカルボニル基、ドデシルオキシカルボニル基、トリフルオロメトキシカルボニル基、ペンタフルオロエトキシカルボニル基、パーフルオロブトキシカルボニル基、パーフルオロヘキシルオキシカルボニル基、パーフルオロオクチルオキシカルボニル基、フェノキシカルボニル基、ナフトキシカルボニル基、及びピリジルオキシカルボニル基が挙げられる。 Specific examples of substituted oxycarbonyl groups include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, tert-butoxycarbonyl group, pentyloxycarbonyl group, and hexyloxycarbonyl group. group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl group, Examples include fluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group, perfluorooctyloxycarbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group, and pyridyloxycarbonyl group.
　「アルキルスルホニル基」は、直鎖状でもあってもよく、分岐状であってもよい。アルキルスルホニル基は、置換基を有していてもよい。アルキルスルホニル基の炭素原子数は、置換基の炭素原子数を含めないで、通常１～３０である。アルキルスルホニル基の具体例としては、メチルスルホニル基、エチルスルホニル基、及びドデシルスルホニル基が挙げられる。 The "alkylsulfonyl group" may be linear or branched. The alkylsulfonyl group may have a substituent. The number of carbon atoms in the alkylsulfonyl group is usually 1 to 30, not including the number of carbon atoms in substituents. Specific examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, and a dodecylsulfonyl group.
　化学式に付される「＊」は、結合手を表す。 The "*" added to the chemical formula represents a bond.
　「π共役系」とは、π電子が複数の結合にわたって非局在化している系を意味する。 "π-conjugated system" means a system in which π electrons are delocalized across multiple bonds.
　「（メタ）アクリル」には、アクリル、メタクリル、及びこれらの組み合わせが含まれる。 "(Meth)acrylic" includes acrylic, methacrylic, and combinations thereof.
　「（メタ）アクリレート」には、アクリレート、メタクリレート、及びこれらの組み合わせが含まれる。 "(Meth)acrylate" includes acrylate, methacrylate, and combinations thereof.
　化学式において、「Ｍｅ」はメチル基を表し、「Ｅｔ」はエチル基を表し、「Ｂｕ」はブチル基を表す。 In the chemical formula, "Me" represents a methyl group, "Et" represents an ethyl group, and "Bu" represents a butyl group.
　「溶媒」は、分散媒でありうる。 "Solvent" can be a dispersion medium.
［２．組成物］
　本発明の一実施形態に係る組成物は、ｐ型半導体、ｎ型半導体、界面活性剤、及び溶媒を含む。組成物は、ｐ型半導体、ｎ型半導体、界面活性剤、及び溶媒に加えて、必要に応じて任意の成分を含んでいてもよい。 [2. Composition]
A composition according to one embodiment of the present invention includes a p-type semiconductor, an n-type semiconductor, a surfactant, and a solvent. In addition to the p-type semiconductor, n-type semiconductor, surfactant, and solvent, the composition may contain arbitrary components as necessary.
　組成物は、溶液であってもよく、分散液、エマルション（乳濁液）、サスペンション（懸濁液）等の分散液であってもよい。 The composition may be a solution, or a dispersion such as a dispersion, an emulsion, or a suspension.
　本実施形態の組成物から得られる膜を含む光電変換素子は、暗電流が低減されている。 A photoelectric conversion element including a film obtained from the composition of this embodiment has reduced dark current.
［２．１．界面活性剤］
　界面活性剤は、添加により界面の性質を変化させる物質を意味する。界面活性剤は、通常、一つの分子中に親水基及び疎水基の両方を有する。 [2.1. Surfactant]
By surfactant is meant a substance that changes the properties of the interface upon addition. Surfactants usually have both a hydrophilic group and a hydrophobic group in one molecule.
　本実施形態に係る組成物が界面活性剤を含む場合、組成物から得られる膜を含む光電変換素子の暗電流を、効果的に低減しうる。 When the composition according to this embodiment contains a surfactant, the dark current of a photoelectric conversion element including a film obtained from the composition can be effectively reduced.
　本実施形態の組成物が界面活性剤を含むことにより、光電変換素子の暗電流を効果的に低減しうる理由については、本発明を限定するものではないが、以下のように推察される。 The reason why the dark current of the photoelectric conversion element can be effectively reduced by containing the surfactant in the composition of the present embodiment is assumed to be as follows, although the present invention is not limited thereto.
　通常、電極、中間層などの塗布対象上に、組成物を塗布して塗膜を形成し、更に塗膜を乾燥させて、膜（活性層）を形成する。塗膜の表面には、界面活性剤が膜状に存在すると考えられ、塗膜が乾燥すると、塗膜の表面に偏在する界面活性剤はそのまま偏析し、固化すると考えられる。その結果、得られた膜（活性層）の表面には、界面活性剤の薄膜が存在して絶縁層として機能し、光電変換素子の暗電流を低減させると考えられる。 Usually, a composition is applied to a coating object such as an electrode or an intermediate layer to form a coating film, and the coating film is further dried to form a film (active layer). It is thought that the surfactant exists in the form of a film on the surface of the coating film, and when the coating film dries, the surfactant unevenly distributed on the surface of the coating film segregates as it is and solidifies. As a result, a thin film of surfactant exists on the surface of the obtained film (active layer) and functions as an insulating layer, which is thought to reduce the dark current of the photoelectric conversion element.
　または、ｐ型半導体及びｎ型半導体によって形成されうる相分離構造が、界面活性剤の作用により変化すると考えられ、その変化により、光電変換素子の暗電流が低減されると考えられる。 Alternatively, it is thought that the phase separation structure formed by the p-type semiconductor and the n-type semiconductor changes due to the action of the surfactant, and this change is thought to reduce the dark current of the photoelectric conversion element.
　本実施形態に係る組成物から得られる膜を含む光電変換素子の暗電流を、効果的に低減しうる界面活性剤としては、分子中の親水基及び疎水基の種類をそれぞれ適切に選択することで好適な界面活性剤を選択することができる。 As a surfactant that can effectively reduce the dark current of a photoelectric conversion element including a film obtained from the composition according to the present embodiment, it is necessary to appropriately select the types of hydrophilic groups and hydrophobic groups in the molecule. A suitable surfactant can be selected.
　本実施形態の組成物に含まれる界面活性剤において、親水基の種類から選定する場合、非イオン性（ノニオン性）に分類される界面活性剤を採用することが好ましい。本実施形態の組成物に含まれる溶媒には芳香族炭化水素溶媒などの非水系溶媒が用いられる。溶媒への溶解性に優れることからも、ノニオン性界面活性剤が好ましい。親水性基の例としては、エチレンオキサイドやプロピレンオキサイドなどのエポキシ基を有する基、アミノ基、ケトン基、カルボキシル基、スルホン基などが挙げられる。界面活性剤は、親水基として、これらから選ばれる１種又は２種以上の基を有していてもよい。 When selecting the surfactant contained in the composition of the present embodiment based on the type of hydrophilic group, it is preferable to use a surfactant classified as nonionic. A non-aqueous solvent such as an aromatic hydrocarbon solvent is used as the solvent contained in the composition of this embodiment. Nonionic surfactants are preferred also because they have excellent solubility in solvents. Examples of hydrophilic groups include groups having epoxy groups such as ethylene oxide and propylene oxide, amino groups, ketone groups, carboxyl groups, and sulfone groups. The surfactant may have one or more groups selected from these as hydrophilic groups.
　本実施形態の組成物に含まれる界面活性剤において、疎水基の種類から選定する場合、疎水基がポリ（メタ）アクリレート構造を有するアクリル系界面活性剤、オルガノポリシロキサン構造を有するシリコーン系界面活性剤、これらの基が有する水素原子の一部又は全部が、フッ素原子に置換されたフッ素系界面活性剤が挙げられる。 When selecting the surfactants contained in the composition of the present embodiment based on the type of hydrophobic group, acrylic surfactants whose hydrophobic groups have a poly(meth)acrylate structure, silicone surfactants whose hydrophobic groups have a poly(meth)acrylate structure, and silicone surfactants whose hydrophobic groups have a poly(meth)acrylate structure and fluorine-based surfactants in which some or all of the hydrogen atoms of these groups are substituted with fluorine atoms.
　一実施形態において、界面活性剤は、ポリ（メタ）アクリレート構造を有することが好ましい。ここで、ポリ（メタ）アクリレート構造は、下記式（ＳＦ－１）で表される構造である。組成物が、ポリ（メタ）アクリレート構造を有することにより、光電変換素子の暗電流を効果的に低減しうる。界面活性剤は、ポリ（メタ）アクリレート構造に加えて、任意の構成単位を含んでいてもよい。ポリ（メタ）アクリレート構造を有する界面活性剤は、オリゴマー、ポリマーであり得る。 In one embodiment, the surfactant preferably has a poly(meth)acrylate structure. Here, the poly(meth)acrylate structure is a structure represented by the following formula (SF-1). When the composition has a poly(meth)acrylate structure, the dark current of the photoelectric conversion element can be effectively reduced. The surfactant may contain any structural unit in addition to the poly(meth)acrylate structure. Surfactants having a poly(meth)acrylate structure can be oligomers or polymers.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　式（ＳＦ－１）中、複数存在するＲｓｆ１は、それぞれ独立して、水素原子又はメチル基を表す。
　複数存在するＲｓｆ２は、それぞれ独立して、有機基を表す。複数のＲｓｆ２のうちの二つ以上が一緒になって、架橋基を形成してもよい。
　Ｒｓｆ２は、好ましくは、それぞれ独立して、アルキル基、シクロアルキル基、アルキルオキシアルキル基、ポリオキシアルキレン基を有する基、アリール基、アリールアルキル基、アリールオキシアルキル基を表し、これらの基は置換基（例えば、フッ素原子）を有していてもよい。
　Ｒｓｆ２により表されるアルキル基の好ましい具体例としては、アルキル基が有する水素原子の一部がフッ素原子により置換されているフッ素原子置換アルキル基（例、ジフルオロメチル基、２，２－ジフルオロエチル基、２，２，２－トリフルオロエチル基、２，２，３，３－テトラフルオロプロピル基、３，３，３－トリフルオロプロピル基、２，２，３，３，４，４－ヘキサフルオロブチル基、１，１－ジメチル－２，２，３，３－テトラフルオロプロピル基、１，１－ジメチル－２，２，３，３，３－ペンタフルオロプロピル基、２－（パーフルオロプロピル）エチル基、２，２，３，３，４，４，５，５－オクタフルオロペンチル基、１，１－ジメチル－２，２，３，３，４，４－ヘキサフルオロブチル基、１，１－ジメチル－２，２，３，３，４，４，４－ヘプタフルオロブチル基、２－（パーフルオロブチル）エチル基、２，２，３，３，４，４，５，５，６，６－デカフルオロヘキシル基、パーフルオロペンチルメチル基、１，１－ジメチル－２，２，３，３，４，４，５，５－オクタフルオロペンチル基、１，１－ジメチル－２，２，３，３，４，４，５，５，５－ノナフルオロペンチル基、２－（パーフルオロペンチル）エチル基、２，２，３，３，４，４，５，５，６，６，７，７－ドデカフルオロヘプチル基、パーフルオロヘキシルメチル基、２－（パーフルオロヘキシル）エチル基、２，２，３，３，４，４，５，５，６，６，７，７，８，８－テトラデカフルオロオクチル基、パーフルオロヘプチルメチル基、２－（パーフルオロヘプチル）エチル基、２，２，３，３，４，４，５，５，６，６，７，７，８，８，９，９－ヘキサデカフルオロノニル基、パーフルオロオクチルメチル基、２－（パーフルオロオクチル）エチル基、２，２，３，３，４，４，５，５，６，６，７，７，８，８，９，９，１０，１０－オクタデカフルオロデシル基、パーフルオロノニルメチル基、２，２，３，４，４，４－ヘキサフルオロブチル基、２，２，３，３，４，４，４－ヘプタフルオロブチル基、３，３，４，４，５，５，６，６，６－ノナフルオロヘキシル基、３，３，４，４，５，５，６，６，７，７，８，８，８－トリドデカフルオロオクチル基）、アルキル基が有する水素原子のすべてがフッ素原子により置換されているフッ素原子置換アルキル基（パーフルオロアルキル基）（例、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロ－ｎ－プロピル基、ヘプタフルオロイソプロピル基、ノナフルオロ－ｎ－ブチル基、ノナフルオロイソブチル基、ノナフルオロ－ｓ－ブチル基、ノナフルオロ－ｔ－ブチル基、パーフルオロペンチル基、パーフルオロヘキシル基、パーフルオロヘプチル基、パーフルオロオクチル基、パーフルオロノニル基、パーフルオロデシル基）が挙げられる。 In formula (SF-1), multiple R sf1 's each independently represent a hydrogen atom or a methyl group.
A plurality of R sf2 's each independently represent an organic group. Two or more of the plurality of R sf2 may be combined to form a crosslinking group.
R sf2 preferably each independently represents an alkyl group, a cycloalkyl group, an alkyloxyalkyl group, a group having a polyoxyalkylene group, an aryl group, an arylalkyl group, an aryloxyalkyl group, and these groups are It may have a substituent (for example, a fluorine atom).
Preferred specific examples of the alkyl group represented by R sf2 include fluorine atom-substituted alkyl groups in which some of the hydrogen atoms of the alkyl group are substituted with fluorine atoms (e.g., difluoromethyl group, 2,2-difluoroethyl group). group, 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3,4,4-hexa Fluorobutyl group, 1,1-dimethyl-2,2,3,3-tetrafluoropropyl group, 1,1-dimethyl-2,2,3,3,3-pentafluoropropyl group, 2-(perfluoropropyl group) ) Ethyl group, 2,2,3,3,4,4,5,5-octafluoropentyl group, 1,1-dimethyl-2,2,3,3,4,4-hexafluorobutyl group, 1, 1-dimethyl-2,2,3,3,4,4,4-heptafluorobutyl group, 2-(perfluorobutyl)ethyl group, 2,2,3,3,4,4,5,5,6 , 6-decafluorohexyl group, perfluoropentylmethyl group, 1,1-dimethyl-2,2,3,3,4,4,5,5-octafluoropentyl group, 1,1-dimethyl-2,2 , 3,3,4,4,5,5,5-nonafluoropentyl group, 2-(perfluoropentyl)ethyl group, 2,2,3,3,4,4,5,5,6,6, 7,7-dodecafluoroheptyl group, perfluorohexylmethyl group, 2-(perfluorohexyl)ethyl group, 2,2,3,3,4,4,5,5,6,6,7,7,8 , 8-tetradecafluorooctyl group, perfluoroheptylmethyl group, 2-(perfluoroheptyl)ethyl group, 2,2,3,3,4,4,5,5,6,6,7,7,8 , 8,9,9-hexadecafluorononyl group, perfluorooctylmethyl group, 2-(perfluorooctyl)ethyl group, 2,2,3,3,4,4,5,5,6,6,7 , 7,8,8,9,9,10,10-octadecafluorodecyl group, perfluorononylmethyl group, 2,2,3,4,4,4-hexafluorobutyl group, 2,2,3, 3,4,4,4-heptafluorobutyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, 3,3,4,4,5,5,6, 6,7,7,8,8,8-tridodecafluorooctyl group), a fluorine atom-substituted alkyl group (perfluoroalkyl group) in which all the hydrogen atoms of the alkyl group are replaced with fluorine atoms (e.g., tridodecafluorooctyl group), Fluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group, heptafluoroisopropyl group, nonafluoro-n-butyl group, nonafluoroisobutyl group, nonafluoro-s-butyl group, nonafluoro-t-butyl group, perfluoro (pentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, perfluorodecyl group).
　式（ＳＦ－１）中、ｎ（繰り返し単位数）は、例えば、２以上、３以上、４以上、５以上、１０以上であり、例えば、３０００以下である。 In formula (SF-1), n (number of repeating units) is, for example, 2 or more, 3 or more, 4 or more, 5 or more, 10 or more, and, for example, 3000 or less.
　ポリ（メタ）アクリレート構造を有する界面活性剤として、市販品を使用できる。
　ポリ（メタ）アクリレート構造を有する市販のノニオン性界面活性剤の例としては、「Ｆ－５５６」、「Ｒ－４０」、「メガファック　Ｆ－１１０（ＭＥＧＡＦＡＣＥ　Ｆ－１１０）」、「メガファック　Ｆ－１１３（ＭＥＧＡＦＡＣＥ　Ｆ－１１３）」、「メガファック　Ｆ－１２０（ＭＥＧＡＦＡＣＥ　Ｆ－１２０）」、「メガファック　Ｆ－８１２（ＭＥＧＡＦＡＣＥ　Ｆ－８１２）」、「メガファック　Ｆ－１４２Ｄ（ＭＥＧＡＦＡＣＥ　Ｆ－１４２Ｄ）」、「メガファック　Ｆ－１４４Ｄ（ＭＥＧＡＦＡＣＥ　Ｆ－１４４Ｄ）」、「メガファック　Ｆ－１５０（ＭＥＧＡＦＡＣＥ　Ｆ－１５０）」、「メガファック　Ｆ－１７１（ＭＥＧＡＦＡＣＥ　Ｆ－１７１）」、「メガファック　Ｆ－１７３（ＭＥＧＡＦＡＣＥ　Ｆ－１７３）」、「メガファック　Ｆ－１７７（ＭＥＧＡＦＡＣＥ　Ｆ－１７７）」、「メガファック　Ｆ－１８３（ＭＥＧＡＦＡＣＥ　Ｆ－１８３）」、「メガファック　Ｆ－１９５（ＭＥＧＡＦＡＣＥ　Ｆ－１９５）」、「メガファック　Ｆ－８２４（ＭＥＧＡＦＡＣＥ　Ｆ－８２４）」、「メガファック　Ｆ－８３３（ＭＥＧＡＦＡＣＥ　Ｆ－８３３）」、「メガファック　Ｆ－１１４（ＭＥＧＡＦＡＣＥ　Ｆ－１１４）」、「メガファック　Ｆ－４１０（ＭＥＧＡＦＡＣＥ　Ｆ－４１０）」、「メガファック　Ｆ－４９３（ＭＥＧＡＦＡＣＥ　Ｆ－４９３）」、「メガファック　Ｆ－４９４（ＭＥＧＡＦＡＣＥ　Ｆ－４９４）」、「メガファック　Ｆ－４４３（ＭＥＧＡＦＡＣＥ　Ｆ－４４３）」、「メガファック　Ｆ－４４４（ＭＥＧＡＦＡＣＥ　Ｆ－４４４）」、「メガファック　Ｆ－４４５（ＭＥＧＡＦＡＣＥ　Ｆ－４４５）」、「メガファック　Ｆ－４４６（ＭＥＧＡＦＡＣＥ　Ｆ－４４６）」、「メガファック　Ｆ－４７０（ＭＥＧＡＦＡＣＥ　Ｆ－４７０）」、「メガファック　Ｆ－４７１（ＭＥＧＡＦＡＣＥ　Ｆ－４７１）」、「メガファック　Ｆ－４７４（ＭＥＧＡＦＡＣＥ　Ｆ－４７４）」、「メガファック
　Ｆ－４７５（ＭＥＧＡＦＡＣＥ　Ｆ－４７５）」、「メガファック　Ｆ－４７７（ＭＥＧＡＦＡＣＥ　Ｆ－４７７）」、「メガファック　Ｆ－４７８（ＭＥＧＡＦＡＣＥ　Ｆ－４７８）」、「メガファック　Ｆ－４７９（ＭＥＧＡＦＡＣＥ　Ｆ－４７９）」、「メガファック　Ｆ－４８０ＳＦ（ＭＥＧＡＦＡＣＥ　Ｆ－４８０ＳＦ）」、「メガファック　Ｆ－４８２（ＭＥＧＡＦＡＣＥ　Ｆ－４８２）」、「メガファック　Ｆ－４８３（ＭＥＧＡＦＡＣＥ　Ｆ－４８３）」、「メガファック　Ｆ－４８４（ＭＥＧＡＦＡＣＥ　Ｆ－４８４）」、「メガファック　Ｆ－４８６（ＭＥＧＡＦＡＣＥ　Ｆ－４８６）」、「メガファック　Ｆ－４８７（ＭＥＧＡＦＡＣＥ　Ｆ－４８７）」、「メガファック　Ｆ－４８９（ＭＥＧＡＦＡＣＥ　Ｆ－４８９）」、「メガファック　Ｆ－１７２Ｄ（ＭＥＧＡＦＡＣＥ　Ｆ－１７２Ｄ）」、「メガファック　Ｆ－１７８Ｋ（ＭＥＧＡＦＡＣＥ　Ｆ－１７８
　Ｋ）」、「メガファック　Ｆ－１７８ＲＭ（ＭＥＧＡＦＡＣＥ　Ｆ－１７８ＲＭ）」、「メガファック　Ｒ－０８（ＭＥＧＡＦＡＣＥ　Ｒ－０８）」、「メガファック　Ｒ－３０（ＭＥＧＡＦＡＣＥ　Ｒ－３０）」、「メガファック　Ｆ－４７２ＳＦ（ＭＥＧＡＦＡＣＥ　Ｆ－４７２ＳＦ）」、「メガファック　ＢＬ－２０（ＭＥＧＡＦＡＣＥ　ＢＬ－２０）」、「メガファック　Ｒ－６１（ＭＥＧＡＦＡＣＥ　Ｒ－６１）」、「メガファック
　Ｒ－９０（ＭＥＧＡＦＡＣＥ　Ｒ－９０）」、「メガファック　ＥＳＭ－１（ＭＥＧＡＦＡＣＥ　ＥＳＭ－１）」、「メガファック　ＭＣＦ－３５０ＳＦ（ＭＥＧＡＦＡＣＥ　ＭＣＦ－３５０ＳＦ）」（以上、ＤＩＣ社製）、
「フタージェント１００」、「フタージェント１００Ｃ」、「フタージェント１１０」、「フタージェント１５０」、「フタージェント１５０ＣＨ」、「フタージェントＡ」、「フタージェント１００Ａ－Ｋ」、「フタージェント５０１」、「フタージェント３００」、「フタージェント３１０」、「フタージェント３２０」、「フタージェント４００ＳＷ」、「ＦＴＸ－４００Ｐ」、「フタージェント２５１」、「フタージェント２１５Ｍ」、「フタージェント２１２ＭＨ」、「フタージェント２５０」、「フタージェント２２２Ｆ」、「フタージェント２１２Ｄ」、「ＦＴＸ－２１８」、「ＦＴＸ－２０９Ｆ」、「ＦＴＸ－２１３Ｆ」、「ＦＴＸ－２３３Ｆ」、「フタージェント２４５Ｆ」、「ＦＴＸ－２０８Ｇ」、「ＦＴＸ－２４０Ｇ」、「ＦＴＸ－２０６Ｄ」、「ＦＴＸ－２２０Ｄ」、「ＦＴＸ－２３０Ｄ」、「ＦＴＸ－２４０Ｄ」、「ＦＴＸ－２０７Ｓ」、「ＦＴＸ－２１１Ｓ」、「ＦＴＸ－２２０Ｓ」、「ＦＴＸ－２３０Ｓ」、「ＦＴＸ－７５０ＦＭ」、「ＦＴＸ－７３０ＦＭ」、「ＦＴＸ－７３０ＦＬ」、「ＦＴＸ－７１０ＦＳ」、「ＦＴＸ－７１０ＦＭ」、「ＦＴＸ－７１０ＦＬ」、「ＦＴＸ－７５０ＬＬ」、「ＦＴＸ－７３０ＬＳ」、「ＦＴＸ－７３０ＬＭ」、「ＦＴＸ－７３０ＬＬ」、「ＦＴＸ－７１０ＬＬ」（以上、ネオス社製）、
「ＢＹＫ－３００」、「ＢＹＫ－３０２」、「ＢＹＫ－３０６」、「ＢＹＫ－３０７」、「ＢＹＫ－３１０」、「ＢＹＫ－３１５」、「ＢＹＫ－３２０」、「ＢＹＫ－３２２」、「ＢＹＫ－３２３」、「ＢＹＫ－３２５」、「ＢＹＫ－３３０」、「ＢＹＫ－３３１」、「ＢＹＫ－３３３」、「ＢＹＫ－３３７」、「ＢＹＫ－３４０」、「ＢＹＫ－３４４」、「ＢＹＫ－３７０」、「ＢＹＫ－３７５」、「ＢＹＫ－３７７」、「ＢＹＫ－３５０」、「ＢＹＫ－３５２」、「ＢＹＫ－３５４」、「ＢＹＫ－３５５」、「ＢＹＫ－３５６」、「ＢＹＫ－３５８Ｎ」、「ＢＹＫ－３６１Ｎ」、「ＢＹＫ－３５７」、「ＢＹＫ－３９０」、「ＢＹＫ－３９２」、「ＢＹＫ－ＵＶ３５００」、「ＢＹＫ－ＵＶ３５１０」、「ＢＹＫ－ＵＶ３５７０」、「ＢＹＫ－Ｓｉｌｃｌｅａｎ　３７００」（以上、ビックケミー・ジャパン社製）、
「ＴＥＧＯ　Ｒａｄ２１００」、「ＴＥＧＯ　Ｒａｄ２２００　Ｎ」、「ＴＥＧＯ　Ｒａｄ２２５０」、「ＴＥＧＯ　Ｒａｄ２３００」、「ＴＥＧＯ　Ｒａｄ２５００」、「ＴＥＧＯ　Ｒａｄ２６００」、「ＴＥＧＯ　Ｒａｄ２７００」（以上、エボニック・インダストリーズ社製）が挙げられる。 Commercially available products can be used as the surfactant having a poly(meth)acrylate structure.
