WO2023100719A1 - DÉRIVÉ DE FULLERÈNE, MATÉRIAU SEMI-CONDUCTEUR DE TYPE n, COUCHE DE GÉNÉRATION D'ÉNERGIE ORGANIQUE ET ÉLÉMENT DE CONVERSION PHOTOÉLECTRIQUE - Google Patents

DÉRIVÉ DE FULLERÈNE, MATÉRIAU SEMI-CONDUCTEUR DE TYPE n, COUCHE DE GÉNÉRATION D'ÉNERGIE ORGANIQUE ET ÉLÉMENT DE CONVERSION PHOTOÉLECTRIQUE Download PDF

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WO2023100719A1
WO2023100719A1 PCT/JP2022/043184 JP2022043184W WO2023100719A1 WO 2023100719 A1 WO2023100719 A1 WO 2023100719A1 JP 2022043184 W JP2022043184 W JP 2022043184W WO 2023100719 A1 WO2023100719 A1 WO 2023100719A1
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group
substituents
alkyl group
substituent
fullerene derivative
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Japanese (ja)
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隆文 永井
啓人 大瀧
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株式会社ハーベス
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/58—[b]- or [c]-condensed
    • C07D209/70—[b]- or [c]-condensed containing carbocyclic rings other than six-membered
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • 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 fullerene derivatives, n-type semiconductor materials, organic power generation layers, and photoelectric conversion elements.
  • An organic thin-film solar cell uses an organic compound as a photoelectric conversion material and is generally formed by a coating method from a solution.
  • Organic thin-film solar cells are inexpensive to fabricate, easy to scale up, flexible compared to inorganic materials such as silicon and can be used in a wider range of locations, and are less likely to deplete resources. It has various advantages such as. Therefore, in recent years, the development of organic thin-film solar cells has been promoted.
  • Patent Document 1 describes an organic photoelectric conversion element having a transparent electrode, a counter electrode, and a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are mixed, wherein the n-type organic semiconductor material of the bulk heterojunction layer is a crystal.
  • Patent Document 2 discloses an aryl group which has a pyrrolidine ring and may be substituted with one or more substituents, an alkyl group which may be substituted with one or more substituents, or 1 Inventions relating to fullerene derivatives characterized by having an alkyl ether optionally substituted with one or more substituents have been disclosed.
  • a photoelectric conversion device provided with an organic power generation layer using a conventional fullerene derivative as an n-type semiconductor material cannot obtain high conversion efficiency. Furthermore, a conventional photoelectric conversion device provided with an organic power generation layer using a fullerene derivative as an n-type semiconductor material cannot maintain high conversion efficiency for a long period of time, and there is room for improvement in durability. There was also limited information on compounds that could improve durability. Furthermore, generally, a photoelectric conversion element is produced by applying a solution composed of a p-type semiconductor material and an n-type semiconductor material. For this reason, the solubility of the semiconductor material used here in the organic solvent used for device fabrication is important. PCBM, which has been widely used as an n-type semiconductor material, has a solubility of about 1% by mass in toluene, and PCBM with a much lower solubility than this poses a problem in device fabrication by solution coating.
  • the present invention has been made in view of such circumstances, and in a photoelectric conversion device provided with an organic power generation layer using a fullerene derivative as an n-type semiconductor material, the device can be easily manufactured by solution coating, and high conversion efficiency can be achieved.
  • R 1 represents an aryl group optionally having one or more substituents
  • R 2 represents an organic group
  • R 3 represents an organic group, at least one of R 2 and R 3 represents an aryl group optionally having one or more substituents
  • Ring A represents a fullerene ring
  • Formula (1) satisfies at least one of the following two conditions. i) R 1 , R 2 and R 3 are aryl groups optionally having one or more substituents, and at least one of R 1 , R 2 and R 3 is substituted is an aryl group having a group. ii) R2 and/or R3 are aryl groups with fluorine-containing substituents; )
  • a photoelectric conversion element having an organic power generation layer using a fullerene derivative having a structure represented by a specific formula (1) as an n-type semiconductor material achieves high conversion efficiency. Furthermore, the photoelectric conversion element can maintain a high conversion efficiency for a long period of time, leading to the completion of the present invention.
  • an n-type semiconductor material comprising the above-described fullerene derivative, and according to another aspect of the present invention, the above-described n-type semiconductor material and p-type semiconductor material Provided is an organic power-generating layer containing According to another aspect of the present invention, there is provided a photoelectric conversion device comprising the organic power generation layer described above.
  • R 1 represents an aryl group optionally having one or more substituents
  • R 2 represents an organic group
  • R 3 represents an organic group
  • R 2 and At least one of R 3 represents an aryl group optionally having one or more substituents
  • Ring A represents a fullerene ring
  • formula (1) satisfies at least satisfy any one of i)
  • R 1 , R 2 and R 3 are aryl groups optionally having one or more substituents, and R 1 , R 2 and R 3 at least one of is an aryl group having a substituent.