Examples of commercially available nonionic surfactants having a poly(meth)acrylate structure include "F-556,""R-40,""MEGAFACEF-110," and "Megaface F. -113 (MEGAFACE F-113)", "Megafac F-120 (MEGAFACE F-120)", "Megafac F-812 (MEGAFACE F-812)", "Megafac F-142D (MEGAFACE F-142D) ”, “MEGAFACE F-144D”, “MEGAFACE F-150”, “MEGAFACE F-171”, “MEGAFACE F-173” (MEGAFACE F-173),” “Mega Fuck F-177 (MEGAFACE F-177),” “Mega Fuck F-183 (MEGAFACE F-183),” “Mega Fuck F-195 (MEGAFACE F-195),” "MEGAFACE F-824", "MEGAFACE F-833", "MEGAFACE F-114", "MEGAFACE F-410"F-410)","Mega Fac F-493 (MEGAFACE F-493)", "Mega Fac F-494 (MEGAFACE F-494)", "Mega Fac F-443 (MEGAFACE F-443)", "Mega FUCK F-444 (MEGAFACE F-444)", ``MEGAFACE F-445", ``MEGAFACE F-446'', ``MEGAFACE F-470''470)'', ``MEGAFACE F-471'', ``MEGAFACE F-474'', ``MEGAFACE F-475'', ``MEGAFACE F-475'', ``MEGAFACE F-475'', ``MEGAFACE -477 (MEGAFACE F-477)", "Megafac F-478 (MEGAFACE F-478)", "Megafac F-479 (MEGAFACE F-479)", "Megafac F-480SF (MEGAFACE F-480SF) ”, “MEGAFACE F-482”, “MEGAFACE F-483”, “MEGAFACE F-484”, “MEGAFACE F-486” (MEGAFACE F-486)", "Megafac F-487 (MEGAFACE F-487)", "Megafac F-489 (MEGAFACE F-489)", "Megafac F-172D (MEGAFACE F-172D)", "MEGAFACE F-178K (MEGAFACE F-178
K)", "MEGAFACE F-178RM", "MEGAFACE R-08", "MEGAFACE R-30", "MEGAFACE F -472SF (MEGAFACE F-472SF)", "Megafac BL-20 (MEGAFACE BL-20)", "Megafac R-61 (MEGAFACE R-61)", "Megafac R-90 (MEGAFACE R-90) ”, “Megafac ESM-1 (MEGAFACE ESM-1)”, “Megafac MCF-350SF (MEGAFACE MCF-350SF)” (manufactured by DIC),
"Futergent 100", "Futergent 100C", "Futergent 110", "Futergent 150", "Futergent 150CH", "Futergent A", "Futergent 100A-K", "Futergent 501", "Futergent 300", "Futergent 310", "Futergent 320", "Futergent 400SW", "FTX-400P", "Futergent 251", "Futergent 215M", "Futergent 212MH", "Futergent Gent 250", "Ftergent 222F", "Ftergent 212D", "FTX-218", "FTX-209F", "FTX-213F", "FTX-233F", "Ftergent 245F", "FTX-208G"","FTX-240G","FTX-206D","FTX-220D","FTX-230D","FTX-240D","FTX-207S","FTX-211S","FTX-220S","FTX-230S","FTX-750FM","FTX-730FM","FTX-730FL","FTX-710FS","FTX-710FM","FTX-710FL","FTX-750LL","FTX -730LS”, “FTX-730LM”, “FTX-730LL”, “FTX-710LL” (all manufactured by Neos),
"BYK-300", "BYK-302", "BYK-306", "BYK-307", "BYK-310", "BYK-315", "BYK-320", "BYK-322", "BYK -323'', ``BYK-325'', ``BYK-330'', ``BYK-331'', ``BYK-333'', ``BYK-337'', ``BYK-340'', ``BYK-344'', ``BYK-370''","BYK-375","BYK-377","BYK-350","BYK-352","BYK-354","BYK-355","BYK-356","BYK-358N","BYK-361N","BYK-357","BYK-390","BYK-392","BYK-UV3500","BYK-UV3510","BYK-UV3570","BYK-Silclean3700" (and above) , manufactured by BIC Chemie Japan),
"TEGO Rad2100", "TEGO Rad2200 N", "TEGO Rad2250", "TEGO Rad2300", "TEGO Rad2500", "TEGO Rad2600", "TEGO Rad2700" (all manufactured by Evonik Industries) were listed. It will be done.
　一実施形態において、界面活性剤は、オルガノポリシロキサン構造を有することが好ましい。ここで、オルガノポリシロキサン構造は、下記式（ＳＦ－２）で表される構造である。組成物が、オルガノポリシロキサン構造を有することにより、光電変換素子の暗電流を効果的に低減しうる。界面活性剤は、オルガノポリシロキサン構造に加えて、任意の構成単位を含んでいてもよい。オルガノポリシロキサン構造を有する界面活性剤は、オリゴマー、ポリマーであり得る。 In one embodiment, the surfactant preferably has an organopolysiloxane structure. Here, the organopolysiloxane structure is a structure represented by the following formula (SF-2). When the composition has an organopolysiloxane structure, dark current of a photoelectric conversion element can be effectively reduced. The surfactant may contain any structural unit in addition to the organopolysiloxane structure. Surfactants having an organopolysiloxane structure can be oligomers or polymers.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　式（ＳＦ－２）中、複数存在するＲｓｆ３は、それぞれ独立して、有機基を表す。
　Ｒｓｆ３は、好ましくは、それぞれ独立して、アルキル基、シクロアルキル基、アリール基、アリールアルキル基、ポリオキシアルキレン基を有する基、又は－（Ｃ＝Ｏ）－Ｏ－で表される構造を有する基（例えば、－（Ｃ＝Ｏ）－Ｏ－で表される構造を１以上、２以上、又は３以上有する基）を表し、これらの基は、置換基を有していてもよい。 In formula (SF-2), multiple R sf3 's each independently represent an organic group.
R sf3 preferably each independently represents a group having an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, a polyoxyalkylene group, or a structure represented by -(C=O)-O-. (for example, a group having one or more, two or more, or three or more structures represented by -(C=O)-O-), and these groups may have a substituent.
　オルガノポリシロキサン構造を有する界面活性剤は、任意の末端基を有しうる。
　オルガノポリシロキサン構造を有する界面活性剤が有しうる末端基の例としては、アルキル基、シクロアルキル基、アルキルオキシ基、シクロアルキルオキシ基、ポリオキシアルキレン基を有する基、アリール基、アリールアルキル基、及びポリ（メタ）アクリロイル基が挙げられ、これらの基は置換基（例、フッ素原子）を有していてもよい。 Surfactants having an organopolysiloxane structure can have any terminal group.
Examples of terminal groups that a surfactant having an organopolysiloxane structure may have include an alkyl group, a cycloalkyl group, an alkyloxy group, a cycloalkyloxy group, a group having a polyoxyalkylene group, an aryl group, and an arylalkyl group. , and a poly(meth)acryloyl group, and these groups may have a substituent (eg, a fluorine atom).
　式（ＳＦ－２）中、ｎ（繰り返し単位数）の範囲は、例えば、２以上、３以上、４以上、５以上、１０以上であり、例えば３０００以下である。 In formula (SF-2), the range of n (number of repeating units) is, for example, 2 or more, 3 or more, 4 or more, 5 or more, 10 or more, and, for example, 3000 or less.
　オルガノポリシロキサン構造を有する界面活性剤として、市販品を使用できる。
　オルガノポリシロキサン構造を有する市販のノニオン性界面活性剤の例としては、
　商品名「ＢＹＫ－３００」、「ＢＹＫ－３０１／３０２」、「ＢＹＫ－３０６」、「ＢＹＫ－３０７」、「ＢＹＫ－３１０」、「ＢＹＫ－３１５」、「ＢＹＫ－３１３」、「ＢＹＫ－３２０」、「ＢＹＫ－３２２」、「ＢＹＫ－３２３」、「ＢＹＫ－３２５」、「ＢＹＫ－３３０」、「ＢＹＫ－３３１」、「ＢＹＫ－３３３」、「ＢＹＫ－３３７」、「ＢＹＫ－３４１」、「ＢＹＫ－３４４」、「ＢＹＫ－３４５／３４６」、「ＢＹＫ－３４７」、「ＢＹＫ－３４８」、「ＢＹＫ－３４９」、「ＢＹＫ－３７０」、「ＢＹＫ－３７５」、「ＢＹＫ－３７７」、「ＢＹＫ－３７８」、「ＢＹＫ－ＵＶ３５００」、「ＢＹＫ－ＵＶ３５１０」、「ＢＹＫ－ＵＶ３５７０」、「ＢＹＫ－３５５０」、「ＢＹＫ－ＳＩＬＣＬＥＡＮ３７００」、「ＢＹＫ－ＳＩＬＣＬＥＡＮ３７２０」（以上、ビックケミー・ジャパン社製）、
　商品名「ＡＣ　ＦＳ　１８０」、「ＡＣ　ＦＳ　３６０」、「ＡＣ　Ｓ　２０」（以上、Ａｌｇｉｎ　Ｃｈｅｍｉｅ製）、商品名「ポリフローＫＬ－４００Ｘ」、「ポリフローＫＬ－４００ＨＦ」、「ポリフローＫＬ－４０１」、「ポリフローＫＬ－４０２」、「ポリフローＫＬ－４０３」、「ポリフローＫＬ－４０４」、「ポリフローＫＬ－７００」（以上、共栄社化学社製）、
　商品名「ＫＰ－３０１」、「ＫＰ－３０６」、「ＫＰ－１０９」、「ＫＰ－３１０」、「ＫＰ－３１０Ｂ」、「ＫＰ－３２３」、「ＫＰ－３２６」、「ＫＰ－３４１」、「ＫＰ－１０４」、「ＫＰ－１１０」、「ＫＰ－１１２」、「ＫＰ－３６０Ａ」、「ＫＰ－３６１」、「ＫＰ－３５４」、「ＫＰ－３５５」、「ＫＰ－３５６」、「ＫＰ－３５７」、「ＫＰ－３５８」、「ＫＰ－３５９」、「ＫＰ－３６２」、「ＫＰ－３６５」、「ＫＰ－３６６」、「ＫＰ－３６８」、「ＫＰ－３６９」、「ＫＰ－３３０」、「ＫＰ－６２０」、「ＫＰ－６２５」「ＫＰ－６５０」、「ＫＰ－６５１」、「ＫＰ－３９０」、「ＫＰ－３９１」、「ＫＰ－３９２」（以上、信越化学工業社製）、
　商品名「ＬＰ－７００１」、「ＬＰ－７００２」、「ＳＨ２８ＰＡ」、「８０３２　ＡＤＤＩＴＩＶＥ」、「５７　ＡＤＤＩＴＩＶＥ」、「Ｌ－７６０４」、「ＦＺ－２１１０」、「ＦＺ－２１０５」、「６７　ＡＤＤＩＴＩＶＥ」、「８６１８　ＡＤＤＩＴＩＶＥ」、「３　ＡＤＤＩＴＩＶＥ」、「５６　ＡＤＤＩＴＩＶＥ」（以上、東レ・ダウコーニング社製）、「ＴＥＧＯ　ＷＥＴ　２７０」（エボニック・デグサ・ジャパン社製）、「ＮＢＸ－１５」（ネオス社製）が挙げられる。 Commercially available products can be used as the surfactant having an organopolysiloxane structure.
Examples of commercially available nonionic surfactants having an organopolysiloxane structure include:
Product name "BYK-300", "BYK-301/302", "BYK-306", "BYK-307", "BYK-310", "BYK-315", "BYK-313", "BYK-320"","BYK-322","BYK-323","BYK-325","BYK-330","BYK-331","BYK-333","BYK-337","BYK-341","BYK-344","BYK-345/346","BYK-347","BYK-348","BYK-349","BYK-370","BYK-375","BYK-377","BYK-378","BYK-UV3500","BYK-UV3510","BYK-UV3570","BYK-3550","BYK-SILCLEAN3700","BYK-SILCLEAN3720" (manufactured by BYK-SILCLEAN3720) ,
Product names "AC FS 180", "AC FS 360", "AC S 20" (all manufactured by Algin Chemie), product names "Polyflow KL-400X", "Polyflow KL-400HF", "Polyflow KL-401", "Polyflow KL-402", "Polyflow KL-403", "Polyflow KL-404", "Polyflow KL-700" (manufactured by Kyoeisha Chemical Co., Ltd.),
Product name "KP-301", "KP-306", "KP-109", "KP-310", "KP-310B", "KP-323", "KP-326", "KP-341", "KP-104", "KP-110", "KP-112", "KP-360A", "KP-361", "KP-354", "KP-355", "KP-356", "KP -357'', ``KP-358'', ``KP-359'', ``KP-362'', ``KP-365'', ``KP-366'', ``KP-368'', ``KP-369'', ``KP-330''","KP-620","KP-625","KP-650","KP-651","KP-390","KP-391","KP-392" (all products manufactured by Shin-Etsu Chemical Co., Ltd. ),
Product name "LP-7001", "LP-7002", "SH28PA", "8032 ADDITIVE", "57 ADDITIVE", "L-7604", "FZ-2110", "FZ-2105", "67 ADDITIVE" , "8618 ADDITIVE", "3 ADDITIVE", "56 ADDITIVE" (manufactured by Toray Dow Corning), "TEGO WET 270" (manufactured by Evonik Degussa Japan), "NBX-15" (manufactured by Neos) ).
　一実施形態において、界面活性剤は、フッ素系界面活性剤であることが好ましい。ここで、フッ素系界面活性剤とは、その分子中に、フッ素原子を含む界面活性剤を意味する。組成物がフッ素系界面活性剤を含むことにより、光電変換素子の暗電流を効果的に低減しうる。 In one embodiment, the surfactant is preferably a fluorosurfactant. Here, the fluorine-based surfactant means a surfactant containing a fluorine atom in its molecule. When the composition contains a fluorine-based surfactant, the dark current of the photoelectric conversion element can be effectively reduced.
　フッ素系界面活性剤として、市販品を使用できる。
　市販のフッ素系界面活性剤の例としては、「Ｆ－５５６」、「Ｒ－４０」、メガファックＦ１７１、同Ｆ１７２、同Ｆ１７３、同Ｆ１７６、同Ｆ１７７、同Ｆ１４１、同Ｆ１４２、同Ｆ１４３、同Ｆ１４４、同Ｒ３０、同Ｆ４３７、同Ｆ４７５、同Ｆ４７９、同Ｆ４８２、同Ｆ５５４、同Ｆ７８０、ＲＳ－７２－Ｋ（以上、ＤＩＣ社製）、
　フロラードＦＣ４３０、同ＦＣ４３１、同ＦＣ１７１、ノベックＦＣ４４３０、同ＦＣ４４３２（以上、スリーエムジャパン社製）、
　サーフロンＳ－３８２、同ＳＣ－１０１、同ＳＣ－１０３、同ＳＣ－１０４、同ＳＣ－１０５、同ＳＣ－１０６８、同ＳＣ－３８１、同ＳＣ－３８３、同Ｓ－３９３、同ＫＨ－４０（以上、旭硝子社製）、
　ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０、ＰＦ６５２０、ＰＦ７００２（以上、ＯＭＮＯＶＡ社製）が挙げられる。 Commercially available products can be used as the fluorosurfactant.
Examples of commercially available fluorosurfactants include "F-556", "R-40", Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141, Megafac F142, Megafac F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (manufactured by DIC),
Florado FC430, FC431, FC171, Novec FC4430, FC4432 (manufactured by 3M Japan),
Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 ( (manufactured by Asahi Glass Co., Ltd.),
Examples include PF636, PF656, PF6320, PF6520, and PF7002 (all manufactured by OMNOVA).
　（性状）
　界面活性剤は、２５℃、１ａｔｍにおいて、液体であることが好ましい。界面活性剤が２５℃、１ａｔｍにおいて液体であることにより、組成物中における溶解性が良好となる。 (Properties)
The surfactant is preferably liquid at 25° C. and 1 atm. Since the surfactant is liquid at 25° C. and 1 atm, it has good solubility in the composition.
　（粘度）
　界面活性剤の粘度ηは、好ましくは１ｍＰａ・ｓ以上、より好ましくは１０ｍＰａ・ｓ以上、更に好ましくは１００ｍＰａ・ｓ以上であり、好ましくは１０，０００ｍＰａ・ｓ以下、より好ましくは５，０００ｍＰａ・ｓ以下である。界面活性剤の粘度ηが、前記範囲内にある場合、光電変換素子の暗電流を効果的に低減しうる。 (viscosity)
The viscosity η of the surfactant is preferably 1 mPa·s or more, more preferably 10 mPa·s or more, even more preferably 100 mPa·s or more, and preferably 10,000 mPa·s or less, more preferably 5,000 mPa·s. It is as follows. When the viscosity η of the surfactant is within the above range, the dark current of the photoelectric conversion element can be effectively reduced.
　ここで、粘度ηは、レオメーターにより、温度２５℃、せん断速度１００（１／ｓ）において測定された値である。 Here, the viscosity η is a value measured using a rheometer at a temperature of 25° C. and a shear rate of 100 (1/s).
　（分子量）
　界面活性剤のピーク分子量Ｍｐは、好ましくは１００以上、より好ましくは１０００以上であり、好ましくは１０，０００以下、より好ましくは５，０００以下である。界面活性剤のピーク分子量Ｍｐが、前記範囲内にある場合、光電変換素子の暗電流を効果的に低減しうる。 (molecular weight)
The peak molecular weight Mp of the surfactant is preferably 100 or more, more preferably 1000 or more, and preferably 10,000 or less, more preferably 5,000 or less. When the peak molecular weight Mp of the surfactant is within the above range, the dark current of the photoelectric conversion element can be effectively reduced.
　ここで、界面活性剤のピーク分子量Ｍｐは、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）により、測定された値である。ピーク分子量Ｍｐは、下記の測定条件で測定されるＧＰＣクロマトグラムにおける、ピークトップの値としうる。 Here, the peak molecular weight Mp of the surfactant is a value measured by gel permeation chromatography (GPC). The peak molecular weight Mp may be the peak top value in a GPC chromatogram measured under the following measurement conditions.
　ＧＰＣの移動相としてはｏ－ジクロロベンゼンを用い、１．０ｍＬ／ｍｉｎの流速で流す。カラムとしては、昭和電工社製、Ｓｈｏｄｅｘ　ＫＤ－８０６Ｍを用い、ガードカラムとしては、昭和電工社製、Ｓｈｏｄｅｘ　ＫＤ－Ｇを用いる。 O-dichlorobenzene is used as the mobile phase for GPC, and it is flowed at a flow rate of 1.0 mL/min. As the column, Shodex KD-806M manufactured by Showa Denko Co., Ltd. is used, and as the guard column, Shodex KD-G manufactured by Showa Denko Co., Ltd. is used.
　検出器としてはＵＶ－ｖｉｓ検出器（島津製作所社製、ＳＰＤ－Ｍ２０Ａ）及び示差屈折率検出器（島津製作所社製、ＲＩＤ－１０Ａ）を用いる。 As the detectors, a UV-vis detector (manufactured by Shimadzu Corporation, SPD-M20A) and a differential refractive index detector (manufactured by Shimadzu Corporation, RID-10A) are used.
　測定対象の化合物（重合体）は、溶媒である１－クロロナフタレンに、０．０５質量％の濃度になるように混合して、８０℃で２時間撹拌することで溶解させた溶解液とする。 The compound (polymer) to be measured is mixed in the solvent 1-chloronaphthalene to a concentration of 0.05% by mass, and stirred at 80°C for 2 hours to form a solution. .
　得られた溶解液を、上記測定装置（ＧＰＣ）にサンプルとして１０μＬ注入することで、ピーク分子量（Ｍｐ）を測定する。 The peak molecular weight (Mp) is measured by injecting 10 μL of the obtained solution into the above-mentioned measuring device (GPC) as a sample.
　（フッ素含有量）
　界面活性剤が、フッ素系界面活性剤である場合、界面活性剤のフッ素含有量は、好ましくはフッ素系界面活性剤中の溶媒を除く固形分を１００質量％として、好ましくは１質量％以上、より好ましくは５質量％以上であり、好ましくは５０質量％以下、より好ましくは３０質量％以下である。界面活性剤のフッ素含有率が前記範囲内にある場合、光電変換素子の暗電流を効果的に低減しうる。界面活性剤のフッ素含有率が、前記上限値以下である場合、組成物から得られる膜（活性膜）の撥水性が低下して、膜上に水系塗布液を容易に塗布しうる。 (Fluorine content)
When the surfactant is a fluorosurfactant, the fluorine content of the surfactant is preferably 1% by mass or more, based on the solid content excluding the solvent in the fluorosurfactant as 100% by mass, The content is more preferably 5% by mass or more, preferably 50% by mass or less, and even more preferably 30% by mass or less. When the fluorine content of the surfactant is within the above range, the dark current of the photoelectric conversion element can be effectively reduced. When the fluorine content of the surfactant is below the above upper limit, the water repellency of the film (active film) obtained from the composition decreases, and a water-based coating liquid can be easily applied onto the film.
　界面活性剤中のフッ素含有率は、燃焼イオンクロマトグラフィー等により測定できる。 The fluorine content in the surfactant can be measured by combustion ion chromatography or the like.
　（界面活性剤の含有割合）
　組成物中の界面活性剤の含有割合は、溶媒の総質量を１００質量％として、好ましくは０．０１質量％以上、より好ましくは０．１質量％以上であり、好ましくは１．０質量％以下、より好ましくは０．５質量％以下である。 (Content ratio of surfactant)
The content of the surfactant in the composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and preferably 1.0% by mass, based on the total mass of the solvent as 100% by mass. The content is preferably 0.5% by mass or less.
　組成物中の界面活性剤の含有割合は、ｎ型半導体、ｐ型半導体、及び界面活性剤の総質量を１００質量％として、好ましくは０．１質量％以上、より好ましくは１質量％以上であり、さらに好ましくは３質量％以上である。また、組成物中の界面活性剤の含有割合は、ｎ型半導体、ｐ型半導体、及び界面活性剤の総質量を１００質量％として、好ましくは２６質量％以下、より好ましくは２４．５質量％以下、さらに好ましくは１０質量％以下、ことさら好ましくは５質量％以下である。 The content of the surfactant in the composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, based on the total mass of the n-type semiconductor, p-type semiconductor, and surfactant as 100% by mass. The content is more preferably 3% by mass or more. Further, the content of the surfactant in the composition is preferably 26% by mass or less, more preferably 24.5% by mass, based on the total mass of the n-type semiconductor, p-type semiconductor, and surfactant as 100% by mass. The content is preferably 10% by mass or less, particularly preferably 5% by mass or less.
　組成物中の界面活性剤の含有割合が、前記範囲内にある場合、光電変換素子の暗電流を効果的に低減しうる。 When the content of the surfactant in the composition is within the above range, the dark current of the photoelectric conversion element can be effectively reduced.
［２．２．ｐ型半導体］
　本実施形態の組成物に含まれるｐ型半導体は、一種単独であっても、二種以上の組み合わせであってもよい。 [2.2. p-type semiconductor]
The p-type semiconductor contained in the composition of this embodiment may be a single type or a combination of two or more types.
　ｐ型半導体は、低分子化合物であってもよく、高分子化合物であってもよく、好ましくは高分子化合物であり、更に好ましくはπ共役系高分子化合物である。 The p-type semiconductor may be a low-molecular compound or a high-molecular compound, preferably a high-molecular compound, and more preferably a π-conjugated high-molecular compound.
　高分子化合物であるｐ型半導体の例としては、ポリビニルカルバゾール及びその誘導体、ポリシラン及びその誘導体、側鎖又は主鎖に芳香族アミン構造を含むポリシロキサン誘導体、ポリアニリン及びその誘導体、ポリチオフェン及びその誘導体、ポリピロール及びその誘導体、ポリフェニレンビニレン及びその誘導体、ポリチエニレンビニレン及びその誘導体、ポリフルオレン及びその誘導体が挙げられる。 Examples of p-type semiconductors that are polymeric compounds include polyvinylcarbazole and its derivatives, polysilane and its derivatives, polysiloxane derivatives containing an aromatic amine structure in the side chain or main chain, polyaniline and its derivatives, polythiophene and its derivatives, Examples include polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, and polyfluorene and its derivatives.
　（ドナー・アクセプター構造）
　ｐ型半導体は、ドナー・アクセプター構造を有する高分子化合物であることが好ましい。ドナー・アクセプター構造は、ドナー構成単位とアクセプター構成単位とを含む。ドナー構成単位は、π電子が過剰である構成単位であり、アクセプター構成単位は、π電子が欠乏している構成単位である。 (Donor-acceptor structure)
The p-type semiconductor is preferably a polymer compound having a donor-acceptor structure. The donor-acceptor structure includes a donor building block and an acceptor building block. A donor constitutional unit is a constitutional unit that is in excess of π electrons, and an acceptor constitutional unit is a constitutional unit that is deficient in π electrons.
　ドナー・アクセプター構造を有する高分子化合物を構成しうる構成単位には、ドナー構成単位とアクセプター構成単位とが直接的に結合した構成単位、さらにはドナー構成単位とアクセプター構成単位とが、任意好適なスペーサー（基又は構成単位）を介して結合した構成単位も含まれる。 The structural units that can constitute a polymer compound having a donor-acceptor structure include a structural unit in which a donor structural unit and an acceptor structural unit are directly bonded, and further a donor structural unit and an acceptor structural unit. Also included are structural units bonded via spacers (groups or structural units).
　ｐ型半導体は、暗電流を効果的に低減する観点から、下記式（Ｉ）で表される構成単位及び下記式（ＩＩ）で表される構成単位からなる群より選択される一種以上の構成単位を含む高分子化合物であることが好ましい。 From the viewpoint of effectively reducing dark current, the p-type semiconductor has one or more configurations selected from the group consisting of the structural unit represented by the following formula (I) and the structural unit represented by the following formula (II). A polymer compound containing units is preferable.
　（式（Ｉ）で表される構成単位） (Constituent unit represented by formula (I))
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　式（Ｉ）中、Ａｒ１及びＡｒ２は、それぞれ独立して、置換基を有していてもよい３価の芳香族複素環基を表し、Ｚは下記式（Ｚ－１）～式（Ｚ－７）のいずれか１つで表される基を表す。 In formula (I), Ar 1 and Ar 2 each independently represent a trivalent aromatic heterocyclic group which may have a substituent, and Z represents the following formula (Z-1) to formula ( Represents a group represented by any one of Z-7).
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　式（Ｚ－１）～（Ｚ－７）中、Ｒは、
　水素原子、
　ハロゲン原子、
　置換基を有していてもよいアルキル基、
　置換基を有していてもよいシクロアルキル基、
　置換基を有していてもよいアルケニル基、
　置換基を有していてもよいシクロアルケニル基、
　置換基を有していてもよいアルキニル基、
　置換基を有していてもよいシクロアルキニル基、
　置換基を有していてもよいアリール基、
　置換基を有していてもよいアルキルオキシ基、
　置換基を有していてもよいシクロアルキルオキシ基、
　置換基を有していてもよいアリールオキシ基、
　置換基を有していてもよいアルキルチオ基、
　置換基を有していてもよいシクロアルキルチオ基、
　置換基を有していてもよいアリールチオ基、
　置換基を有していてもよい１価の複素環基、
　置換基を有していてもよい置換アミノ基、
　置換基を有していてもよいイミン残基、
　置換基を有していてもよいアミド基、
　置換基を有していてもよい酸イミド基、
　置換基を有していてもよい置換オキシカルボニル基、
　シアノ基、
　ニトロ基、
　－Ｃ（＝Ｏ）－Ｒｃで表される基、又は
　－ＳＯ２－Ｒｄで表される基を表し、
　Ｒｃ及びＲｄは、それぞれ独立して、
　水素原子、
　置換基を有していてもよいアルキル基、
　置換基を有していてもよいシクロアルキル基、
　置換基を有していてもよいアリール基、
　置換基を有していてもよいアルキルオキシ基、
　置換基を有していてもよいシクロアルキルオキシ基、
　置換基を有していてもよいアリールオキシ基、又は
　置換基を有していてもよい１価の複素環基を表す。
　式（Ｚ－１）～式（Ｚ－７）中、Ｒが２つある場合、２つあるＲは同一であっても異なっていてもよい。Ｚは、好ましくは式（Ｚ－４）又は式（Ｚ－５）で表される基である。 In formulas (Z-1) to (Z-7), R is
hydrogen atom,
halogen atom,
an alkyl group that may have a substituent,
cycloalkyl group which may have a substituent,
Alkenyl group which may have a substituent,
Cycloalkenyl group which may have a substituent,
an alkynyl group which may have a substituent,
cycloalkynyl group which may have a substituent,
an aryl group which may have a substituent,
an alkyloxy group which may have a substituent,
cycloalkyloxy group which may have a substituent,
an aryloxy group which may have a substituent,
an alkylthio group which may have a substituent,
cycloalkylthio group which may have a substituent,
Arylthio group which may have a substituent,
a monovalent heterocyclic group which may have a substituent,
a substituted amino group which may have a substituent,
imine residue which may have a substituent,
An amide group which may have a substituent,
acid imide group which may have a substituent,
a substituted oxycarbonyl group which may have a substituent,
cyano group,
nitro group,
-C(=O)-R represents a group represented by c , or -SO 2 represents a group represented by R d ,
R c and R d are each independently,
hydrogen atom,
an alkyl group that may have a substituent,
cycloalkyl group which may have a substituent,
an aryl group which may have a substituent,
an alkyloxy group which may have a substituent,
cycloalkyloxy group which may have a substituent,
Represents an aryloxy group which may have a substituent or a monovalent heterocyclic group which may have a substituent.
In formulas (Z-1) to (Z-7), when there are two R's, the two R's may be the same or different. Z is preferably a group represented by formula (Z-4) or formula (Z-5).
　式（Ｚ－１）～（Ｚ－７）中のＲは、好ましくは水素原子、アルキル基、シクロアルキル基、又はアリール基であり、より好ましくは水素原子又はアルキル基であり、更に好ましくは、水素原子又は炭素原子数１～４０のアルキル基であり、より好ましくは水素原子又は炭素原子数１～３０のアルキル基であり、特に好ましくは水素原子又は炭素原子数１～２０のアルキル基である。これらの基は、置換基を有していてもよい。Ｒが複数存在する場合、複数存在するＲは、互いに同一であっても異なっていてもよい。 R in formulas (Z-1) to (Z-7) is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, more preferably a hydrogen atom or an alkyl group, and even more preferably, A hydrogen atom or an alkyl group having 1 to 40 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, and particularly preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. . These groups may have a substituent. When a plurality of R's exist, the plurality of R's may be the same or different.
　式（Ｉ）で表される構成単位は、下記式（Ｉ－１）で表される構成単位であることが好ましい。 The structural unit represented by formula (I) is preferably a structural unit represented by formula (I-1) below.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　式（Ｉ－１）中、Ｚは前記と同様の意味を表す。 In formula (I-1), Z represents the same meaning as above.
　式（Ｉ－１）で表される構成単位の例としては、下記式（５０１）～式（５０５）で表される構成単位が挙げられる。 Examples of the structural unit represented by formula (I-1) include structural units represented by the following formulas (501) to (505).
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　上記式（５０１）～式（５０５）中、Ｒは前記と同様の意味を表す。Ｒが２つ存在する場合、２つのＲは互いに同一であっても異なっていてもよい。 In the above formulas (501) to (505), R represents the same meaning as above. When two R's exist, the two R's may be the same or different.
　式（Ｉ）で表される構成単位は、好ましくは前記式（５０１）で表される基である。 The structural unit represented by formula (I) is preferably a group represented by formula (501) above.
　（式（ＩＩ）で表される構成単位） (Structural unit represented by formula (II))
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　前記式（ＩＩ）中、Ａｒ３は２価の芳香族複素環基を表す。Ａｒ３で表される２価の芳香族複素環基の炭素原子数は、通常２～６０であり、好ましくは４～６０であり、より好ましくは４～２０である。Ａｒ３で表される２価の芳香族複素環基は置換基を有していてもよい。 In the formula (II), Ar 3 represents a divalent aromatic heterocyclic group. The number of carbon atoms in the divalent aromatic heterocyclic group represented by Ar 3 is usually 2 to 60, preferably 4 to 60, more preferably 4 to 20. The divalent aromatic heterocyclic group represented by Ar 3 may have a substituent.
　式（ＩＩ）で表される構成単位としては、下記式（ＩＩ－１）～（ＩＩ－８）のいずれかで表される構成単位が好ましい。 The structural unit represented by formula (II) is preferably a structural unit represented by any of the following formulas (II-1) to (II-8).
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　式（ＩＩ－１）～式（ＩＩ－８）中、Ｘ１及びＸ２は、それぞれ独立して、硫黄原子又は酸素原子を表し、Ｚ１及びＺ２は、それぞれ独立して、＝Ｃ（Ｒ）－で表される基又は窒素原子を表し、Ｒは、式（Ｚ－１）～（Ｚ－７）における定義と同じである。複数存在するＲは、互いに同一であっても異なっていてもよい。 In formulas (II-1) to (II-8), X 1 and X 2 each independently represent a sulfur atom or an oxygen atom, and Z 1 and Z 2 each independently represent =C( R)-- or a nitrogen atom, R is the same as defined in formulas (Z-1) to (Z-7). A plurality of R's may be the same or different.
　式（ＩＩ－６）中、２つのＲは、好ましくは、それぞれ独立して、水素原子、アルキル基、又はハロゲン原子であり、より好ましくは、同時に水素原子又はハロゲン原子であり、更に好ましくは、同時にハロゲン原子である。 In formula (II-6), the two R's are preferably each independently a hydrogen atom, an alkyl group, or a halogen atom, more preferably a hydrogen atom or a halogen atom at the same time, and even more preferably, At the same time, it is a halogen atom.
　原料化合物の入手性の観点から、式（ＩＩ－１）～式（ＩＩ－８）中のＸ１及びＸ２は、いずれも硫黄原子であることが好ましい。 From the viewpoint of availability of raw material compounds, it is preferable that X 1 and X 2 in formulas (II-1) to (II-8) are both sulfur atoms.
　Ａｒ３で表される２価の芳香族複素環基の例としては、下記式（１０１）～式（１９０）で表される基が挙げられる。これらの基は、置換基を有していてもよい。 Examples of the divalent aromatic heterocyclic group represented by Ar 3 include groups represented by the following formulas (101) to (190). These groups may have a substituent.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　式（１０１）～式（１９０）中、Ｒは前記と同じ意味を表す。Ｒが複数存在する場合、複数のＲは、互いに同一であっても異なっていてもよい。 In formulas (101) to (190), R represents the same meaning as above. When a plurality of R's exist, the plurality of R's may be the same or different.
　ｐ型半導体は、前記式（Ｉ）で表される構成単位及び／又は前記式（ＩＩ）で表される構成単位に加えて、アリーレン基を有していてもよい。アリーレン基は、２価の芳香族炭素環基を意味する。アリーレン基は、置換基を有していてもよい。 The p-type semiconductor may have an arylene group in addition to the structural unit represented by the formula (I) and/or the structural unit represented by the formula (II). An arylene group means a divalent aromatic carbocyclic group. The arylene group may have a substituent.
　アリーレン基における、置換基を除いた部分の炭素原子数は、通常６～６０であり、好ましくは６～２０である。置換基を含めたアリーレン基の炭素原子数は、通常６～１００である。 The number of carbon atoms in the arylene group excluding substituents is usually 6 to 60, preferably 6 to 20. The number of carbon atoms in the arylene group including substituents is usually 6 to 100.
　アリーレン基の例としては、フェニレン基、ナフタレン－ジイル基、アントラセン－ジイル基、ビフェニル－ジイル基、ターフェニル－ジイル基、フルオレン－ジイル基、及びベンゾフルオレン－ジイル基が挙げられる。 Examples of the arylene group include a phenylene group, a naphthalene-diyl group, an anthracene-diyl group, a biphenyl-diyl group, a terphenyl-diyl group, a fluorene-diyl group, and a benzofluorene-diyl group.
　ｐ型半導体が、式（Ｉ）で表される構成単位及び／又は式（ＩＩ）で表される構成単位を含む高分子化合物である場合、式（Ｉ）で表される構成単位及び式（ＩＩ）で表される構成単位の合計量は、通常２０～１００モル％であり、ｐ型半導体としての電荷輸送性を向上させるので、好ましくは４０～１００モル％であり、より好ましくは５０～１００モル％である。ただし、高分子化合物が含むすべての構成単位の量を１００モル％とする。 When the p-type semiconductor is a polymer compound containing the structural unit represented by formula (I) and/or the structural unit represented by formula (II), the structural unit represented by formula (I) and the structural unit represented by formula ( The total amount of the structural units represented by II) is usually 20 to 100 mol%, and is preferably 40 to 100 mol%, more preferably 50 to 100 mol%, since it improves charge transport properties as a p-type semiconductor. It is 100 mol%. However, the amount of all structural units contained in the polymer compound is 100 mol%.
　ｐ型半導体の好適な具体例としては、下記の高分子化合物が挙げられる。 Preferred specific examples of the p-type semiconductor include the following polymer compounds.
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　（ｐ型半導体の含有量）
　組成物におけるｐ型半導体の含有量は、必要とされる機能層（活性層）の厚さ、所望の特性等に応じて、任意好適な含有量とすることができる。
　例えば、組成物におけるｐ型半導体の含有量は、組成物を１００質量％として、好ましくは０．１質量％以上、より好ましくは１質量％以上であり、好ましくは２０質量％以下、より好ましくは１０質量％以下である。 (Content of p-type semiconductor)
The content of the p-type semiconductor in the composition can be set to any suitable content depending on the required thickness of the functional layer (active layer), desired characteristics, and the like.
For example, the content of the p-type semiconductor in the composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and preferably 20% by mass or less, more preferably It is 10% by mass or less.
［２．３．ｎ型半導体］
　本実施形態の組成物に含まれるｎ型半導体は、一種単独であっても、二種以上の組み合わせであってもよい。 [2.3. n-type semiconductor]
The n-type semiconductor contained in the composition of this embodiment may be a single type or a combination of two or more types.
　ｎ型半導体は、低分子化合物であっても高分子化合物であってもよい。ｎ型半導体の例としては、オキサジアゾール誘導体、アントラキノジメタン及びその誘導体、ベンゾキノン及びその誘導体、ナフトキノン及びその誘導体、アントラキノン及びその誘導体、テトラシアノアントラキノジメタン及びその誘導体、フルオレノン誘導体、ジフェニルジシアノエチレン及びその誘導体、ジフェノキノン誘導体、８－ヒドロキシキノリン及びその誘導体の金属錯体、Ｃ６０フラーレン等のフラーレン及びその誘導体であるフラーレン誘導体（以下、フラーレン化合物という場合がある。）、並びに、バソクプロイン等のフェナントレン誘導体が挙げられる。 The n-type semiconductor may be a low-molecular compound or a high-molecular compound. Examples of n-type semiconductors include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, and diphenyl. Dicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, fullerenes such as C 60 fullerene and fullerene derivatives thereof (hereinafter sometimes referred to as fullerene compounds), bathocuproine, etc. Examples include phenanthrene derivatives.
　ｎ型半導体は、Ｃ６０フラーレン等のフラーレン及びその誘導体であるフラーレン誘導体であってもよく、非フラーレン化合物であってもよい。以下、フラーレン及びフラーレン誘導体を、フラーレン化合物という場合がある。非フラーレン化合物は、フラーレン及びフラーレン誘導体以外の化合物を意味する。 The n-type semiconductor may be fullerene such as C 60 fullerene and a fullerene derivative thereof, or may be a non-fullerene compound. Hereinafter, fullerene and fullerene derivatives may be referred to as fullerene compounds. A non-fullerene compound means a compound other than fullerene and fullerene derivatives.
　（フラーレン化合物）
　一実施形態において、組成物に含まれるｎ型半導体としては、フラーレン及びフラーレン誘導体から選ばれる１種以上が好ましく、フラーレン誘導体がより好ましい。 (Fullerene compound)
In one embodiment, the n-type semiconductor contained in the composition is preferably one or more selected from fullerene and fullerene derivatives, and more preferably fullerene derivatives.
　フラーレンの例としては、Ｃ６０フラーレン、Ｃ７０フラーレン、Ｃ７６フラーレン、Ｃ７８フラーレン、及びＣ８４フラーレンが挙げられる。フラーレン誘導体の例としては、これらのフラーレンの誘導体が挙げられる。フラーレン誘導体とは、フラーレンの少なくとも一部が修飾された化合物を意味する。 Examples of fullerenes include C 60 fullerene, C 70 fullerene, C 76 fullerene, C 78 fullerene, and C 84 fullerene. Examples of fullerene derivatives include these fullerene derivatives. Fullerene derivative means a compound in which at least a portion of fullerene is modified.
　フラーレン誘導体の例としては、下記式で表される化合物が挙げられる。 Examples of fullerene derivatives include compounds represented by the following formula.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　式中、
　Ｒａは、アルキル基、シクロアルキル基、アリール基、１価の複素環基、又はエステル構造を有する基を表し、これらの基は置換基を有していてもよい。複数あるＲａは、互いに同一であっても異なっていてもよい。
　Ｒｂは、アルキル基、シクロアルキル基、又はアリール基を表し、これらの基は置換基を有していてもよい。複数あるＲｂは、互いに同一であっても異なっていてもよい。 During the ceremony,
R a represents an alkyl group, a cycloalkyl group, an aryl group, a monovalent heterocyclic group, or a group having an ester structure, and these groups may have a substituent. A plurality of R a 's may be the same or different.
R b represents an alkyl group, a cycloalkyl group, or an aryl group, and these groups may have a substituent. A plurality of R b 's may be the same or different.
　Ｒａで表されるエステル構造を有する基の例としては、下記式で表される基が挙げられる。 Examples of the group having an ester structure represented by R a include a group represented by the following formula.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　式中、ｕ１は、１～６の整数を表す。ｕ２は、０～６の整数を表す。Ｒｅは、アルキル基、シクロアルキル基、アリール基、又は１価の複素環基を表し、これらの基は置換基を有していてもよい。 In the formula, u1 represents an integer from 1 to 6. u2 represents an integer from 0 to 6. R e represents an alkyl group, a cycloalkyl group, an aryl group, or a monovalent heterocyclic group, and these groups may have a substituent.