  • R2 and/or R3 are aryl groups with fluorine-containing substituents; ) [2]
  • R 1 is an unsubstituted aryl group or an aryl group with one or more substituents, and R 1 is an aryl group with one or more substituents
  • the first substituent is an alkyl group optionally having one or more substituents
  • the fullerene derivative according to [1] comprising at least one selected from the group consisting of aralkyl groups optionally having one or more substituents.
  • At least one of R 1 , R 2 and R 3 is an aryl group having an electron donating group at the meta position, and/or R 2 and R 3 at least one of which is an aryl group having an electron-withdrawing group at the ortho-position and/or para-position, the fullerene derivative according to [1] or [2].
  • at least one of R 1 , R 2 , and R 3 contains an alkyl group optionally having one or more substituents, and the alkyl group has a carbon number
  • R 2 and R 3 contains any one of a fluorine atom and a fluorinated alkyl group having 2 or less carbon atoms, [1] to [4 ] The fullerene derivative according to any one of the above.
  • the fullerene derivative according to any one of [1] to [5] which has a LUMO level value of less than ⁇ 3.67 eV and a toluene solubility of 0.5% or more.
  • An n-type semiconductor material comprising the fullerene derivative according to any one of [1] to [6].
  • An organic power generating layer containing the n-type semiconductor material of [7] and a p-type semiconductor material.
  • a photoelectric conversion device comprising the organic power generation layer according to [8].
  • the photoelectric conversion device according to [9] which is an organic thin film solar cell.
  • the photoelectric conversion device according to [9] wherein the decrease in energy conversion efficiency after heating at 85°C for 2 hours relative to the initial energy conversion efficiency is within 5%.
  • a photoelectric conversion device having an organic power generation layer using the fullerene derivative as an n-type semiconductor material can obtain high conversion efficiency. A high conversion efficiency can be maintained.
  • R 1 represents an aryl group optionally having one or more substituents
  • R 2 represents an organic group
  • R 3 represents an organic group, at least one of R 2 and R 3 represents an aryl group optionally having one or more substituents
  • Ring A represents a fullerene ring
  • Formula (1) satisfies at least one of the following two conditions. i) R 1 , R 2 and R 3 are aryl groups optionally having one or more substituents, and at least one of R 1 , R 2 and R 3 is substituted is an aryl group having a group. ii) R2 and/or R3 are aryl groups with fluorine-containing substituents;
  • the fullerene derivative according to the present invention has a structure represented by the above formula (1), so that a photoelectric conversion element having an organic power generation layer using the fullerene derivative as an n-type semiconductor material can obtain high conversion efficiency. Furthermore, the photoelectric conversion element can maintain high conversion efficiency for a long period of time. Although the reason why a photoelectric conversion device having high conversion efficiency and high durability can be obtained by using the fullerene derivative according to the present invention is not clear, the fullerene derivative according to the present invention can be used to improve the conversion efficiency and durability.
  • the fullerene derivative according to the present invention has a structure represented by formula (1), so that it is sufficiently soluble in an organic solvent such as toluene, and the organic power generation layer forming solution can be easily prepared.
  • a thin film can be easily formed on a substrate by adopting the thin film forming method of (1).
  • R 1 , R 2 , R 3 and ring A each have a specific structure, and formula (1) satisfies conditions i) and ii). It is characterized by satisfying at least one of them.
  • Common preferred embodiments for cases i) and ii) Particularly preferred embodiments for i) Especially preferred embodiments for ii) The embodiments of the present invention will be described in this order.
  • R 1 represents an aryl group optionally having one or more substituents.
  • R 1 can be an unsubstituted aryl group or an aryl group with one or more substituents.
  • Aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl groups, and the aryl group is preferably a phenyl group.
  • R 1 is an aryl group having one or more substituents
  • the substituent of the aryl group included in R 1 is referred to as a first substituent.
  • R 1 can consist of the first substituent and an aryl group.
  • the first substituent is at least one selected from the group consisting of an alkyl group optionally having one or more substituents and an aralkyl group optionally having one or more substituents and may include one or more, and may include one or two.
  • the first substituent further preferably contains at least one selected from the group consisting of alkyl groups optionally having one or more substituents, and may contain one or more of these, It can contain one or two.
  • the first substituent is preferably constructed with hydrocarbon groups that do not contain heteroatoms such as oxygen, sulfur and nitrogen. That is, R 1 preferably does not contain an ether bond or an ester bond in the bonding portion between the aryl group and any substituent, and preferably does not contain an ether bond or an ester bond.
  • alkyl group optionally having one or more substituents that the first substituent may contain a linear or branched alkyl group optionally having one or more substituents Alkyl groups may be mentioned.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • Alkyl groups can also be unsubstituted.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Alkyl groups include n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, isobutyl, sec-butyl and isopentyl groups.