　Ｃ６０フラーレン誘導体の例としては、下記の化合物が挙げられる。 Examples of C 60 fullerene derivatives include the following compounds.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　Ｃ７０フラーレン誘導体の例としては、下記の化合物が挙げられる。 Examples of C70 fullerene derivatives include the following compounds.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　フラーレン誘導体の具体例としては、［６，６］－フェニル－Ｃ６１酪酸メチルエステル（Ｃ６０ＰＣＢＭ、［６，６］－Ｐｈｅｎｙｌ　Ｃ６１　ｂｕｔｙｒｉｃ　ａｃｉｄ　ｍｅｔｈｙｌ　ｅｓｔｅｒ）、［６，６］－フェニル－Ｃ７１酪酸メチルエステル（Ｃ７０ＰＣＢＭ、［６，６］－Ｐｈｅｎｙｌ　Ｃ７１　ｂｕｔｙｒｉｃ　ａｃｉｄ　ｍｅｔｈｙｌ　ｅｓｔｅｒ）、［６，６］－フェニル－Ｃ８５酪酸メチルエステル（Ｃ８４ＰＣＢＭ、［６，６］－Ｐｈｅｎｙｌ　Ｃ８５　ｂｕｔｙｒｉｃ　ａｃｉｄ　ｍｅｔｈｙｌ　ｅｓｔｅｒ）、及び［６，６］－チエニル－Ｃ６１酪酸メチルエステル（［６，６］－Ｔｈｉｅｎｙｌ　Ｃ６１　ｂｕｔｙｒｉｃ　ａｃｉｄ　ｍｅｔｈｙｌ　ｅｓｔｅｒ）が挙げられる。 Specific examples of 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 aci d methyl ester), and [6,6 ]-Thienyl-C61 butyric acid methyl ester ([6,6]-Thienyl C61 butyric acid methyl ester).
　（非フラーレン化合物）
　別の実施形態において、組成物に含まれるｎ型半導体は、非フラーレン化合物であることが好ましい。非フラーレン化合物としては、多種の化合物が公知であり、従来公知の任意好適な非フラーレン化合物を本実施形態においてｎ型半導体として用いることができる。 (Non-fullerene compound)
In another embodiment, the n-type semiconductor contained in the composition is preferably a non-fullerene compound. Various kinds of compounds are known as non-fullerene compounds, and any conventionally known suitable non-fullerene compounds can be used as the n-type semiconductor in this embodiment.
　一実施形態において、組成物に含まれるｎ型半導体は、ペリレンテトラカルボン酸ジイミド構造を含む化合物であることが好ましい。非フラーレン化合物であるペリレンテトラカルボン酸ジイミド構造を含む化合物の例としては、下記式で表される化合物が挙げられる。 In one embodiment, the n-type semiconductor contained in the composition is preferably a compound containing a perylenetetracarboxylic acid diimide structure. Examples of compounds containing a perylenetetracarboxylic acid diimide structure that are non-fullerene compounds include compounds represented by the following formula.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
　式中、Ｒは、前記定義のとおりである。複数あるＲは、互いに同一であっても異なっていてもよい。 In the formula, R is as defined above. A plurality of R's may be the same or different.
　一実施形態において、ｎ型半導体は、好ましくは、下記式（Ｖ）で表される化合物である。下記式（Ｖ）で表される化合物は、ペリレンテトラカルボン酸ジイミド構造を含む非フラーレン化合物である。 In one embodiment, the n-type semiconductor is preferably a compound represented by the following formula (V). The compound represented by the following formula (V) is a non-fullerene compound containing a perylenetetracarboxylic acid diimide structure.
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
　前記式（Ｖ）中、Ｒ１は、水素原子、ハロゲン原子、置換基を有していてもよいアルキル基、置換基を有していてもよいシクロアルキル基、置換基を有していてもよいアルキルオキシ基、置換基を有していてもよいシクロアルキルオキシ基、置換基を有していてもよいアリール基、又は置換基を有していてもよい１価の芳香族複素環基を表す。複数あるＲ１は互いに同一であっても異なっていてもよい。 In the formula (V), R 1 is a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, or a cycloalkyl group that may have a substituent. A good alkyloxy group, a cycloalkyloxy group that may have a substituent, an aryl group that may have a substituent, or a monovalent aromatic heterocyclic group that may have a substituent. represent. A plurality of R 1 's may be the same or different.
　好ましくは、複数あるＲ１は、それぞれ独立して、置換基を有していてもよいアルキル基である。 Preferably, each of the plurality of R 1 's independently represents an alkyl group which may have a substituent.
　Ｒ２は、水素原子、ハロゲン原子、置換基を有していてもよいアルキル基、置換基を有していてもよいシクロアルキル基、置換基を有していてもよいアルキルオキシ基、置換基を有していてもよいシクロアルキルオキシ基、置換基を有していてもよいアリール基、又は置換基を有していてもよい１価の芳香族複素環基を表す。複数あるＲ２は同一であっても異なっていてもよい。 R2 is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkyloxy group, a substituent represents a cycloalkyloxy group which may have a substituent, an aryl group which may have a substituent, or a monovalent aromatic heterocyclic group which may have a substituent. A plurality of R 2 may be the same or different.
　別の実施形態において、ｎ型半導体は、下記式（ＶＩ）で表される化合物であることが好ましい。

　Ａ１－Ｂ１０－Ａ２　（ＶＩ）
In another embodiment, the n-type semiconductor is preferably a compound represented by the following formula (VI).

A 1 -B 10 -A 2 (VI)
　式（ＶＩ）中、
　Ａ１及びＡ２は、それぞれ独立に、電子求引性の基を表し、Ｂ１０は、π共役系を含む基を表す。 In formula (VI),
A 1 and A 2 each independently represent an electron-withdrawing group, and B 10 represents a group containing a π-conjugated system.
　Ａ１及びＡ２である電子求引性の基の例としては、－ＣＨ＝Ｃ（－ＣＮ）２で表される基、及び下記式（ａ－１）～式（ａ－９）で表される基が挙げられる。 Examples of electron-withdrawing groups that are A 1 and A 2 include groups represented by -CH=C(-CN) 2 and groups represented by the following formulas (a-1) to (a-9). The following groups are mentioned.
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
　式（ａ－１）～式（ａ－７）中、
　Ｔは、置換基を有していてもよい炭素環、又は置換基を有していてもよい複素環を表す。炭素環及び複素環は、単環であってもよく、縮合環であってもよい。これらの環が置換基を複数有する場合、複数ある置換基は、同一であっても異なっていてもよい。 In formulas (a-1) to (a-7),
T represents a carbocycle which may have a substituent or a heterocycle which may have a substituent. Carbocycles and heterocycles may be monocyclic or fused rings. When these rings have multiple substituents, the multiple substituents may be the same or different.
　Ｔである置換基を有していてもよい炭素環の例としては、芳香族炭素環が挙げられ、好ましくは芳香族炭素環である。Ｔである置換基を有していてもよい炭素環の具体例としては、ベンゼン環、ナフタレン環、アントラセン環、テトラセン環、ペンタセン環、ピレン環、及びフェナントレン環が挙げられ、好ましくはベンゼン環、ナフタレン環、及びフェナントレン環であり、より好ましくはベンゼン環及びナフタレン環であり、更に好ましくはベンゼン環である。これらの環は、置換基を有していてもよい。 Examples of the carbocycle which may have a substituent which is T include an aromatic carbocycle, and preferably an aromatic carbocycle. Specific examples of the carbocyclic ring which may have a substituent which is T include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a pyrene ring, and a phenanthrene ring, preferably a benzene ring, They are a naphthalene ring and a phenanthrene ring, more preferably a benzene ring and a naphthalene ring, and still more preferably a benzene ring. These rings may have a substituent.
　Ｔである置換基を有していてもよい複素環の例としては、芳香族複素環が挙げられ、好ましくは芳香族複素環である。Ｔである置換基を有していてもよい複素環の具体例としては、ピリジン環、ピリダジン環、ピリミジン環、ピラジン環、ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、及びチエノチオフェン環が挙げられ、好ましくはチオフェン環、ピリジン環、ピラジン環、チアゾール環、及びチエノチオフェン環であり、より好ましくはチオフェン環である。これらの環は、置換基を有していてもよい。 Examples of the heterocycle which may have a substituent which is T include an aromatic heterocycle, and preferably an aromatic heterocycle. Specific examples of the heterocycle which may have a substituent which is T include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, and a thienothiophene ring, preferably a thiophene ring, a pyridine ring, a pyrazine ring, a thiazole ring, and a thienothiophene ring, and more preferably a thiophene ring. These rings may have a substituent.
　Ｔである炭素環又は複素環が有し得る置換基の例としては、ハロゲン原子、アルキル基、アルキルオキシ基、アリール基、及び１価の複素環基が挙げられ、好ましくはフッ素原子、及び／又は炭素原子数１～６のアルキル基である。 Examples of substituents that the carbocyclic or heterocyclic ring T may have include a halogen atom, an alkyl group, an alkyloxy group, an aryl group, and a monovalent heterocyclic group, preferably a fluorine atom and/or or an alkyl group having 1 to 6 carbon atoms.
　Ｘ４、Ｘ５、及びＸ６は、それぞれ独立して、酸素原子、硫黄原子、アルキリデン基、又は＝Ｃ（－ＣＮ）２で表される基を表し、好ましくは、酸素原子、硫黄原子、又は＝Ｃ（－ＣＮ）２で表される基である。 X 4 , X 5 , and X 6 each independently represent an oxygen atom, a sulfur atom, an alkylidene group, or a group represented by =C(-CN) 2 , and preferably represent an oxygen atom, a sulfur atom, or a group represented by =C(-CN) 2 .
　Ｘ７は、水素原子、ハロゲン原子、シアノ基、置換基を有していてもよいアルキル基、置換基を有していてもよいアルキルオキシ基、置換基を有していてもよいアリール基又は１価の複素環基を表す。 X 7 is a hydrogen atom, a halogen atom, a cyano group, an alkyl group that may have a substituent, an alkyloxy group that may have a substituent, an aryl group that may have a substituent, or Represents a monovalent heterocyclic group.
　Ｒａ１、Ｒａ２、Ｒａ３、Ｒａ４、及びＲａ５は、それぞれ独立して、水素原子、置換基を有していてもよいアルキル基、ハロゲン原子、置換基を有していてもよいアルキルオキシ基、置換基を有していてもよいアリール基又は１価の複素環基を表し、好ましくは、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基である。 R a1 , R a2 , R a3 , R a4 , and R a5 each independently represent a hydrogen atom, an optionally substituted alkyl group, a halogen atom, and an optionally substituted alkyl group. Represents an oxy group, an aryl group that may have a substituent, or a monovalent heterocyclic group, preferably an alkyl group that may have a substituent or an aryl group that may have a substituent It is.
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
　式（ａ－８）及び式（ａ－９）中、Ｒａ６及びＲａ７は、それぞれ独立して、水素原子、ハロゲン原子、置換基を有していてもよいアルキル基、置換基を有していてもよいシクロアルキル基、置換基を有していてもよいアルキルオキシ基、置換基を有していてもよいシクロアルキルオキシ基、置換基を有していてもよい１価の芳香族炭素環基、又は置換基を有していてもよい１価の芳香族複素環基を表し、複数あるＲａ６及びＲａ７は、同一であっても異なっていてもよい。 In formula (a-8) and formula (a-9), R a6 and R a7 are each independently a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, or a substituent. a cycloalkyl group that may have a substituent, an alkyloxy group that may have a substituent, a cycloalkyloxy group that may have a substituent, a monovalent aromatic carbon that may have a substituent It represents a cyclic group or a monovalent aromatic heterocyclic group which may have a substituent, and a plurality of R a6 and R a7 may be the same or different.
　Ａ１及びＡ２である電子求引性の基としては、下記の式（ａ－１－１）～式（ａ－１－４）並びに式（ａ－６－１）及び式（ａ－７－１）のいずれかで表される基が好ましく、式（ａ－１－１）で表される基がより好ましい。ここで、複数あるＲａ１０は、それぞれ独立して、水素原子又は置換基を表し、好ましくは水素原子、ハロゲン原子、シアノ基、又は置換基を有していてもよいアルキル基を表す。Ｒａ３、Ｒａ４、及びＲａ５は、それぞれ独立して、前記と同義であり、好ましくはそれぞれ独立して置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表す。 The electron-withdrawing groups A 1 and A 2 include the following formulas (a-1-1) to (a-1-4), formula (a-6-1) and formula (a-7). A group represented by any of formula (a-1-1) is preferred, and a group represented by formula (a-1-1) is more preferred. Here, each of the plural R a10 's independently represents a hydrogen atom or a substituent, and preferably represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent. R a3 , R a4 , and R a5 each independently have the same meaning as above, and preferably each independently represents an alkyl group that may have a substituent or an aryl group that may have a substituent. represents a group.
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
　Ｂ１０であるπ共役系を含む基の例としては、後述する式（ＶＩＩ）で表される化合物における、－（Ｓ１）ｎ１－Ｂ１１－（Ｓ２）ｎ２－で表される基が挙げられる。 An example of a group containing a π-conjugated system that is B 10 is a group represented by -(S 1 ) n1 -B 11 -(S 2 ) n2 - in a compound represented by formula (VII) described below. Can be mentioned.
　本実施形態において、ｎ型半導体は、下記式（ＶＩＩ）で表される化合物であることが好ましい。

Ａ１－（Ｓ１）ｎ１－Ｂ１１－（Ｓ２）ｎ２－Ａ２　（ＶＩＩ）
　 In this embodiment, the n-type semiconductor is preferably a compound represented by the following formula (VII).

A 1 -(S 1 ) n1 -B 11 -(S 2 ) n2 -A 2 (VII)
　式（ＶＩＩ）中、Ａ１及びＡ２は、それぞれ独立に、電子求引性の基を表す。Ａ１及びＡ２の例及び好ましい例は、前記式（ＶＩ）におけるＡ１及びＡ２について説明した例及び好ましい例と同様である。 In formula (VII), A 1 and A 2 each independently represent an electron-withdrawing group. Examples and preferred examples of A 1 and A 2 are the same as those described for A 1 and A 2 in formula (VI) above.
　Ｓ１及びＳ２は、それぞれ独立に、置換基を有していてもよい２価の炭素環基、置換基を有していてもよい２価の複素環基、－Ｃ（Ｒｓ１）＝Ｃ（Ｒｓ２）－で表される基（ここで、Ｒｓ１及びＲｓ２は、それぞれ独立に、水素原子、又は置換基（好ましくは、水素原子、ハロゲン原子、置換基を有していてもよいアルキル基、又は置換基を有していてもよい１価の複素環基）を表す。）、又は－Ｃ≡Ｃ－で表される基を表す。 S 1 and S 2 each independently represent a divalent carbocyclic group which may have a substituent, a divalent heterocyclic group which may have a substituent, -C(R s1 )= A group represented by C(R s2 )- (where R s1 and R s2 are each independently a hydrogen atom or a substituent (preferably a hydrogen atom, a halogen atom, or a substituent) represents a good alkyl group or a monovalent heterocyclic group which may have a substituent), or a group represented by -C≡C-.
　Ｓ１及びＳ２で表される、置換基を有していてもよい２価の炭素環基及び置換基を有していてもよい２価の複素環基は、縮合環であってもよい。２価の炭素環基又は２価の複素環基が、複数の置換基を有する場合、複数ある置換基は、同一であっても異なっていてもよい。 The optionally substituted divalent carbocyclic group and the optionally substituted divalent heterocyclic group represented by S 1 and S 2 may be a fused ring. . When a divalent carbocyclic group or a divalent heterocyclic group has a plurality of substituents, the plurality of substituents may be the same or different.
　式（ＶＩＩ）中、ｎ１及びｎ２は、それぞれ独立に、０以上の整数を表し、好ましくはそれぞれ独立に、０又は１を表し、より好ましくは、同時に０又は１を表す。 In formula (VII), n1 and n2 each independently represent an integer of 0 or more, preferably each independently represents 0 or 1, and more preferably represents 0 or 1 at the same time.
　２価の炭素環基の例としては、２価の芳香族炭素環基が挙げられる。
　２価の複素環基の例としては、２価の芳香族複素環基が挙げられる。
　２価の芳香族炭素環基又は２価の芳香族複素環基が縮合環である場合、縮合環を構成する環の全部が芳香族性を有する縮合環であってもよく、一部のみが芳香族性を有する縮合環であってもよい。 Examples of divalent carbocyclic groups include divalent aromatic carbocyclic groups.
Examples of divalent heterocyclic groups include divalent aromatic heterocyclic groups.
When the divalent aromatic carbocyclic group or the divalent aromatic heterocyclic group is a condensed ring, all of the rings constituting the condensed ring may be aromatic, or only some of the rings may be aromatic. It may be a condensed ring having aromaticity.
　Ｓ１及びＳ２の例としては、既に説明したＡｒ３で表される２価の芳香族複素環基の例として挙げられた式（１０１）～（１９０）のいずれかで表される基、及びこれらの基における水素原子が置換基で置換された基が挙げられる。 Examples of S 1 and S 2 include groups represented by any of the formulas (101) to (190) listed as examples of the divalent aromatic heterocyclic group represented by Ar 3 as described above; and groups in which hydrogen atoms in these groups are substituted with substituents.
　Ｓ１及びＳ２は、好ましくは、それぞれ独立に、下記式（ｓ－１）又は（ｓ－２）で表される基を表す。 S 1 and S 2 preferably each independently represent a group represented by the following formula (s-1) or (s-2).
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
　式（ｓ－１）及び（ｓ－２）中、
　Ｘ３は、酸素原子又は硫黄原子を表す。
　Ｒａ１０は、前記定義のとおりである。 In formulas (s-1) and (s-2),
X 3 represents an oxygen atom or a sulfur atom.
R a10 is as defined above.
　Ｓ１及びＳ２は、好ましくは、それぞれ独立に、式（１４２）、式（１４８）、若しくは式（１８４）で表される基、又はこれらの基における水素原子が置換基で置換された基であり、より好ましくは、前記式（１４２）若しくは式（１８４）で表される基、又は式（１８４）で表される基における１つの水素原子が、アルキルオキシ基で置換された基である。 S 1 and S 2 are preferably each independently a group represented by formula (142), formula (148), or formula (184), or a group in which the hydrogen atom in these groups is substituted with a substituent. More preferably, one hydrogen atom in the group represented by formula (142) or formula (184) or the group represented by formula (184) is substituted with an alkyloxy group. .
　Ｂ１１は、炭素環構造及び複素環構造からなる群から選択された２以上の構造の縮合環基であり、かつオルト－ペリ縮合構造を含まない縮合環基であり、かつ置換基を有していてもよい縮合環基を表す。 B11 is a fused ring group having two or more structures selected from the group consisting of a carbocyclic structure and a heterocyclic structure, and is a fused ring group that does not contain an ortho-perifused structure, and has a substituent. represents a fused ring group that may be fused.
　Ｂ１１で表される縮合環基は、互いに同一である２以上の構造を縮合した構造を含んでいてもよい。 The fused ring group represented by B 11 may include a structure in which two or more mutually identical structures are condensed.
　Ｂ１１で表される縮合環基が複数の置換基を有する場合、複数ある置換基は、同一であっても異なっていてもよい。 When the fused ring group represented by B 11 has a plurality of substituents, the plurality of substituents may be the same or different.
　Ｂ１１で表される縮合環基を構成し得る炭素環構造の例としては、下記式（Ｃｙ１）又は式（Ｃｙ２）で表される環構造が挙げられる。 Examples of carbocyclic structures that can constitute the fused ring group represented by B 11 include ring structures represented by the following formula (Cy1) or (Cy2).
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
　Ｂ１１で表される縮合環基を構成し得る複素環構造の例としては、下記式（Ｃｙ３）～式（Ｃｙ１０）のいずれかで表される環構造が挙げられる。 Examples of the heterocyclic structure that can constitute the fused ring group represented by B 11 include ring structures represented by any of the following formulas (Cy3) to (Cy10).
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
　式（ＶＩＩ）中、Ｂ１１は、好ましくは、前記式（Ｃｙ１）～式（Ｃｙ１０）で表される構造からなる群から選択された２以上の構造の縮合環基であって、オルト－ペリ縮合構造を含まない縮合環基であり、かつ置換基を有していてもよい縮合環基である。Ｂ１１は、式（Ｃｙ１）～式（Ｃｙ１０）で表される構造のうち、２以上の同一の構造が縮合した構造を含んでいてもよい。 In formula (VII), B 11 is preferably a fused ring group having two or more structures selected from the group consisting of the structures represented by formulas (Cy1) to (Cy10), and is ortho-peripheral. It is a fused ring group that does not contain a fused structure and may have a substituent. B 11 may include a structure in which two or more of the same structures among the structures represented by formulas (Cy1) to (Cy10) are condensed.
　Ｂ１１は、より好ましくは、式（Ｃｙ１）～式（Ｃｙ６）及び式（Ｃｙ８）で表される構造からなる群から選択された２以上の構造の縮合環基であって、オルト－ペリ縮合構造を含まない縮合環基であり、かつ置換基を有していてもよい縮合環基である。 B 11 is more preferably a fused ring group having two or more structures selected from the group consisting of structures represented by formulas (Cy1) to (Cy6) and formula (Cy8), and is an ortho-pericondensed ring group. It is a fused ring group that does not contain any structure and may have a substituent.
　Ｂ１１である縮合環基が有していてもよい置換基は、好ましくは置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルキルオキシ基、及び置換基を有していてもよい１価の複素環基である。Ｂ１１で表される縮合環基が有していてもよいアリール基は、例えば、アルキル基により置換されていてもよい。 The substituent that the fused ring group B11 may have is preferably an alkyl group that may have a substituent, an aryl group that may have a substituent, or an aryl group that may have a substituent. an optionally substituted alkyloxy group, and a monovalent heterocyclic group optionally having a substituent. The aryl group that the fused ring group represented by B 11 may have may be substituted with, for example, an alkyl group.
　Ｂ１１である縮合環基の例としては、下記式（ｂ－１）～式（ｂ－１４）で表される基、及びこれらの基における水素原子が、置換基（好ましくは、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルキルオキシ基、又は置換基を有していてもよい１価の複素環基）で置換された基が挙げられる。 Examples of the fused ring group that is B 11 include groups represented by formulas (b-1) to (b-14) below, and hydrogen atoms in these groups that have a substituent (preferably a substituent). An alkyl group that may have an optional substituent, an aryl group that may have a substituent, an alkyloxy group that may have a substituent, or a monovalent heterocyclic group that may have a substituent ) is included.
　Ｂ１１である縮合環基としては、下記式（ｂ－２）又は（ｂ－３）で表される基、又はこれらの基における水素原子が、置換基（好ましくは、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、置換基を有していてもよいアルキルオキシ基、又は置換基を有していてもよい１価の複素環基）で置換された基が好ましく、下記式（ｂ－２）又は（ｂ－３）で表される基がより好ましい。 The fused ring group B11 is a group represented by the following formula (b-2) or (b-3), or a hydrogen atom in these groups has a substituent (preferably a substituent). an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkyloxy group, or an optionally substituted monovalent heterocyclic group) A group represented by the following formula (b-2) or (b-3) is more preferable.
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
　式（ｂ－１）～式（ｂ－１４）中、
　Ｒａ１０は、前記定義のとおりである。
　式（ｂ－１）～式（ｂ－１４）中、複数あるＲａ１０は、それぞれ独立して、好ましくは置換基を有していてもよいアルキル基、又は置換基を有していてもよいアリール基である。 In formulas (b-1) to (b-14),
R a10 is as defined above.
In formulas (b-1) to formula (b-14), each of the plurality of R a10s is preferably an alkyl group that may have a substituent, or an alkyl group that may have a substituent. It is an aryl group.
　式（ＶＩ）又は式（ＶＩＩ）で表される化合物の例としては、下記式で表される化合物が挙げられる。 Examples of the compound represented by formula (VI) or formula (VII) include compounds represented by the following formula.
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
　上記式中、Ｒは、前記定義のとおりであり、Ｘは、水素原子、ハロゲン原子、シアノ基又は置換基を有していてもよいアルキル基を表す。
　上記式中、Ｒは、好ましくは水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基又は置換基を有していてもよいアルキルオキシ基である。 In the above formula, R is as defined above, and X represents a hydrogen atom, a halogen atom, a cyano group, or an alkyl group which may have a substituent.
In the above formula, R is preferably a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkyloxy group. .
　組成物は、ｎ型半導体として、非フラーレン化合物のみを含んでいてもよく、フラーレン化合物のみを含んでいてもよく、非フラーレン化合物とフラーレン化合物とを組み合わせて含んでいてもよい。 The composition may contain only a non-fullerene compound, only a fullerene compound, or a combination of a non-fullerene compound and a fullerene compound as an n-type semiconductor.
　組成物に含まれるｎ型半導体の好適な具体例として、下記式で表される化合物が挙げられる。 A preferred specific example of the n-type semiconductor contained in the composition is a compound represented by the following formula.
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
　（ｎ型半導体の含有量）
　組成物におけるｎ型半導体の含有量は、必要とされる機能層（活性層）の厚さ、所望の特性等に応じて、任意好適な含有量とすることができる。
　例えば、組成物におけるｎ型半導体の含有量は、組成物を１００質量％として、好ましくは０．１質量％以上、より好ましくは１質量％以上であり、好ましくは２０質量％以下、より好ましくは１０質量％以下である。 (N-type semiconductor content)
The content of the n-type semiconductor in the composition can be set to any suitable content depending on the required thickness of the functional layer (active layer), desired characteristics, and the like.
For example, the content of the n-type semiconductor in the composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and preferably 20% by mass or less, more preferably It is 10% by mass or less.
　（ｐ型半導体のｎ型半導体に対する質量比（ｐ型半導体／ｎ型半導体））
　組成物中のｐ型半導体のｎ型半導体に対する質量比（ｐ型半導体／ｎ型半導体）は、好ましくは１／９以上であり、より好ましくは１／５以上であり、更に好ましくは１／３以上であり、好ましくは９／１以下であり、より好ましくは５／１以下であり、更に好ましくは３／１以下である。ここで、当該質量比は、組成物がｐ型半導体を複数種含む場合は、ｐ型半導体の総質量についての比であり、組成物がｎ型半導体を複数種含む場合は、ｎ型半導体の総質量についての比である。 (Mass ratio of p-type semiconductor to n-type semiconductor (p-type semiconductor/n-type semiconductor))
The mass ratio of the p-type semiconductor to the n-type semiconductor in the composition (p-type semiconductor/n-type semiconductor) is preferably 1/9 or more, more preferably 1/5 or more, and even more preferably 1/3. or more, preferably 9/1 or less, more preferably 5/1 or less, still more preferably 3/1 or less. Here, the mass ratio is a ratio of the total mass of p-type semiconductors when the composition includes multiple types of p-type semiconductors, and a ratio of the total mass of the p-type semiconductors when the composition includes multiple types of n-type semiconductors. It is a ratio with respect to the total mass.
［２．４．溶媒］
　本実施形態の組成物に含まれる溶媒は、一種単独でもよく、二種以上の組み合わせであってもよい。 [2.4. solvent]
The solvents contained in the composition of this embodiment may be used alone or in combination of two or more.
　本実施形態の組成物は、溶媒として、芳香族炭化水素を含んでいてもよく、芳香族炭化水素を含むことが好ましい。当該芳香族炭化水素は置換基を有していてもよい。芳香族炭化水素としては、特に既に説明したｐ型半導体を溶解させることができる化合物であることが好ましい。 The composition of this embodiment may contain an aromatic hydrocarbon as a solvent, and preferably contains an aromatic hydrocarbon. The aromatic hydrocarbon may have a substituent. The aromatic hydrocarbon is preferably a compound that can dissolve the p-type semiconductor described above.
　溶媒として用いられうる芳香族炭化水素としては、例えば、トルエン、キシレン（例、ｏ－キシレン、ｍ－キシレン、ｐ－キシレン）、トリメチルベンゼン（例、メシチレン、１，２，４－トリメチルベンゼン（プソイドクメン））、ブチルベンゼン（例、ｎ－ブチルベンゼン、ｓｅｃ－ブチルベンゼン、ｔｅｒｔ－ブチルベンゼン）、メチルナフタレン（例、１－メチルナフタレン）、１，２，３，４－テトラヒドロナフタレン（テトラリン）、インダン、１－クロロナフタレン、クロロベンゼン及びジクロロベンゼン（１，２－ジクロロベンゼン）が挙げられる。 Examples of aromatic hydrocarbons that can be used as solvents include toluene, xylene (e.g. o-xylene, m-xylene, p-xylene), trimethylbenzene (e.g. mesitylene, 1,2,4-trimethylbenzene (pseudocumene), )), butylbenzene (e.g., n-butylbenzene, sec-butylbenzene, tert-butylbenzene), methylnaphthalene (e.g., 1-methylnaphthalene), 1,2,3,4-tetrahydronaphthalene (tetralin), indan , 1-chloronaphthalene, chlorobenzene and dichlorobenzene (1,2-dichlorobenzene).
　溶媒は、１種のみの芳香族炭化水素から構成されていても、２種以上の芳香族炭化水素から構成されていてもよい。 The solvent may be composed of only one type of aromatic hydrocarbon, or may be composed of two or more types of aromatic hydrocarbons.
　溶媒を構成しうる芳香族炭化水素は、好ましくは、トルエン、ｏ－キシレン、ｍ－キシレン、ｐ－キシレン、メシチレン、１，２，４－トリメチルベンゼン、ｎ－ブチルベンゼン、ｓｅｃ－ブチルベンゼン、ｔｅｒｔ－ブチルベンゼン、メチルナフタレン、テトラリン、１－クロロナフタレン、クロロベンゼン及びジクロロベンゼン（１，２－ジクロロベンゼン）からなる群から選択される１種以上である。 Aromatic hydrocarbons that can constitute the solvent are preferably toluene, o-xylene, m-xylene, p-xylene, mesitylene, 1,2,4-trimethylbenzene, n-butylbenzene, sec-butylbenzene, tert - One or more selected from the group consisting of butylbenzene, methylnaphthalene, tetralin, 1-chloronaphthalene, chlorobenzene, and dichlorobenzene (1,2-dichlorobenzene).
　溶媒中の芳香族炭化水素溶媒の含有量は、溶媒の総質量を１００質量％として、好ましくは８０質量％以上、より好ましくは９０質量％以上であり、通常１００質量％以下である。 The content of the aromatic hydrocarbon solvent in the solvent is preferably 80% by mass or more, more preferably 90% by mass or more, and usually 100% by mass or less, based on the total mass of the solvent as 100% by mass.
　本実施形態の組成物は、溶媒として、ハロゲン化アルキルを含んでいてもよい。溶媒として用いられうるハロゲン化アルキルとしては、例えば、クロロホルムが挙げられる。 The composition of this embodiment may contain an alkyl halide as a solvent. Examples of the alkyl halide that can be used as a solvent include chloroform.
　本実施形態の組成物は、前記の溶媒に加えて、特にｎ型半導体の溶解性を高める観点から選択されるさらなる溶媒を組み合わせて用いてもよい。 In addition to the above-mentioned solvents, the composition of the present embodiment may be used in combination with an additional solvent selected from the viewpoint of particularly increasing the solubility of the n-type semiconductor.
　本実施形態において、さらなる溶媒の例としては、芳香族カルボニル化合物、芳香族エステル化合物及び含窒素複素環式化合物が挙げられる。本実施形態の組成物は、溶媒として、芳香族カルボニル化合物、芳香族エステル化合物及び含窒素複素環式化合物からなる群より選択される一種又は二種以上の化合物を含んでいてもよい。 In this embodiment, examples of further solvents include aromatic carbonyl compounds, aromatic ester compounds, and nitrogen-containing heterocyclic compounds. The composition of the present embodiment may contain, as a solvent, one or more compounds selected from the group consisting of aromatic carbonyl compounds, aromatic ester compounds, and nitrogen-containing heterocyclic compounds.
　芳香族カルボニル化合物としては、例えば、アセトフェノン、プロピオフェノン、ブチロフェノン、シクロへキシルフェニルケトン、ベンゾフェノンが挙げられ、これらの化合物は置換基を有していてもよい。 Examples of the aromatic carbonyl compound include acetophenone, propiophenone, butyrophenone, cyclohexylphenyl ketone, and benzophenone, and these compounds may have a substituent.
　芳香族エステル化合物としては、例えば、安息香酸メチル、安息香酸エチル、安息香酸プロピル、安息香酸ブチル、安息香酸イソプロピル、安息香酸ベンジル、安息香酸シクロへキシル、安息香酸フェニルが挙げられ、これらの化合物は置換基を有していてもよい。 Examples of aromatic ester compounds include methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isopropyl benzoate, benzyl benzoate, cyclohexyl benzoate, and phenyl benzoate. It may have a substituent.
　含窒素複素環式化合物としては、例えば、ピリジン、キノリン、キノキサリン、１，２，３，４－テトラヒドロキノリン、ピリミジン、ピラジン、及びキナゾリンが挙げられ、これらの含窒素複素環式化合物は置換基を有していてもよい。 Examples of nitrogen-containing heterocyclic compounds include pyridine, quinoline, quinoxaline, 1,2,3,4-tetrahydroquinoline, pyrimidine, pyrazine, and quinazoline, and these nitrogen-containing heterocyclic compounds have a substituent. may have.
　含窒素複素環式化合物は、環構造に直接的に結合する置換基を有していてもよい。含窒素複素環式化合物の環構造が有していてもよい置換基としては、例えば、炭素原子数１～５のアルキル基、炭素原子数１～５のアルコキシ基、ハロゲン原子、及びアルキルチオ基が挙げられる。 The nitrogen-containing heterocyclic compound may have a substituent directly bonded to the ring structure. Examples of substituents that the ring structure of the nitrogen-containing heterocyclic compound may have include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, and an alkylthio group. Can be mentioned.
　本実施形態の組成物に含まれる溶媒の総質量は、組成物の全質量を１００質量％としたときに、ｐ型半導体及びｎ型半導体の溶解性をより向上させる観点から、好ましくは９０質量％以上であり、より好ましくは９２質量％以上であり、更に好ましくは９５質量％以上であり、組成物中のｐ型半導体及びｎ型半導体の濃度をより高くして一定の厚さ以上の層を形成し易くする観点から、好ましくは９９．９質量％以下である。 The total mass of the solvent contained in the composition of this embodiment is preferably 90% by mass from the viewpoint of further improving the solubility of the p-type semiconductor and the n-type semiconductor, when the total mass of the composition is 100% by mass. % or more, more preferably 92% by mass or more, still more preferably 95% by mass or more, and the concentration of the p-type semiconductor and n-type semiconductor in the composition is increased to form a layer with a certain thickness or more. From the viewpoint of making it easier to form, the content is preferably 99.9% by mass or less.
［２．５．任意成分］
　本実施形態に係る組成物は、前記のｐ型半導体、ｎ型半導体、界面活性剤、及び溶媒に加えて、本発明の目的及び効果を損なわない限度において、任意の成分を含んでいてもよい。任意の成分の例としては、紫外線吸収剤、酸化防止剤、吸収した光により電荷を発生させる機能を増感するための増感剤、及び紫外線からの安定性を増すための光安定剤が挙げられる。 [2.5. Optional ingredients]
In addition to the above-mentioned p-type semiconductor, n-type semiconductor, surfactant, and solvent, the composition according to the present embodiment may contain arbitrary components as long as the objects and effects of the present invention are not impaired. . Examples of optional ingredients include UV absorbers, antioxidants, sensitizers to enhance the ability of absorbed light to generate a charge, and photostabilizers to increase stability from UV radiation. It will be done.
　組成物における任意成分の合計の含有量は、好ましくは１０質量％以下、より好ましくは５質量％以下であり、通常０質量％以上であり、０質量％であってもよい。 The total content of optional components in the composition is preferably 10% by mass or less, more preferably 5% by mass or less, and usually 0% by mass or more, and may be 0% by mass.
［２．６．組成物の性状など］
　組成物中、ｐ型半導体及びｎ型半導体は溶解していても分散していてもよい。組成物中、ｐ型半導体及びｎ型半導体は、少なくとも一部が溶解していることが好ましい。 [2.6. Properties of the composition, etc.]
In the composition, the p-type semiconductor and the n-type semiconductor may be dissolved or dispersed. It is preferable that at least a portion of the p-type semiconductor and the n-type semiconductor be dissolved in the composition.
　本実施形態の組成物における、ｐ型半導体及びｎ型半導体の合計の濃度は、必要とされる機能層（活性層）の厚さ、所望の特性等に応じて、任意好適な濃度とすることができる。ｐ型半導体及びｎ型半導体の合計の濃度は、好ましくは０．０１質量％以上であり、より好ましくは０．１質量％以上であり、好ましくは１０質量％以下であり、より好ましくは５質量％以下であり、更に好ましくは０．０１質量％以上２０質量％以下であり、更に好ましくは０．０１質量％以上１０質量％以下であり、更に好ましくは０．０１質量％以上５質量％以下であり、特に好ましくは０．１質量％以上５質量％以下である。 The total concentration of the p-type semiconductor and n-type semiconductor in the composition of this embodiment can be set to any suitable concentration depending on the required thickness of the functional layer (active layer), desired characteristics, etc. I can do it. The total concentration of the p-type semiconductor and the n-type semiconductor is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, preferably 10% by mass or less, and more preferably 5% by mass. % or less, more preferably 0.01% by mass or more and 20% by mass or less, still more preferably 0.01% by mass or more and 10% by mass or less, even more preferably 0.01% by mass or more and 5% by mass or less. The content is particularly preferably 0.1% by mass or more and 5% by mass or less.
［２．７．組成物の製造方法］
　組成物は、従来公知の方法により製造することができる。溶媒と、ｐ型半導体、ｎ型半導体、及び界面活性剤とを、溶媒の沸点以下の温度まで加温して混合してもよい。 [2.7. Method for producing composition]
The composition can be manufactured by a conventionally known method. The solvent, p-type semiconductor, n-type semiconductor, and surfactant may be mixed by heating to a temperature below the boiling point of the solvent.
　溶媒と、ｐ型半導体、ｎ型半導体、及び界面活性剤とを混合した後、得られた混合物をフィルターを用いて濾過し、得られた濾液を組成物としてよい。フィルターとしては、例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）等のフッ素樹脂で形成されたフィルターを用いることができる。 After mixing the solvent, the p-type semiconductor, the n-type semiconductor, and the surfactant, the resulting mixture may be filtered using a filter, and the resulting filtrate may be used as a composition. As the filter, for example, a filter made of a fluororesin such as polytetrafluoroethylene (PTFE) can be used.
［２．８．組成物の用途］
　組成物は、塗布法によりｐ型半導体、ｎ型半導体、及び界面活性剤を含む膜を形成するためのインクとして好適に用いられ得る。 [2.8. Use of composition]
The composition can be suitably used as an ink for forming a film containing a p-type semiconductor, an n-type semiconductor, and a surfactant by a coating method.
　本明細書において、「インク」は、塗布法に用いられる液状物を意味しており、着色した液に限定されない。また、「塗布法」は、液状物を用いて膜（層）を形成する方法を包含する。塗布法の例としては、スロットダイコート法、スリットコート法、ナイフコート法、キャスティング法、マイクログラビアコート法、グラビアコート法、バーコート法、ロールコート法、ワイヤーバーコート法、ディップコート法、スプレーコート法、スクリーン印刷法、グラビア印刷法、フレキソ印刷法、オフセット印刷法、インクジェットコート法、ディスペンサー印刷法、ノズルコート法、及びキャピラリーコート法が挙げられる。 In this specification, "ink" means a liquid substance used in a coating method, and is not limited to a colored liquid. Moreover, the "coating method" includes a method of forming a film (layer) using a liquid material. Examples of coating methods include slot die coating, slit coating, knife coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, and spray coating. method, screen printing method, gravure printing method, flexographic printing method, offset printing method, inkjet coating method, dispenser printing method, nozzle coating method, and capillary coating method.
［３．膜］
　本発明の一実施形態に係る膜は、ｐ型半導体、ｎ型半導体、及び界面活性剤を含む。当該膜は、光電変換素子に含まれる活性層として好適に用いられうる。 [3. film]
A film according to an embodiment of the present invention includes a p-type semiconductor, an n-type semiconductor, and a surfactant. The film can be suitably used as an active layer included in a photoelectric conversion element.
　膜に含まれるｐ型半導体、ｎ型半導体、及び界面活性剤の例及び好ましい例はそれぞれ、前記組成物に含まれうる、ｐ型半導体、ｎ型半導体、及び界面活性剤の例及び好ましい例と同様である。 The examples and preferred examples of the p-type semiconductor, n-type semiconductor, and surfactant contained in the film are the examples and preferred examples of the p-type semiconductor, n-type semiconductor, and surfactant that may be contained in the composition, respectively. The same is true.
　本実施形態の膜におけるｐ型半導体の含有量は、所望の特性等に応じて、任意好適な含有量とすることができる。
　例えば、膜におけるｐ型半導体の含有量は、好ましくは１質量％以上、より好ましくは１０質量％以上、更に好ましくは２０質量％以上であり、好ましくは９９質量％以下、より好ましくは９０質量％以下、更に好ましくは８０質量％以下である。 The content of the p-type semiconductor in the film of this embodiment can be set to any suitable content depending on desired characteristics and the like.
For example, the content of the p-type semiconductor in the film is preferably 1% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and preferably 99% by mass or less, more preferably 90% by mass. The content is preferably 80% by mass or less.
　本実施形態の膜におけるｎ型半導体の含有量は、所望の特性等に応じて、任意好適な含有量とすることができる。
　例えば、膜におけるｎ型半導体の含有量は、好ましくは１質量％以上、より好ましくは１０質量％以上、更に好ましくは２０質量％以上であり、好ましくは９９質量％以下、より好ましくは９０質量％以下、更に好ましくは８０質量％以下である。 The content of the n-type semiconductor in the film of this embodiment can be set to any suitable content depending on desired characteristics and the like.
For example, the content of the n-type semiconductor in the film is preferably 1% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and preferably 99% by mass or less, more preferably 90% by mass. The content is preferably 80% by mass or less.
　本実施形態の膜における、ｐ型半導体のｎ型半導体に対する質量割合（ｐ型半導体／ｎ型半導体）は、通常、膜を製造するための組成物におけるｐ型半導体のｎ型半導体に対する質量割合と同じである。 In the film of this embodiment, the mass ratio of the p-type semiconductor to the n-type semiconductor (p-type semiconductor/n-type semiconductor) is usually the mass ratio of the p-type semiconductor to the n-type semiconductor in the composition for manufacturing the film. It's the same.
　本実施形態の膜における、界面活性剤の含有割合は、ｎ型半導体、ｐ型半導体、及び界面活性剤の総質量を１００質量％として、好ましくは０．１質量％以上、より好ましくは１質量％以上であり、好ましくは１０質量％以下、より好ましくは５質量％以下である。 The content ratio of the surfactant in the film of this embodiment is preferably 0.1% by mass or more, more preferably 1% by mass, with the total mass of the n-type semiconductor, p-type semiconductor, and surfactant being 100% by mass. % or more, preferably 10% by mass or less, more preferably 5% by mass or less.
　本実施形態の膜は、溶媒を実質的に含まないことが好ましい。
　本実施形態の膜における、溶媒の含有量は、好ましくは１質量％以下、より好ましくは０．１質量％以下であり、通常０質量％以上であり、０質量％であってもよい。 Preferably, the membrane of this embodiment does not substantially contain a solvent.
The content of the solvent in the membrane of this embodiment is preferably 1% by mass or less, more preferably 0.1% by mass or less, and usually 0% by mass or more, and may be 0% by mass.
　本実施形態の膜は、任意の方法により製造されうる。例えば、本実施形態の膜は、前記組成物を塗布対象に塗布して塗膜を得る工程（ｉ）、及び得られた塗膜から溶媒を除去する工程（ｉｉ）を含む製造方法により製造されうる。 The membrane of this embodiment can be manufactured by any method. For example, the film of this embodiment is manufactured by a manufacturing method including a step (i) of applying the composition to a coating object to obtain a coating film, and a step (ii) of removing the solvent from the obtained coating film. sell.
　（工程（ｉ））
　工程（ｉ）において、組成物を塗布対象に塗布する方法としては、既に説明した従来公知の任意の塗布法を用いることができる。 (Step (i))
In step (i), any of the conventionally known coating methods described above can be used to apply the composition to the object to be coated.
　工程（ｉ）において、組成物は、任意の塗布対象に塗布される。組成物は、光電変換素子の製造工程において、例えば、電極（陽極又は陰極）、電子輸送層、又は正孔輸送層などの光電変換素子が含みうる機能層に塗布されうる。 In step (i), the composition is applied to an arbitrary application target. In the manufacturing process of a photoelectric conversion element, the composition can be applied to, for example, a functional layer that may be included in the photoelectric conversion element, such as an electrode (anode or cathode), an electron transport layer, or a hole transport layer.
　（工程（ｉｉ））
　工程（ｉｉ）において、工程（ｉ）により形成された組成物の塗膜から、溶媒を除去する方法としては、任意好適な方法を用いることができる。溶媒を除去する方法の例としては、熱風乾燥法、赤外線加熱乾燥法、フラッシュランプアニール乾燥法、減圧乾燥法などの乾燥法が挙げられる。 (Step (ii))
In step (ii), any suitable method can be used to remove the solvent from the coating film of the composition formed in step (i). Examples of methods for removing the solvent include drying methods such as hot air drying, infrared heat drying, flash lamp annealing drying, and reduced pressure drying.
［４．有機光電変換素子］
［４．１．光電変換素子の構成］
　本実施形態にかかる光電変換素子は、第１電極と、第２の電極と、該第１電極及び第２の電極の間に設けられている活性層とを含み、該活性層が既に説明した膜である。
　以下、図面を参照して本実施形態の光電変換素子の構成例について具体的に説明する。 [4. Organic photoelectric conversion element]
[4.1. Configuration of photoelectric conversion element]
The photoelectric conversion element according to this embodiment includes a first electrode, a second electrode, and an active layer provided between the first electrode and the second electrode, and the active layer is as described above. It is a membrane.
Hereinafter, a configuration example of the photoelectric conversion element of this embodiment will be specifically described with reference to the drawings.
　図１は、光電変換素子の構成例を模式的に示す図である。 FIG. 1 is a diagram schematically showing a configuration example of a photoelectric conversion element.
　図１に示されるように、光電変換素子１０は、支持基板１１に設けられている。光電変換素子１０は、支持基板１１に接するように設けられている第１の電極１２と、第１の電極１２に接するように設けられている第１の中間層１３と、第１の中間層１３に接するように設けられている活性層１４と、活性層１４に接するように設けられている第２の中間層１５と、第２の中間層１５に接するように設けられている第２の電極１６とを備えている。この構成例では、第２の電極１６に接するように封止部材１７がさらに設けられている。本実施形態では、第１の中間層１３及び第２の中間層１５の両方が設けられているが、第１の中間層１３及び第２の中間層１５のいずれか一つのみが設けられていてもよい。例えば、第１の中間層１３が設けられていなくてもよい。例えば、第２の中間層１５が設けられていなくてもよい。 As shown in FIG. 1, the photoelectric conversion element 10 is provided on a support substrate 11. The photoelectric conversion element 10 includes a first electrode 12 provided in contact with a support substrate 11, a first intermediate layer 13 provided in contact with the first electrode 12, and a first intermediate layer. 13, a second intermediate layer 15 provided in contact with the active layer 14, and a second intermediate layer 15 provided in contact with the second intermediate layer 15. and an electrode 16. In this configuration example, a sealing member 17 is further provided in contact with the second electrode 16. In this embodiment, both the first intermediate layer 13 and the second intermediate layer 15 are provided, but only one of the first intermediate layer 13 and the second intermediate layer 15 is provided. It's okay. For example, the first intermediate layer 13 may not be provided. For example, the second intermediate layer 15 may not be provided.
　以下、本実施形態の光電変換素子に含まれ得る構成要素について具体的に説明する。 Hereinafter, components that may be included in the photoelectric conversion element of this embodiment will be specifically described.
　（基板）
　光電変換素子は、通常、基板（支持基板）上に形成される。また、さらに基板（封止基板）により封止される場合もある。基板には、通常、第１の電極及び第２の電極からなる一対の電極のうちの一方が形成される。基板の材料は、特に有機化合物を含む層を形成する際に化学的に変化しない材料であれば特に限定されない。 (substrate)
A photoelectric conversion element is usually formed on a substrate (supporting substrate). In addition, there are cases where the device is further sealed with a substrate (sealing substrate). One of a pair of electrodes consisting of a first electrode and a second electrode is usually formed on the substrate. The material of the substrate is not particularly limited as long as it is a material that does not chemically change when forming a layer containing an organic compound.
　基板の材料としては、例えば、ガラス、プラスチック、高分子フィルム、シリコンが挙げられる。不透明な基板が用いられる場合には、不透明な基板側に設けられる電極とは反対側の電極（換言すると、不透明な基板から遠い側の電極）が透明又は半透明の電極とされることが好ましい。 Examples of the material for the substrate include glass, plastic, polymer film, and silicon. When an opaque substrate is used, it is preferable that the electrode on the opposite side of the electrode provided on the opaque substrate (in other words, the electrode on the side far from the opaque substrate) be a transparent or semitransparent electrode. .
　（電極）
　光電変換素子は、一対の電極である第１の電極及び第２の電極を含んでいる。第１の電極及び第２の電極のうち、少なくとも一方の電極は、光を入射させるために、透明又は半透明の電極とすることが好ましい。 (electrode)
The photoelectric conversion element includes a pair of electrodes, a first electrode and a second electrode. At least one of the first electrode and the second electrode is preferably a transparent or semitransparent electrode in order to allow light to enter.
　透明又は半透明の電極の材料の例としては、導電性の金属酸化物膜、半透明の金属薄膜が挙げられる。具体的には、酸化インジウム、酸化亜鉛、酸化スズ、及びそれらの複合体であるインジウムスズ酸化物（ＩＴＯ）、インジウム亜鉛酸化物（ＩＺＯ）、ＮＥＳＡ等の導電性材料、金、白金、銀、銅が挙げられる。透明又は半透明である電極の材料としては、ＩＴＯ、ＩＺＯ、酸化スズが好ましい。また、電極として、ポリアニリン及びその誘導体、ポリチオフェン及びその誘導体などの有機化合物が材料として用いられる透明導電膜を用いてもよい。透明又は半透明の電極は、第１の電極であっても第２の電極であってもよい。 Examples of transparent or translucent electrode materials include conductive metal oxide films and translucent metal thin films. Specifically, indium oxide, zinc oxide, tin oxide, indium tin oxide (ITO) which is a composite thereof, indium zinc oxide (IZO), conductive materials such as NESA, gold, platinum, silver, Copper is an example. As the transparent or translucent electrode material, ITO, IZO, and tin oxide are preferable. Further, as the electrode, a transparent conductive film using an organic compound such as polyaniline and its derivatives, polythiophene and its derivatives as a material may be used. The transparent or translucent electrode may be the first electrode or the second electrode.
　一対の電極のうちの一方の電極が透明又は半透明であれば、他方の電極は光透過性の低い電極であってもよい。光透過性の低い電極の材料の例としては、金属、及び導電性高分子が挙げられる。光透過性の低い電極の材料の具体例としては、リチウム、ナトリウム、カリウム、ルビジウム、セシウム、マグネシウム、カルシウム、ストロンチウム、バリウム、アルミニウム、スカンジウム、バナジウム、亜鉛、イットリウム、インジウム、セリウム、サマリウム、ユーロピウム、テルビウム、イッテルビウム等の金属、及びこれらのうちの２種以上の合金、又は、これらのうちの１種以上の金属と、金、銀、白金、銅、マンガン、チタン、コバルト、ニッケル、タングステン及び錫からなる群から選ばれる１種以上の金属との合金、グラファイト、グラファイト層間化合物、ポリアニリン及びその誘導体、ポリチオフェン及びその誘導体が挙げられる。合金としては、マグネシウム－銀合金、マグネシウム－インジウム合金、マグネシウム－アルミニウム合金、インジウム－銀合金、リチウム－アルミニウム合金、リチウム－マグネシウム合金、リチウム－インジウム合金、及びカルシウム－アルミニウム合金が挙げられる。 As long as one of the pair of electrodes is transparent or semitransparent, the other electrode may be an electrode with low light transmittance. Examples of electrode materials with low optical transparency include metals and conductive polymers. Specific examples of electrode materials with low optical transparency include lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, Metals such as terbium and ytterbium, alloys of two or more of these, or one or more of these metals and gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin Examples include alloys with one or more metals selected from the group consisting of, graphite, graphite intercalation compounds, polyaniline and its derivatives, polythiophene and its derivatives. Examples of the alloy 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.
　（活性層）
　本実施形態の光電変換素子は、活性層として、既に説明した膜を含む。本実施形態の活性層は、バルクヘテロジャンクション型の構造を有している。 (active layer)
The photoelectric conversion element of this embodiment includes the above-described film as an active layer. The active layer of this embodiment has a bulk heterojunction type structure.
　本実施形態において、活性層の厚さは、特に限定されない。活性層の厚さは、例えば、暗電流の抑制と生じた光電流の取り出しとのバランスを考慮して、任意好適な厚さとすることができる。活性層の厚さは、特に暗電流をより低減する観点から、好ましくは１００ｎｍ以上であり、より好ましくは１５０ｎｍ以上であり、更に好ましくは２００ｎｍ以上である。また、活性層の厚さは、好ましくは１０μｍ以下であり、より好ましくは５μｍ以下であり、更に好ましくは１μｍ以下である。 In this embodiment, the thickness of the active layer is not particularly limited. The thickness of the active layer can be set to any suitable thickness, taking into consideration, for example, the balance between suppression of dark current and extraction of generated photocurrent. The thickness of the active layer is preferably 100 nm or more, more preferably 150 nm or more, and still more preferably 200 nm or more, especially from the viewpoint of further reducing dark current. Further, the thickness of the active layer is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 1 μm or less.
　（中間層）
　図１に示されるとおり、本実施形態の光電変換素子は、光電変換効率などの特性を向上させるための構成要素として、例えば、電荷輸送層（電子輸送層、正孔輸送層、電子注入層、正孔注入層）などの中間層（バッファー層）を備えていることが好ましい。 (middle class)
As shown in FIG. 1, the photoelectric conversion element of this embodiment includes, for example, charge transport layers (electron transport layer, hole transport layer, electron injection layer, It is preferable to include an intermediate layer (buffer layer) such as a hole injection layer).
　また、中間層に用いられる材料の例としては、カルシウムなどの金属、酸化モリブデン、酸化亜鉛などの無機酸化物半導体、及びＰＥＤＯＴ（ポリ（３，４－エチレンジオキシチオフェン））とＰＳＳ（ポリ（４－スチレンスルホネート））との混合物（ＰＥＤＯＴ：ＰＳＳ）が挙げられる。 Examples of materials used for the intermediate layer include metals such as calcium, inorganic oxide semiconductors such as molybdenum oxide and zinc oxide, and PEDOT (poly(3,4-ethylenedioxythiophene)) and PSS (poly( 4-styrene sulfonate)) (PEDOT:PSS).
　中間層は、従来公知の任意好適な形成方法により形成することができる。中間層は、真空蒸着法や活性層の形成方法と同様の塗布法により形成することができる。 The intermediate layer can be formed by any conventionally known suitable forming method. The intermediate layer can be formed by a vacuum deposition method or a coating method similar to the method for forming the active layer.
　図１に示されるように、本実施形態の光電変換素子は、第１の電極と活性層との間に、第１の中間層としての電子輸送層を備えることが好ましい。本実施形態の光電変換素子は、第２の電極と活性層との間に、第２の中間層としての正孔輸送層を備えていてもよく、備えていなくてもよい。 As shown in FIG. 1, the photoelectric conversion element of this embodiment preferably includes an electron transport layer as a first intermediate layer between the first electrode and the active layer. The photoelectric conversion element of this embodiment may or may not include a hole transport layer as a second intermediate layer between the second electrode and the active layer.
　また別の実施形態では、光電変換素子は、第２の電極と活性層との間に、第２の中間層としての電子輸送層を備えていることが好ましい。この別の実施形態では、光電変換素子は、第１の電極と活性層との間に、第１の中間層としての正孔輸送層を備えていてもよく、備えていなくてもよい。 In another embodiment, the photoelectric conversion element preferably includes an electron transport layer as a second intermediate layer between the second electrode and the active layer. In this other embodiment, the photoelectric conversion element may or may not include a hole transport layer as a first intermediate layer between the first electrode and the active layer.
　電子輸送層は、活性層から電極へと電子を輸送する機能を有する。正孔輸送層は、活性層から電極へと正孔を輸送する機能を有する。 The electron transport layer has the function of transporting electrons from the active layer to the electrode. The hole transport layer has the function of transporting holes from the active layer to the electrode.
　電極に接して設けられる電子輸送層を、特に電子注入層という場合がある。電極に接して設けられる電子輸送層（電子注入層）は、電極への電子の注入を促進する機能を有する。電子輸送層（電子注入層）は、活性層に接していてもよい。 An electron transport layer provided in contact with an electrode is sometimes referred to as an electron injection layer. The electron transport layer (electron injection layer) provided in contact with the electrode has a function of promoting injection of electrons into the electrode. The electron transport layer (electron injection layer) may be in contact with the active layer.
　電子輸送層は、電子輸送性材料を含む。電子輸送性材料の例としては、ポリアルキレンイミン及びその誘導体、フルオレン構造を含む高分子化合物、カルシウムなどの金属、金属酸化物が挙げられる。 The electron transport layer contains an electron transport material. Examples of electron-transporting materials include polyalkyleneimine and its derivatives, polymer compounds containing a fluorene structure, metals such as calcium, and metal oxides.
　ポリアルキレンイミン及びその誘導体の例としては、エチレンイミン、プロピレンイミン、ブチレンイミン、ジメチルエチレンイミン、ペンチレンイミン、ヘキシレンイミン、ヘプチレンイミン、オクチレンイミンといった炭素原子数２～８のアルキレンイミン、特に炭素原子数２～４のアルキレンイミンの１種又は２種以上を常法により重合して得られるポリマー、並びにそれらを種々の化合物と反応させて化学的に変性させたポリマーが挙げられる。ポリアルキレンイミン及びその誘導体としては、ポリエチレンイミン（ＰＥＩ）及びエトキシ化ポリエチレンイミン（ＰＥＩＥ）が好ましい。 Examples of polyalkyleneimines and derivatives thereof include alkyleneimines having 2 to 8 carbon atoms, especially those having 2 to 8 carbon atoms, such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, octyleneimine. Examples include polymers obtained by polymerizing one or more of 2 to 4 alkylene imines by a conventional method, and polymers chemically modified by reacting them with various compounds. As the polyalkyleneimine and its derivatives, polyethyleneimine (PEI) and ethoxylated polyethyleneimine (PEIE) are preferred.
　フルオレン構造を含む高分子化合物の例としては、ポリ［（９，９－ビス（３’－（Ｎ，Ｎ－ジメチルアミノ）プロピル）－２，７－フルオレン）－オルト－２，７－（９，９’－ジオクチルフルオレン）］（ＰＦＮ）及びＰＦＮ－Ｐ２が挙げられる。 An example of a polymer compound containing a fluorene structure is poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-ortho-2,7-(9 , 9'-dioctylfluorene)] (PFN) and PFN-P2.
　金属酸化物の例としては、酸化亜鉛、ガリウムドープ酸化亜鉛、アルミニウムドープ酸化亜鉛、酸化チタン及び酸化ニオブが挙げられる。金属酸化物としては、亜鉛を含む金属酸化物が好ましく、中でも酸化亜鉛が好ましい。 Examples of metal oxides include zinc oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, titanium oxide, and niobium oxide. As the metal oxide, metal oxides containing zinc are preferred, and zinc oxide is particularly preferred.
　その他の電子輸送性材料の例としては、ポリ（４－ビニルフェノール）、ペリレンジイミドが挙げられる。 Examples of other electron-transporting materials include poly(4-vinylphenol) and perylene diimide.
　電極に接して設けられる正孔輸送層を、特に正孔注入層という場合がある。電極に接して設けられる正孔輸送層（正孔注入層）は、活性層で発生した正孔の電極への注入を促進する機能を有する。 A hole transport layer provided in contact with an electrode is sometimes referred to as a hole injection layer. The hole transport layer (hole injection layer) provided in contact with the electrode has a function of promoting injection of holes generated in the active layer into the electrode.
　正孔輸送層は、正孔輸送性材料を含む。正孔輸送性材料の例としては、ポリチオフェン及びその誘導体、芳香族アミン化合物、芳香族アミン残基を有する構成単位を含む高分子化合物、ＣｕＳＣＮ、ＣｕＩ、ＮｉＯ、酸化タングステン（ＷＯ３）及び酸化モリブデン（ＭｏＯ３）が挙げられる。 The hole transport layer contains a hole transport material. Examples of hole-transporting materials include polythiophene and its derivatives, aromatic amine compounds, polymer compounds containing structural units having aromatic amine residues, CuSCN, CuI, NiO, tungsten oxide (WO 3 ), and molybdenum oxide. (MoO 3 ).
　（封止部材）
　本実施形態の光電変換素子は、封止部材をさらに含み、かかる封止部材により封止された封止体とすることが好ましい。
　封止部材は任意好適な従来公知の部材を用いることができる。封止部材の例としては、基板（封止基板）であるガラス基板とＵＶ硬化性樹脂などの封止材（接着剤）との組合せが挙げられる。 (Sealing member)
Preferably, the photoelectric conversion element of this embodiment further includes a sealing member, and is a sealed body sealed with the sealing member.
Any suitable conventionally known member can be used as the sealing member. An example of the sealing member is a combination of a glass substrate as a substrate (sealing substrate) and a sealing material (adhesive) such as a UV curable resin.
　封止部材は、１層以上の層構造である封止層であってもよい。封止層を構成する層の例としては、ガスバリア層、ガスバリア性フィルムが挙げられる。 The sealing member may be a sealing layer having a layer structure of one or more layers. Examples of layers constituting the sealing layer include a gas barrier layer and a gas barrier film.
　封止層は、水分を遮断する性質（水蒸気バリア性）又は酸素を遮断する性質（酸素バリア性）を有する材料により形成することが好ましい。封止層の材料として好適な材料の例としては、三フッ化ポリエチレン、ポリ三フッ化塩化エチレン（ＰＣＴＦＥ）、ポリイミド、ポリカーボネート、ポリエチレンテレフタレート、脂環式ポリオレフィン、エチレン－ビニルアルコール共重合体などの有機材料、酸化ケイ素、窒化ケイ素、酸化アルミニウム、ダイヤモンドライクカーボンなどの無機材料などが挙げられる。 The sealing layer is preferably formed of a material that has a property of blocking moisture (water vapor barrier property) or a property of blocking oxygen (oxygen barrier property). Examples of materials suitable for the sealing layer include trifluoropolyethylene, polytrifluorochloride ethylene (PCTFE), polyimide, polycarbonate, polyethylene terephthalate, alicyclic polyolefin, and ethylene-vinyl alcohol copolymer. Examples include organic materials, and inorganic materials such as silicon oxide, silicon nitride, aluminum oxide, and diamond-like carbon.
　封止部材は、通常、光電変換素子が適用される、例えば後述する適用例のデバイスに組み込まれる際において実施され得る加熱処理に耐えうる材料により構成される。 The sealing member is usually made of a material that can withstand heat treatment that can be performed when the photoelectric conversion element is applied, for example, when it is incorporated into a device of an application example described below.
　別の実施形態では、第１の中間層１３及び第２の中間層１５の両方、又はいずれかが、設けられていなくてもよい。 In another embodiment, both or either of the first intermediate layer 13 and the second intermediate layer 15 may not be provided.
［４．２．光電変換素子の製造方法］
　本実施形態の光電変換素子は、従来公知の任意好適な製造方法により製造しうる。本実施形態の光電変換素子は、構成要素を形成するにあたり選択された材料に好適な工程を組み合わせて製造しうる。 [4.2. Manufacturing method of photoelectric conversion element]
The photoelectric conversion element of this embodiment can be manufactured by any conventionally known suitable manufacturing method. The photoelectric conversion element of this embodiment can be manufactured by combining suitable processes for the materials selected for forming the constituent elements.
　以下、本発明の実施形態として、基板（支持基板）、第１の電極、正孔輸送層、活性層、電子輸送層、第２の電極がこの順に互いに接する構成を有する光電変換素子の製造方法を説明する。 Hereinafter, as an embodiment of the present invention, a method for manufacturing a photoelectric conversion element having a structure in which a substrate (supporting substrate), a first electrode, a hole transport layer, an active layer, an electron transport layer, and a second electrode are in contact with each other in this order. Explain.
　（基板を用意する工程）
　本工程では、例えば第１の電極が設けられた支持基板を用意する。また、既に説明した電極の材料により形成された導電性の薄膜が設けられた基板を市場より入手し、必要に応じて、導電性の薄膜をパターニングして第１の電極を形成することにより、第１の電極が設けられた支持基板を用意することができる。 (Process of preparing the board)
In this step, for example, a support substrate provided with a first electrode is prepared. In addition, by obtaining a substrate provided with a conductive thin film made of the electrode material already described from the market and patterning the conductive thin film as necessary to form the first electrode, A support substrate provided with a first electrode can be provided.
　本実施形態にかかる光電変換素子の製造方法において、支持基板上に第１の電極を形成する場合の第１の電極の形成方法は特に限定されない。第１の電極は、既に説明した材料を、真空蒸着法、スパッタリング法、イオンプレーティング法、めっき法、塗布法などの従来公知の任意好適な方法によって、第１の電極を形成すべき構成（例、支持基板、活性層、正孔輸送層）上に形成することができる。 In the method for manufacturing a photoelectric conversion element according to the present embodiment, the method for forming the first electrode when forming the first electrode on the support substrate is not particularly limited. The first electrode is formed by using the previously described material by any conventionally known suitable method such as vacuum evaporation, sputtering, ion plating, plating, or coating. for example, a supporting substrate, an active layer, a hole transport layer).
　（正孔輸送層の形成工程）
　光電変換素子の製造方法は、活性層と第１の電極との間に設けられる正孔輸送層（正孔注入層）を形成する工程を含んでいてもよい。 (Formation process of hole transport layer)
The method for manufacturing a photoelectric conversion element may include a step of forming a hole transport layer (hole injection layer) provided between the active layer and the first electrode.
　正孔輸送層の形成方法は特に限定されない。正孔輸送層の形成工程をより簡便にする観点からは、従来公知の任意好適な塗布法によって正孔輸送層を形成することが好ましい。正孔輸送層は、例えば、既に説明した正孔輸送層を構成しうる材料と溶媒とを含む塗布液を用いる塗布法や真空蒸着法により形成することができる。 The method for forming the hole transport layer is not particularly limited. From the viewpoint of simplifying the step of forming the hole transport layer, it is preferable to form the hole transport layer by any suitable coating method known in the art. The hole transport layer can be formed, for example, by a coating method using a coating liquid containing a material capable of forming the hole transport layer and a solvent as described above, or a vacuum evaporation method.
　（活性層の形成工程）
　本実施形態の光電変換素子の製造方法においては、正孔輸送層上に活性層が形成される。活性層は、任意好適な従来公知の形成工程により形成することができる。本実施形態において、活性層は、既に説明した組成物を用いる塗布法により製造することができる。 (Active layer formation process)
In the method for manufacturing a photoelectric conversion element of this embodiment, an active layer is formed on the hole transport layer. The active layer can be formed by any suitable conventional formation process. In this embodiment, the active layer can be manufactured by the coating method using the composition described above.
　活性層は、既に説明した「膜」と同様にして形成することができる。本実施形態では、ｐ型半導体と、ｎ型半導体と、界面活性剤と、溶媒とを含む組成物を、正孔輸送層上に塗布して塗膜を形成する工程、次いで、前記塗膜を乾燥させる工程を含む工程により、活性層を形成することができる。 The active layer can be formed in the same manner as the "film" described above. In this embodiment, a step of applying a composition containing a p-type semiconductor, an n-type semiconductor, a surfactant, and a solvent onto the hole transport layer to form a coating film, and then applying the coating film to the hole transport layer. The active layer can be formed by a process including a drying process.
　（電子輸送層の形成工程）
　本実施形態の光電変換素子の製造方法は、活性層に接するように設けられた電子輸送層（電子注入層）を形成する工程を含みうる。 (Formation process of electron transport layer)
The method for manufacturing a photoelectric conversion element of this embodiment may include a step of forming an electron transport layer (electron injection layer) provided in contact with the active layer.
　電子輸送層の形成方法は特に限定されない。電子輸送層の形成工程をより簡便にする観点からは、従来公知の任意好適な真空蒸着法によって電子輸送層を形成することが好ましい。 The method for forming the electron transport layer is not particularly limited. From the viewpoint of simplifying the step of forming the electron transport layer, it is preferable to form the electron transport layer by any conventionally known suitable vacuum deposition method.
　（第２の電極の形成工程）
　第２の電極の形成方法は特に限定されない。第２の電極は、例えば、上記例示の電極の材料を、塗布法、真空蒸着法、スパッタリング法、イオンプレーティング法、めっき法など従来公知の任意好適な方法によって形成することができる。以上の工程により、本実施形態の光電変換素子が製造される。 (Second electrode formation process)
The method of forming the second electrode is not particularly limited. The second electrode can be formed, for example, using the above-mentioned electrode material by any conventionally known suitable method such as a coating method, a vacuum evaporation method, a sputtering method, an ion plating method, or a plating method. Through the above steps, the photoelectric conversion element of this embodiment is manufactured.
　（封止体の形成工程）
　封止体の形成にあたり、本実施形態では、従来公知の任意好適な封止材（接着剤）及び基板（封止基板）を用いる。具体的には、製造された光電変換素子の周辺を囲むように、支持基板上に、例えばＵＶ硬化性樹脂などの封止材を塗布した後、封止材により隙間なく貼り合わせた後、選択された封止材に好適な、ＵＶ光の照射などの方法を用いて支持基板と封止基板との間隙に光電変換素子を封止することにより、光電変換素子の封止体を得ることができる。 (Formation process of sealed body)
In forming the sealed body, in this embodiment, any conventionally known suitable sealing material (adhesive) and substrate (sealing substrate) are used. Specifically, a sealing material such as a UV curable resin is applied onto the supporting substrate so as to surround the periphery of the manufactured photoelectric conversion element, and then the selected material is bonded together without any gaps using the sealing material. A sealed body of the photoelectric conversion element can be obtained by sealing the photoelectric conversion element in the gap between the supporting substrate and the sealing substrate using a method such as UV light irradiation that is suitable for the sealed sealing material. can.
［４．３．光電変換素子の適用例］
　本実施形態の光電変換素子の用途としては、光検出素子、太陽電池が挙げられる。本実施形態の光電変換素子は、光が照射されることにより、電極間に光起電力を発生させることができ、太陽電池として動作させることができる。光電変換素子を複数集積することにより太陽電池モジュールとすることもできる。 [4.3. Application examples of photoelectric conversion elements]
Applications of the photoelectric conversion element of this embodiment include photodetection elements and solar cells. The photoelectric conversion element of this embodiment can generate photovoltaic force between electrodes when irradiated with light, and can be operated as a solar cell. A solar cell module can also be formed by integrating a plurality of photoelectric conversion elements.
　本実施形態の光電変換素子は、電極間に電圧（逆バイアス電圧）を印加した状態で、透明又は半透明の電極側から光を照射することにより、光電流を流すことができ、光検出素子（光センサー）として動作させることができる。また、光検出素子を複数集積することによりイメージセンサーとして用いることもできる。本実施形態の光電変換素子は、特に光検出素子として好適に用いることができる。 The photoelectric conversion element of this embodiment can cause a photocurrent to flow by irradiating light from the transparent or semitransparent electrode side with a voltage (reverse bias voltage) applied between the electrodes, and the photodetection element (optical sensor). Furthermore, by integrating a plurality of photodetecting elements, it can also be used as an image sensor. The photoelectric conversion element of this embodiment can be particularly suitably used as a photodetection element.
　本実施形態にかかる光電変換素子は、光検出素子として、ワークステーション、パーソナルコンピュータ、携帯情報端末、入退室管理システム、デジタルカメラ、及び医療機器などの種々の電子装置が備える検出部に好適に適用することができる。 The photoelectric conversion element according to this embodiment is suitably applied as a photodetection element to detection units included in various electronic devices such as workstations, personal computers, personal digital assistants, room access control systems, digital cameras, and medical equipment. can do.
　本実施形態の光電変換素子は、上記例示の電子装置が備える、例えば、Ｘ線撮像装置及びＣＭＯＳイメージセンサーなどの固体撮像装置用のイメージ検出部（例えば、Ｘ線センサーなどのイメージセンサー）、指紋検出部、顔検出部、静脈検出部及び虹彩検出部などの生体の一部分の所定の特徴を検出する生体情報認証装置の検出部（例えば、近赤外線センサー）、パルスオキシメータなどの光学バイオセンサーの検出部などに好適に適用することができる。 The photoelectric conversion element of this embodiment includes, for example, an image detection unit (for example, an image sensor such as an X-ray sensor) for a solid-state imaging device such as an X-ray imaging device and a CMOS image sensor, and a fingerprint A detection unit of a biometric information authentication device that detects a predetermined characteristic of a part of a living body, such as a detection unit, a face detection unit, a vein detection unit, and an iris detection unit (for example, a near-infrared sensor), and an optical biosensor such as a pulse oximeter. It can be suitably applied to a detection unit and the like.
　本実施形態の光電変換素子は、固体撮像装置用のイメージ検出部として、さらにはＴｉｍｅ－ｏｆ－ｆｌｉｇｈｔ（ＴＯＦ）型距離測定装置（ＴＯＦ型測距装置）に好適に適用することもできる。 The photoelectric conversion element of this embodiment can also be suitably applied as an image detection unit for a solid-state imaging device, and further to a time-of-flight (TOF) type distance measuring device (TOF type distance measuring device).
　ＴＯＦ型測距装置では、光源からの放射光が測定対象物において反射された反射光を光電変換素子で受光させることにより距離を測定する。具体的には、光源から放射された照射光が測定対象物で反射して反射光として戻るまでの飛行時間を検出して測定対象物までの距離を求める。ＴＯＦ型には、直接ＴＯＦ方式と間接ＴＯＦ方式とが存在する。直接ＴＯＦ方式では光源から光を照射した時刻と反射光を光電変換素子で受光した時刻との差を直接計測し、間接ＴＯＦ方式では飛行時間に依存した電荷蓄積量の変化を時間変化に換算することで距離を計測する。間接ＴＯＦ方式で用いられる電荷蓄積により飛行時間を得る測距原理には、光源からの放射光と測定対象で反射される反射光との位相から飛行時間を求める連続波（特に正弦波）変調方式とパルス変調方式とがあるが、本実施形態の光電変換素子は、これらの方式のいずれの測定装置にも適用することができる。 A TOF distance measuring device measures distance by having a photoelectric conversion element receive reflected light emitted from a light source and reflected by an object to be measured. Specifically, the distance to the measurement target is determined by detecting the flight time of the irradiation light emitted from the light source until it is reflected by the measurement target and returns as reflected light. The TOF type includes a direct TOF method and an indirect TOF method. In the direct TOF method, the difference between the time when the light is irradiated from the light source and the time when the reflected light is received by the photoelectric conversion element is directly measured, and the indirect TOF method converts the change in the amount of charge accumulation depending on the flight time into a time change. This is how you measure distance. The distance measurement principle used in the indirect TOF method, which obtains the flight time by charge accumulation, is a continuous wave (especially sine wave) modulation method that calculates the flight time from the phase of the emitted light from the light source and the reflected light reflected by the measurement target. and a pulse modulation method, and the photoelectric conversion element of this embodiment can be applied to a measuring device using any of these methods.
［５．光検出素子］
　前記のとおり、本実施形態の光電変換素子は、照射された光を、受光量に応じた電気信号に変換し、電極を介して外部回路に出力しうる光検出機能を有しうる。よって、本発明の実施形態にかかる光電変換素子は、光検出機能を有する光検出素子として特に好適に適用されうる。ここで、本実施形態の光検出素子は、光電変換素子そのものであってもよく、光電変換素子に加えて、電圧制御のためなどの機能素子をさらに含んでいてもよい。 [5. Photodetection element]
As described above, the photoelectric conversion element of this embodiment can have a photodetection function that can convert irradiated light into an electrical signal according to the amount of received light and output it to an external circuit via the electrode. Therefore, the photoelectric conversion element according to the embodiment of the present invention can be particularly suitably applied as a photodetection element having a photodetection function. Here, the photodetection element of this embodiment may be a photoelectric conversion element itself, or may further include a functional element for voltage control in addition to the photoelectric conversion element.
　以下、本発明をさらに詳細に説明するために実施例を示す。本発明は下記の実施例に限定されない。以下の実施例は、特に断りのない限り、常温（２０℃±１５℃）及び常圧（１ａｔｍ）の条件下で行った。また、「％」及び「部」は、特に断りのない限り、それぞれ「質量％」及び「質量部」を表す。 Examples are shown below to explain the present invention in more detail. The invention is not limited to the following examples. The following examples were carried out under conditions of normal temperature (20° C.±15° C.) and normal pressure (1 atm) unless otherwise specified. Moreover, "%" and "parts" represent "mass %" and "mass parts", respectively, unless otherwise specified.
＜使用された半導体材料＞
　（ｐ型半導体）
　ｐ型半導体材料Ｐ－１として、国際公開第２０１３／０５１６７６号に記載の方法を参考に合成された高分子化合物を使用した。
　ｐ型半導体材料Ｐ－２として、国際公開第２０１１／０５２７０９号に記載の方法を参考に合成された高分子化合物を使用した。
　ｐ型半導体材料Ｐ－３として、高分子化合物である、１－ｍａｔｅｒｉａｌ社製、商品名：ＰＭ６を使用した。
　ｐ型半導体材料Ｐ－４として、高分子化合物である、１－ｍａｔｅｒｉａｌ社製、商品名：ＰＣＥ１０を使用した。 <Semiconductor materials used>
(p-type semiconductor)
As p-type semiconductor material P-1, a polymer compound synthesized with reference to the method described in International Publication No. 2013/051676 was used.
As the p-type semiconductor material P-2, a polymer compound synthesized with reference to the method described in International Publication No. 2011/052709 was used.
As the p-type semiconductor material P-3, a polymer compound manufactured by 1-Material, trade name: PM6 was used.
As the p-type semiconductor material P-4, a polymer compound manufactured by 1-Material Co., Ltd., trade name: PCE10 was used.
　（ｎ型半導体）
　ｎ型半導体材料Ｎ－１として、ハーベス社製、商品名：Ｇｕａｒｄ　Ｓｕｒｆ　ＮＣ－１０１０を使用した。
　ｎ型半導体材料Ｎ－２として、フロンティアカーボン社製、商品名：Ｅ１００を使用した。
　ｎ型半導体材料Ｎ－３として、１－ｍａｔｅｒｉａｌ社製、商品名：Ｙ６を使用した。 (n-type semiconductor)
As the n-type semiconductor material N-1, Guard Surf NC-1010 manufactured by Harbes Co., Ltd. was used.
As the n-type semiconductor material N-2, product name: E100 manufactured by Frontier Carbon Co., Ltd. was used.
As the n-type semiconductor material N-3, product name: Y6 manufactured by 1-Material was used.
　ｐ型半導体材料Ｐ－１～Ｐ－４及びｎ型半導体材料Ｎ－１～Ｎ－３の具体的構造を、下記表１及び表２に示す。 The specific structures of the p-type semiconductor materials P-1 to P-4 and the n-type semiconductor materials N-1 to N-3 are shown in Tables 1 and 2 below.
Figure JPOXMLDOC01-appb-T000042
Figure JPOXMLDOC01-appb-T000042
Figure JPOXMLDOC01-appb-T000043
Figure JPOXMLDOC01-appb-T000043
＜使用される界面活性剤＞
　実施例において使用される界面活性剤は、下記のとおりである。
「Ｆ－５５６」：ＤＩＣ社製、ノニオン性、ポリ（メタ）アクリレート構造を有するフッ素系界面活性剤。
「Ｒ－４０」：ＤＩＣ社製、ノニオン性、ポリ（メタ）アクリレート構造を有するフッ素系界面活性剤。
「ＫＰ－６２０」：信越化学工業社製、ノニオン性、オルガノポリシロキサン構造を有する界面活性剤。
「ＫＰ－３２３」：信越化学工業社製、ノニオン性、オルガノポリシロキサン構造を有する界面活性剤。 <Surfactant used>
The surfactants used in the examples are as follows.
"F-556": Manufactured by DIC, nonionic, fluorine-based surfactant having a poly(meth)acrylate structure.
"R-40": Manufactured by DIC, nonionic, fluorine-based surfactant having a poly(meth)acrylate structure.
"KP-620": Manufactured by Shin-Etsu Chemical Co., Ltd., a nonionic surfactant having an organopolysiloxane structure.
"KP-323": Manufactured by Shin-Etsu Chemical Co., Ltd., a nonionic surfactant having an organopolysiloxane structure.
　前記界面活性剤の物性を、下表に示す。下表において、「Ｆ」はフッ素原子を表す。 The physical properties of the surfactant are shown in the table below. In the table below, "F" represents a fluorine atom.
Figure JPOXMLDOC01-appb-T000044
Figure JPOXMLDOC01-appb-T000044
　界面活性剤の粘度ηは、以下の方法及び条件により測定された。
　アントンパール社製モジュラーコンパクトレオメータＭＣＲ３０２を用いて、温度２５℃、せん断速度１００（Ｓ－１）の粘度ηを測定した。 The viscosity η of the surfactant was measured by the following method and conditions.
The viscosity η was measured at a temperature of 25° C. and a shear rate of 100 (S −1 ) using a modular compact rheometer MCR302 manufactured by Anton Paar.
　界面活性剤のＭｐ（ピーク分子量）は、以下の方法及び条件により測定された。
　ＧＰＣの移動相としてはｏ－ジクロロベンゼンを用い、１．０ｍＬ／ｍｉｎの流速で流した。カラムとしては、昭和電工社製、Ｓｈｏｄｅｘ　ＫＤ－８０６Ｍを用い、ガードカラムとしては、昭和電工社製、Ｓｈｏｄｅｘ　ＫＤ－Ｇを用いた。 The Mp (peak molecular weight) of the surfactant was measured by the following method and conditions.
O-dichlorobenzene was used as the mobile phase for GPC at a flow rate of 1.0 mL/min. As the column, Shodex KD-806M manufactured by Showa Denko K.K. was used, and as the guard column, Shodex KD-G manufactured by Showa Denko K.K. was used.
　検出器としてはＵＶ－ｖｉｓ検出器（島津製作所社製、ＳＰＤ－Ｍ２０Ａ）及び示差屈折率検出器（島津製作所社製、ＲＩＤ－１０Ａ）を用いた。 As the detectors, a UV-vis detector (manufactured by Shimadzu Corporation, SPD-M20A) and a differential refractive index detector (manufactured by Shimadzu Corporation, RID-10A) were used.
　測定対象の化合物（重合体）は、溶媒である１－クロロナフタレンに、０．０５質量％の濃度になるように混合して、８０℃で２時間撹拌することで溶解させた溶解液とした。 The compound (polymer) to be measured was mixed in 1-chloronaphthalene, a solvent, to a concentration of 0.05% by mass, and stirred at 80°C for 2 hours to create a solution. .
　得られた溶解液を、上記測定装置（ＧＰＣ）にサンプルとして１０μＬ注入することで、ピーク分子量（Ｍｐ）を測定した。 The peak molecular weight (Mp) was measured by injecting 10 μL of the obtained solution into the above-mentioned measuring device (GPC) as a sample.
＜実施例１＞
　プソイドクメン、テトラリン、及び安息香酸ブチルを、それぞれ質量比８７％、１０％、及び３％となるように混合し、インク溶媒を調製した。界面活性剤として、ＤＩＣ社製「Ｆ－５５６」を用いた。インク溶媒と界面活性剤とを、質量比が９９．９％：０．１％となるように混合し、混合物（ａ）を得た。
　混合物（ａ）に対し、ｐ型半導体として材料Ｐ－１及びｎ型半導体として材料Ｎ－１を混合して、混合物（ｂ）を得た。ｐ型半導体の混合量は、インク組成物（混合物（ｂ））全体に対して１．５質量％となる量とした。ｎ型半導体の混合量は、インク組成物（混合物（ｂ））全体の質量に対して１．５質量％となる量とした。得られた混合物（ｂ）を６０℃で６時間撹拌し、次いでフィルターにてろ過を行うことにより、インク組成物Ｉ－１を得た。インク組成物Ｉ－１に含まれる、溶媒、ｐ型半導体、ｎ型半導体、及び界面活性剤の合計を１００質量％とした場合、界面活性剤の含有割合は、０．０９７質量％である。 <Example 1>
An ink solvent was prepared by mixing pseudocumene, tetralin, and butyl benzoate at mass ratios of 87%, 10%, and 3%, respectively. As a surfactant, "F-556" manufactured by DIC was used. The ink solvent and the surfactant were mixed at a mass ratio of 99.9%:0.1% to obtain a mixture (a).
A mixture (b) was obtained by mixing a material P-1 as a p-type semiconductor and a material N-1 as an n-type semiconductor with respect to the mixture (a). The amount of the p-type semiconductor mixed was 1.5% by mass based on the entire ink composition (mixture (b)). The amount of the n-type semiconductor mixed was 1.5% by mass based on the total mass of the ink composition (mixture (b)). The resulting mixture (b) was stirred at 60° C. for 6 hours, and then filtered through a filter to obtain ink composition I-1. When the total of the solvent, p-type semiconductor, n-type semiconductor, and surfactant contained in ink composition I-1 is 100% by mass, the content of the surfactant is 0.097% by mass.
＜実施例２＞
　インク溶媒と界面活性剤とを、質量比が９９．０％：１．０％となるように混合して、混合物（ａ）を得た。
　以上の事項以外は、実施例１と同様に操作して、インク組成物Ｉ－２を得た。インク組成物Ｉ－２に含まれる、溶媒、ｐ型半導体、ｎ型半導体、及び界面活性剤の合計を１００質量％とした場合、界面活性剤の含有割合は、０．９７質量％である。 <Example 2>
The ink solvent and the surfactant were mixed at a mass ratio of 99.0%:1.0% to obtain a mixture (a).
Ink composition I-2 was obtained in the same manner as in Example 1 except for the above matters. When the total of the solvent, p-type semiconductor, n-type semiconductor, and surfactant contained in ink composition I-2 is 100% by mass, the content of the surfactant is 0.97% by mass.
＜実施例３＞
　界面活性剤として、信越化学工業社製「ＫＰ－６２０」を用いた。
　以上の事項以外は、実施例１と同様に操作して、インク組成物Ｉ－３を得た。 <Example 3>
As a surfactant, "KP-620" manufactured by Shin-Etsu Chemical Co., Ltd. was used.
Ink composition I-3 was obtained in the same manner as in Example 1 except for the above matters.
＜比較例１＞
　混合物（ａ）の代わりに、界面活性剤の含まれていないインク溶媒を用いた。
　以上の事項以外は、実施例１と同様に操作して、インク組成物Ｉ－Ｃ１を得た。 <Comparative example 1>
Instead of mixture (a), an ink solvent containing no surfactant was used.
Ink composition I-C1 was obtained in the same manner as in Example 1 except for the above matters.
＜実施例４＞
　プソイドクメン、及び１，２－ジメトキシベンゼンを、それぞれ質量比９７％、３％となるように混合し、インク溶媒を調製した。
　以上の事項以外は、実施例１と同様に操作して、インク組成物Ｉ－４を得た。 <Example 4>
An ink solvent was prepared by mixing pseudocumene and 1,2-dimethoxybenzene at a mass ratio of 97% and 3%, respectively.
Ink composition I-4 was obtained in the same manner as in Example 1 except for the above matters.
＜比較例２＞
　混合物（ａ）の代わりに、界面活性剤の含まれていないインク溶媒を用いた。
　以上の事項以外は、実施例４と同様に操作して、インク組成物Ｉ－Ｃ２を得た。 <Comparative example 2>
Instead of mixture (a), an ink solvent containing no surfactant was used.
Except for the above matters, the same procedure as in Example 4 was carried out to obtain ink composition I-C2.
＜実施例５＞
　ｐ型半導体として、材料Ｐ－２を用い、ｎ型半導体として、材料Ｎ－２を用いた。
　界面活性剤として、ＤＩＣ社製「Ｒ－４０」を用いた。
　以上の事項以外は、実施例１と同様に操作して、インク組成物Ｉ－５を得た。 <Example 5>
Material P-2 was used as the p-type semiconductor, and material N-2 was used as the n-type semiconductor.
As a surfactant, "R-40" manufactured by DIC was used.
Ink composition I-5 was obtained in the same manner as in Example 1 except for the above matters.
＜実施例６＞
　ｐ型半導体として、材料Ｐ－２を用い、ｎ型半導体として、材料Ｎ－２を用いた。
　以上の事項以外は、実施例１と同様に操作して、インク組成物Ｉ－６を得た。 <Example 6>
Material P-2 was used as the p-type semiconductor, and material N-2 was used as the n-type semiconductor.
Ink composition I-6 was obtained in the same manner as in Example 1 except for the above matters.
＜比較例３＞
　混合物（ａ）の代わりに、界面活性剤の含まれていないインク溶媒を用いた。
　以上の事項以外は、実施例５と同様に操作して、インク組成物Ｉ－Ｃ３を得た。 <Comparative example 3>
Instead of mixture (a), an ink solvent containing no surfactant was used.
Except for the above matters, the same operation as in Example 5 was carried out to obtain ink composition I-C3.
＜実施例７＞
　ｐ型半導体として、材料Ｐ－３を用い、ｎ型半導体として、材料Ｎ－２を用いた。
　インク溶媒として、ｏ－ジクロロベンゼンを用いた。
　以上の事項以外は、実施例１と同様に操作して、インク組成物Ｉ－７を得た。 <Example 7>
Material P-3 was used as the p-type semiconductor, and material N-2 was used as the n-type semiconductor.
O-dichlorobenzene was used as the ink solvent.
Ink composition I-7 was obtained in the same manner as in Example 1 except for the above matters.
＜比較例４＞
　混合物（ａ）の代わりに、界面活性剤の含まれていないインク溶媒を用いた。
　以上の事項以外は、実施例７と同様に操作して、インク組成物Ｉ－Ｃ４を得た。 <Comparative example 4>
Instead of mixture (a), an ink solvent containing no surfactant was used.
Except for the above matters, the same procedure as in Example 7 was carried out to obtain ink composition I-C4.
＜実施例８＞
　ｐ型半導体として、材料Ｐ－４を用い、ｎ型半導体として、材料Ｎ－２を用いた。
　インク溶媒として、ｏ－ジクロロベンゼンを用いた。
　以上の事項以外は、実施例１と同様に操作して、インク組成物Ｉ－８を得た。 <Example 8>
Material P-4 was used as the p-type semiconductor, and material N-2 was used as the n-type semiconductor.
O-dichlorobenzene was used as the ink solvent.
Ink composition I-8 was obtained in the same manner as in Example 1 except for the above matters.
＜比較例５＞
　混合物（ａ）の代わりに、界面活性剤の含まれていないインク溶媒を用いた。
　以上の事項以外は、実施例８と同様に操作して、インク組成物Ｉ－Ｃ５を得た。 <Comparative example 5>
Instead of mixture (a), an ink solvent containing no surfactant was used.
Except for the above matters, the same operation as in Example 8 was carried out to obtain ink composition I-C5.
＜実施例９＞
　ｐ型半導体として、材料Ｐ－１を用い、ｎ型半導体として、材料Ｎ－２を用いた。
　以上の事項以外は、実施例１と同様に操作して、インク組成物Ｉ－９を得た。 <Example 9>
Material P-1 was used as the p-type semiconductor, and material N-2 was used as the n-type semiconductor.
Ink composition I-9 was obtained in the same manner as in Example 1 except for the above matters.
＜比較例６＞
　混合物（ａ）の代わりに、界面活性剤の含まれていないインク溶媒を用いた。
　以上の事項以外は、実施例９と同様に操作して、インク組成物Ｉ－Ｃ６を得た。 <Comparative example 6>
Instead of mixture (a), an ink solvent containing no surfactant was used.
Except for the above matters, the same operation as in Example 9 was carried out to obtain ink composition I-C6.
＜実施例１０＞
　ｐ型半導体として、材料Ｐ－１を用い、ｎ型半導体として、材料Ｎ－３を用いた。
　以上の事項以外は、実施例１と同様に操作して、インク組成物Ｉ－１０を得た。 <Example 10>
Material P-1 was used as the p-type semiconductor, and material N-3 was used as the n-type semiconductor.
Ink composition I-10 was obtained in the same manner as in Example 1 except for the above matters.
＜比較例７＞
　混合物（ａ）の代わりに、界面活性剤の含まれていないインク溶媒を用いた。
　以上の事項以外は、実施例１０と同様に操作して、インク組成物Ｉ－Ｃ７を得た。 <Comparative example 7>
Instead of mixture (a), an ink solvent containing no surfactant was used.
Except for the above matters, the same operation as in Example 10 was carried out to obtain ink composition I-C7.
＜実施例１１＞
　ｐ型半導体として、材料Ｐ－３を用い、ｎ型半導体として、材料Ｎ－３を用いた。
　以上の事項以外は、実施例１と同様に操作して、インク組成物Ｉ－１１を得た。 <Example 11>
Material P-3 was used as the p-type semiconductor, and material N-3 was used as the n-type semiconductor.
Ink composition I-11 was obtained in the same manner as in Example 1 except for the above matters.
＜比較例８＞
　混合物（ａ）の代わりに、界面活性剤の含まれていないインク溶媒を用いた。
　以上の事項以外は、実施例１１と同様に操作して、インク組成物Ｉ－Ｃ８を得た。 <Comparative example 8>
Instead of mixture (a), an ink solvent containing no surfactant was used.
Except for the above matters, the same procedure as in Example 11 was carried out to obtain ink composition I-C8.
　実施例及び比較例に係るインク組成物の配合を、下表に示す。
　下表において、界面活性剤の添加量は、混合物（ｂ）を１００質量％とした値を示す。 The formulations of the ink compositions according to Examples and Comparative Examples are shown in the table below.
In the table below, the amount of surfactant added is based on 100% by mass of mixture (b).
Figure JPOXMLDOC01-appb-T000045
Figure JPOXMLDOC01-appb-T000045
＜光電変換素子の製造及び評価＞
　実施例及び比較例で製造した各インク組成物を用いて、下記の光電変換素子の製造方法Ａ又は製造方法Ｂに従って光電変換素子を製造し、暗電流（Ｊｄ）を測定した。 <Manufacture and evaluation of photoelectric conversion element>
Using each ink composition produced in Examples and Comparative Examples, a photoelectric conversion element was produced according to the following photoelectric conversion element production method A or production method B, and the dark current (Jd) was measured.
［光電変換素子の製造方法Ａ］
　（Ａ－１．基板の用意）
　スパッタ法により１００ｎｍの厚さで第１の電極としてのＩＴＯ膜が形成されたガラス基板（以下、単にガラス基板という。）を用意した。次いで、当該ガラス基板に対してオゾン紫外線（ＵＶ）処理による表面処理を行った。 [Manufacturing method A of photoelectric conversion element]
(A-1. Preparation of board)
A glass substrate (hereinafter simply referred to as glass substrate) on which an ITO film as a first electrode was formed to a thickness of 100 nm by sputtering was prepared. Next, the glass substrate was subjected to surface treatment using ozone ultraviolet (UV) treatment.
　（Ａ－２．活性層の形成）
　インク組成物を、ガラス基板のＩＴＯ膜上に、スピンコート法により塗布して、塗膜を形成した。塗膜が形成されたガラス基板をホットプレート上に載せ、大気中において７０℃で２分間の条件で塗膜を乾燥させた。続いて、塗膜が形成されたガラス基板をホットプレート上に載せ、窒素ガス雰囲気下において、１００℃で１０分間の条件で塗膜を更に乾燥させた。これにより、ＩＴＯ膜上に、活性層が形成された。形成された活性層の厚さは、約２５０ｎｍであった。 (A-2. Formation of active layer)
The ink composition was applied onto an ITO film on a glass substrate by a spin coating method to form a coating film. The glass substrate on which the coating film was formed was placed on a hot plate, and the coating film was dried in the atmosphere at 70° C. for 2 minutes. Subsequently, the glass substrate on which the coating film was formed was placed on a hot plate, and the coating film was further dried at 100° C. for 10 minutes in a nitrogen gas atmosphere. As a result, an active layer was formed on the ITO film. The thickness of the formed active layer was about 250 nm.
　（Ａ－３．電子輸送層の形成）
　次いで、酸化亜鉛ナノ粒子（粒径２０～３０ｎｍ）の４５質量％イソプロパノール分散液（テイカ社製、ＨＴＤ－７１１Ｚ）を、当該イソプロパノール分散液の１０倍質量部の３－ペンタノールで希釈し、塗布液を調製した。この塗布液を、スピンコート法により形成された活性層上に、４０ｎｍの厚さで塗布し、７０℃で５分間の加熱処理を施した。これにより、活性層上に電子輸送層が形成された。 (A-3. Formation of electron transport layer)
Next, a 45% by mass isopropanol dispersion (manufactured by Teika, HTD-711Z) of zinc oxide nanoparticles (particle size 20 to 30 nm) was diluted with 3-pentanol in an amount 10 times the mass of the isopropanol dispersion, and applied. A liquid was prepared. This coating liquid was applied to a thickness of 40 nm on the active layer formed by spin coating, and heat-treated at 70° C. for 5 minutes. As a result, an electron transport layer was formed on the active layer.
　（Ａ－４．電極の形成）
　その後、抵抗加熱蒸着装置を用いて、電子輸送層上に、電極（第２の電極）であるＡｇ膜を約８０ｎｍの厚さで形成した。 (A-4. Formation of electrode)
Thereafter, an Ag film serving as an electrode (second electrode) was formed to a thickness of about 80 nm on the electron transport layer using a resistance heating evaporation apparatus.
　（Ａ－５．封止層の形成）
　次いで、紫外線（ＵＶ）硬化性封止剤を、電極（第２の電極）が形成されたガラス基板の周囲に塗布し、さらにガラス板を電極の上方に貼り合わせた後、ＵＶ光を照射することで封止剤を硬化させて封止し、光電変換素子を得た。得られた光電変換素子の形状は２ｍｍ×２ｍｍの正方形であった。 (A-5. Formation of sealing layer)
Next, an ultraviolet (UV) curable sealant is applied around the glass substrate on which the electrode (second electrode) is formed, and after the glass plate is bonded above the electrode, UV light is irradiated. In this way, the sealant was cured and sealed, and a photoelectric conversion element was obtained. The shape of the obtained photoelectric conversion element was a square of 2 mm x 2 mm.
　以上の製造方法により、ガラス基板、第１の電極、活性層、電子輸送層、及び第２の電極が、この順に設けられている、光電変換素子Ａ（光検出素子Ａ）が得られた。 By the above manufacturing method, a photoelectric conversion element A (photodetection element A) in which a glass substrate, a first electrode, an active layer, an electron transport layer, and a second electrode were provided in this order was obtained.
［光電変換素子の製造方法Ｂ］
　（Ｂ－１．基板の用意）
　スパッタ法により１００ｎｍの厚さでＩＴＯ膜が形成されたガラス基板を用意した。次いで、当該ガラス基板に対してオゾンＵＶ処理による表面処理を行った。 [Manufacturing method B of photoelectric conversion element]
(B-1. Preparation of board)
A glass substrate on which an ITO film with a thickness of 100 nm was formed by sputtering was prepared. Next, the glass substrate was subjected to surface treatment by ozone UV treatment.
　（Ｂ－２．電子輸送層の形成）
　次に、ガラス基板を、ポリエチレンイミン８０％エトキシ化水溶液（シグマアルドリッチ社製、３７質量％水溶液）を、濃度が０．１質量％となるように水で希釈して得られた希釈溶液に、５分間浸漬した。次いで、希釈溶液からガラス基板を引き上げた後にホットプレート上に載せ、大気中において１００℃で１０分間の条件で乾燥させた。 (B-2. Formation of electron transport layer)
Next, the glass substrate was placed in a diluted solution obtained by diluting an 80% polyethyleneimine ethoxylated aqueous solution (manufactured by Sigma-Aldrich, 37% by mass aqueous solution) with water to a concentration of 0.1% by mass. Soaked for 5 minutes. Next, the glass substrate was pulled out of the diluted solution, placed on a hot plate, and dried in the atmosphere at 100° C. for 10 minutes.
　次いで、乾燥させたガラス基板を水で洗浄し、洗浄後のガラス基板をホットプレート上に載せ、大気中において１００℃で１０分間の条件で乾燥させた。これにより、第１の電極としてのＩＴＯ膜上に電子輸送層を形成した。 Next, the dried glass substrate was washed with water, and the washed glass substrate was placed on a hot plate and dried in the atmosphere at 100° C. for 10 minutes. As a result, an electron transport layer was formed on the ITO film serving as the first electrode.
　（Ｂ－３．活性層の形成）
　次に、インク組成物を、ＩＴＯ膜上に形成された電子輸送層上に、スロットダイコート法により塗布して塗膜を形成した。次いで、真空乾燥処理（圧力１０Ｐａ、７０℃）を５分間行った。乾燥処理された塗膜が形成されたガラス基板をホットプレート上に載せ、１００℃で１２分間の条件で乾燥させることにより活性層を形成した。形成された活性層の厚さは、約５３０ｎｍであった。 (B-3. Formation of active layer)
Next, the ink composition was applied onto the electron transport layer formed on the ITO film by a slot die coating method to form a coating film. Next, vacuum drying treatment (pressure 10 Pa, 70° C.) was performed for 5 minutes. The glass substrate on which the dried coating film was formed was placed on a hot plate and dried at 100° C. for 12 minutes to form an active layer. The thickness of the formed active layer was about 530 nm.
　（Ｂ－４．電極の形成）
　次いで、ポリ（３，４－エチレンジオキシチオフェン）／ポリスチレンスルホン酸を水に溶解させた懸濁液（ヘレウス社製、Ｃｌｅｖｉｏｓ　Ｆ　ＨＣ　Ｓｏｌａｒ）を、形成された活性層上に、スピンコート法により塗布して塗膜を形成した。塗膜が活性層上に形成されたガラス基板をオーブンに入れ、８５℃で３０分間の条件で乾燥させることにより第２の電極を形成した。形成された第２の電極の厚さは、約１２０ｎｍであった。 (B-4. Formation of electrode)
Next, a suspension of poly(3,4-ethylenedioxythiophene)/polystyrene sulfonic acid dissolved in water (Clevios F HC Solar, manufactured by Heraeus) was applied onto the formed active layer by spin coating. It was applied to form a coating film. The glass substrate on which the coating film was formed on the active layer was placed in an oven and dried at 85° C. for 30 minutes to form a second electrode. The thickness of the second electrode formed was approximately 120 nm.
　（Ｂ－５．封止層の形成）
　次いで、紫外線（ＵＶ）硬化性封止剤を、電極（第２の電極）が形成されたガラス基板の周囲に塗布し、さらにガラス板を電極の上方に貼り合わせた後、ＵＶ光を照射することで封止剤を硬化させて封止し、光電変換素子を得た。得られた光電変換素子の形状は２ｍｍ×２ｍｍの正方形であった。 (B-5. Formation of sealing layer)
Next, an ultraviolet (UV) curable sealant is applied around the glass substrate on which the electrode (second electrode) is formed, and after the glass plate is bonded above the electrode, UV light is irradiated. In this way, the sealant was cured and sealed, and a photoelectric conversion element was obtained. The shape of the obtained photoelectric conversion element was a square of 2 mm x 2 mm.
　以上の製造方法により、ガラス基板、第１の電極、電子輸送層、活性層、及び第２の電極が、この順に設けられている、光電変換素子Ｂ（光検出素子Ｂ）が得られた。 By the above manufacturing method, a photoelectric conversion element B (photodetection element B) in which a glass substrate, a first electrode, an electron transport layer, an active layer, and a second electrode were provided in this order was obtained.
［光電変換素子の評価］
　前記の製造方法Ａ又は製造方法Ｂにより製造された光電変換素子に、暗所においてＪＶ測定を行い、－５Ｖにおける暗電流（Ｊｄ）を求めた。ＪＶ測定にはソースメータ―（２４５０型、ケースレー社製）を用いた。 [Evaluation of photoelectric conversion element]
A JV measurement was performed on the photoelectric conversion element manufactured by the above manufacturing method A or manufacturing method B in a dark place, and the dark current (Jd) at -5V was determined. A source meter (model 2450, manufactured by Keithley) was used for the JV measurement.
＜評価結果＞
　評価結果を下表に示す。
　下表において、評価１～４の暗電流（Ｊｄ）相対値は、評価１の暗電流を１００とした場合の相対値である。評価５～６のＪｄ相対値は、評価５の暗電流を１００とした場合の相対値である。評価７～９のＪｄ相対値は、評価７の暗電流を１００とした場合の相対値である。評価１０～１１、評価１２～１３、評価１４～１５、評価１６～１７、評価１８～１９のＪｄ相対値は、それぞれ評価１０、評価１２、評価１４、評価１６、評価１８の暗電流を１００とした場合の相対値である。
　下表において、「素子Ａ」は、製造方法Ａにより製造された光電変換素子Ａを表し、「素子Ｂ」は、製造方法Ｂにより製造された光電変換素子Ｂを表す。 <Evaluation results>
The evaluation results are shown in the table below.
In the table below, the relative dark current (Jd) values for evaluations 1 to 4 are relative values when the dark current for evaluation 1 is taken as 100. The Jd relative values of evaluations 5 to 6 are relative values when the dark current of evaluation 5 is set to 100. The Jd relative values of evaluations 7 to 9 are relative values when the dark current of evaluation 7 is set to 100. The Jd relative values of evaluations 10 to 11, evaluations 12 to 13, evaluations 14 to 15, evaluations 16 to 17, and evaluations 18 to 19 are the dark currents of evaluations 10, 12, 14, 16, and 18, respectively. This is the relative value when .
In the table below, "Element A" represents photoelectric conversion element A manufactured by manufacturing method A, and "Element B" represents photoelectric conversion element B manufactured by manufacturing method B.
Figure JPOXMLDOC01-appb-T000046
Figure JPOXMLDOC01-appb-T000046
　以上の結果より、界面活性剤を含む組成物から製造された活性層を備える光電変換素子は、界面活性剤を含まない組成物から製造された活性層を備える光電変換素子と比較して、暗電流が低下することが分かる。
　また界面活性剤を含む組成物から製造された活性層を備える光電変換素子は、光電変換素子Ａ及び光電変換素子Ｂのいずれの構造を有していても、暗電流が低下することが分かる。 From the above results, a photoelectric conversion element with an active layer manufactured from a composition containing a surfactant has a higher dark It can be seen that the current decreases.
Further, it can be seen that a photoelectric conversion element including an active layer manufactured from a composition containing a surfactant has a reduced dark current regardless of the structure of photoelectric conversion element A or photoelectric conversion element B.
　１０　光電変換素子
　１１　支持基板
　１２　第１の電極
　１３　第１の中間層
　１４　活性層
　１５　第２の中間層
　１６　第２の電極
　１７　封止部材 10 Photoelectric conversion element 11 Support substrate 12 First electrode 13 First intermediate layer 14 Active layer 15 Second intermediate layer 16 Second electrode 17 Sealing member

Claims (13)

  1. 　ｐ型半導体、ｎ型半導体、界面活性剤、及び溶媒を含む、組成物。 A composition containing a p-type semiconductor, an n-type semiconductor, a surfactant, and a solvent.
  2. 　前記ｐ型半導体が、ドナー・アクセプター構造を有する高分子化合物である、請求項１に記載の組成物。 The composition according to claim 1, wherein the p-type semiconductor is a polymer compound having a donor-acceptor structure.
  3. 　前記ｐ型半導体が、下記式（Ｉ）で表される構成単位及び下記式（ＩＩ）で表される構成単位からなる群より選択される一種以上の構成単位を含む高分子化合物である、請求項１に記載の組成物。
    Figure JPOXMLDOC01-appb-C000001
     　（式（Ｉ）中、
    　Ａｒ１及びＡｒ２は、それぞれ独立して、置換基を有していてもよい３価の芳香族複素環基を表し、
    　Ｚは下記式（Ｚ－１）～式（Ｚ－７）のいずれか１つで表される基を表す。
    Figure JPOXMLDOC01-appb-C000002
     　（式（Ｚ－１）～（Ｚ－７）中、Ｒは、
    　水素原子、
    　ハロゲン原子、
    　置換基を有していてもよいアルキル基、
    　置換基を有していてもよいシクロアルキル基、
    　置換基を有していてもよいアルケニル基、
    　置換基を有していてもよいシクロアルケニル基、
    　置換基を有していてもよいアルキニル基、
    　置換基を有していてもよいシクロアルキニル基、
    　置換基を有していてもよいアリール基、
    　置換基を有していてもよいアルキルオキシ基、
    　置換基を有していてもよいシクロアルキルオキシ基、
    　置換基を有していてもよいアリールオキシ基、
    　置換基を有していてもよいアルキルチオ基、
    　置換基を有していてもよいシクロアルキルチオ基、
    　置換基を有していてもよいアリールチオ基、
    　置換基を有していてもよい１価の複素環基、
    　置換基を有していてもよい置換アミノ基、
    　置換基を有していてもよいイミン残基、
    　置換基を有していてもよいアミド基、
    　置換基を有していてもよい酸イミド基、
    　置換基を有していてもよい置換オキシカルボニル基、
    　シアノ基、
    　ニトロ基、
    　－Ｃ（＝Ｏ）－Ｒｃで表される基、又は
    　－ＳＯ２－Ｒｄで表される基を表し、
    　Ｒｃ及びＲｄは、それぞれ独立して、
    　水素原子、
    　置換基を有していてもよいアルキル基、
    　置換基を有していてもよいシクロアルキル基、
    　置換基を有していてもよいアリール基、
    　置換基を有していてもよいアルキルオキシ基、
    　置換基を有していてもよいシクロアルキルオキシ基、
    　置換基を有していてもよいアリールオキシ基、又は
    　置換基を有していてもよい１価の複素環基を表す。
    　式（Ｚ－１）～式（Ｚ－７）中、Ｒが２つある場合、２つあるＲは同一であっても異なっていてもよい。））
    Figure JPOXMLDOC01-appb-C000003
     　（式（ＩＩ）中、Ａｒ３は２価の芳香族複素環基を表す。）     A claim in which the p-type semiconductor is a polymer compound containing one or more structural units selected from the group consisting of a structural unit represented by the following formula (I) and a structural unit represented by the following formula (II). Item 1. The composition according to item 1.
    Figure JPOXMLDOC01-appb-C000001
     (In formula (I),
    Ar 1 and Ar 2 each independently represent a trivalent aromatic heterocyclic group which may have a substituent,
    Z represents a group represented by any one of the following formulas (Z-1) to (Z-7).
    Figure JPOXMLDOC01-appb-C000002
     (In formulas (Z-1) to (Z-7), R is
    hydrogen atom,
    halogen atom,
    an alkyl group that may have a substituent,
    cycloalkyl group which may have a substituent,
    Alkenyl group which may have a substituent,
    Cycloalkenyl group which may have a substituent,
    an alkynyl group which may have a substituent,
    cycloalkynyl group which may have a substituent,
    an aryl group which may have a substituent,
    an alkyloxy group which may have a substituent,
    cycloalkyloxy group which may have a substituent,
    an aryloxy group which may have a substituent,
    an alkylthio group which may have a substituent,
    cycloalkylthio group which may have a substituent,
    Arylthio group which may have a substituent,
    a monovalent heterocyclic group which may have a substituent,
    a substituted amino group which may have a substituent,
    imine residue which may have a substituent,
    An amide group which may have a substituent,
    acid imide group which may have a substituent,
    a substituted oxycarbonyl group which may have a substituent,
    cyano group,
    nitro group,
    -C(=O)-R represents a group represented by c , or -SO 2 represents a group represented by R d ,
    R c and R d are each independently,
    hydrogen atom,
    an alkyl group that may have a substituent,
    cycloalkyl group which may have a substituent,
    an aryl group which may have a substituent,
    an alkyloxy group which may have a substituent,
    cycloalkyloxy group which may have a substituent,
    Represents an aryloxy group which may have a substituent or a monovalent heterocyclic group which may have a substituent.
    In formulas (Z-1) to (Z-7), when there are two R's, the two R's may be the same or different. ))
    Figure JPOXMLDOC01-appb-C000003
     (In formula (II), Ar 3 represents a divalent aromatic heterocyclic group.)
  4. 　前記ｎ型半導体が、フラーレン誘導体である、請求項１に記載の組成物。 The composition according to claim 1, wherein the n-type semiconductor is a fullerene derivative.
  5. 　前記ｎ型半導体が、非フラーレン化合物である、請求項１に記載の組成物。 The composition according to claim 1, wherein the n-type semiconductor is a non-fullerene compound.
  6. 　前記溶媒が、芳香族炭化水素溶媒を含む、請求項１に記載の組成物。 The composition according to claim 1, wherein the solvent comprises an aromatic hydrocarbon solvent.
  7. 　前記界面活性剤が、ノニオン性界面活性剤である、請求項１に記載の組成物。 The composition according to claim 1, wherein the surfactant is a nonionic surfactant.
  8. 　前記界面活性剤が、ポリ（メタ）アクリレート構造を有する化合物である、請求項１に記載の組成物。 The composition according to claim 1, wherein the surfactant is a compound having a poly(meth)acrylate structure.
  9. 　前記界面活性剤が、オルガノポリシロキサン構造を有する化合物である、請求項１に記載の組成物。 The composition according to claim 1, wherein the surfactant is a compound having an organopolysiloxane structure.
  10. 　前記界面活性剤が、フッ素系界面活性剤である、請求項１に記載の組成物。 The composition according to claim 1, wherein the surfactant is a fluorosurfactant.
  11. 　ｐ型半導体、ｎ型半導体、及び界面活性剤を含む膜。 A film containing a p-type semiconductor, an n-type semiconductor, and a surfactant.
  12. 　第１の電極と、請求項１１に記載の膜と、第２の電極とをこの順で含む、有機光電変換素子。 An organic photoelectric conversion element comprising a first electrode, the film according to claim 11, and a second electrode in this order.
  13. 　請求項１２に記載の有機光電変換素子を含む、光検出素子。 A photodetection element comprising the organic photoelectric conversion element according to claim 12.
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