  • the aralkyl group can have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of aralkyl groups include benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 3-phenylpropyl, 4-phenylbutyl and 5-phenylpentyl groups.
  • R2 represents an organic group.
  • an organic group means a group containing one or more carbon atoms (or a group formed by removing a hydrogen atom from an organic compound).
  • the organic group can be a hydrocarbon group optionally having one or more substituents.
  • Hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, and aralkyl groups, and groups in which two or more of these are linked. be able to.
  • R 2 is an alkyl group optionally having one or more substituents, an aralkyl group optionally having one or more substituents, or having one or more substituents An aryl group that has a low molecular weight is preferred.
  • R 2 is an alkyl group optionally having one or more substituents
  • R 2 is a linear or branched alkyl group optionally having one or more substituents It can be an alkyl group.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • Alkyl groups can also be unsubstituted.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the alkyl group include the alkyl groups listed as the alkyl group that the first substituent may contain.
  • the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the aralkyl group include the aralkyl groups listed as the aralkyl group that the first substituent may contain.
  • R 2 When R 2 represents an aryl group optionally having one or more substituents, R 2 can be an unsubstituted aryl group or an aryl group having one or more substituents.
  • Aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl groups, and the aryl group is preferably a phenyl group.
  • R 2 is an aryl group having one or more substituents
  • the substituent of the aryl group included in R 2 is referred to as a second substituent.
  • R2 can consist of a second substituent and an aryl group.
  • the second substituent consists of a fluorine atom, a fluorinated alkyl group, an alkyl group optionally having one or more substituents, and an aralkyl group optionally having one or more substituents It is preferable to include at least one selected from the group, one or more of these may be included, and one or two may be included.
  • the second substituent further preferably contains at least one selected from the group consisting of a fluorine atom, a fluorinated alkyl group, and an alkyl group optionally having one or more substituents. One or more may be included, and one or two may be included.
  • the second substituent may contain fluorine, but is preferably a substituent that does not contain other heteroatoms such as oxygen, sulfur, and nitrogen.
  • R 2 preferably does not contain an ether bond or an ester bond, for example, in the bonding portion between the aryl group and any substituent, and preferably R 2 does not contain an ether bond or an ester bond.
  • a fluorinated alkyl group that the second substituent may comprise can be a fluoroalkyl group, wherein the alkyl group is substituted with one or more fluorine atoms.
  • the fluorinated alkyl group may have a substituent other than a fluorine atom.
  • the fluorinated alkyl group can also be an alkyl group having no substituents other than fluorine atoms.
  • the fluorinated alkyl group is preferably a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.
  • the fluorinated alkyl group preferably has 1 or 2 carbon atoms.
  • the fluorinated alkyl group is preferably a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, or a pentafluoroethyl group.
  • a trifluoromethyl group and a pentafluoroethyl group are more preferred, and a trifluoromethyl group is even more preferred.
  • alkyl group optionally having one or more substituents that the second substituent may contain a linear or branched alkyl group optionally having one or more substituents Alkyl groups may be mentioned.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • Alkyl groups can also be unsubstituted.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the alkyl group that the second substituent may contain include the alkyl groups listed as the alkyl group that the first substituent may contain.
  • the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the aralkyl group that the second substituent may contain include the aralkyl groups listed as the aralkyl groups that the first substituent may contain.
  • R3 represents an organic group.
  • an organic group means a group containing one or more carbon atoms (or a group formed by removing a hydrogen atom from an organic compound).
  • the organic group can be a hydrocarbon group optionally having one or more substituents.
  • Hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, and aralkyl groups, and groups in which two or more of these are linked. be able to.
  • R 3 is an alkyl group optionally having one or more substituents, an aralkyl group optionally having one or more substituents, or having one or more substituents An aryl group that has a low molecular weight is preferred.
  • R 3 is an alkyl group optionally having one or more substituents
  • R 3 is a linear or branched alkyl group optionally having one or more substituents It can be an alkyl group.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • Alkyl groups can also be unsubstituted.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the alkyl group include the alkyl groups listed as the alkyl group that the first substituent may contain.
  • the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the aralkyl group include the aralkyl groups listed as the aralkyl group that the first substituent may contain.
  • R 3 is an aryl group optionally having one or more substituents
  • the substituent of the aryl group contained in R 3 is referred to as the third substituent.
  • R3 can consist of a third substituent and an aryl group.
  • the third substituent consists of a fluorine atom, a fluorinated alkyl group, an alkyl group optionally having one or more substituents, and an aralkyl group optionally having one or more substituents It is preferable to include at least one selected from the group, one or more of these may be included, and one or two may be included.
  • the third substituent preferably contains at least one selected from the group consisting of a fluorine atom, a fluorinated alkyl group, and an alkyl group optionally having one or more substituents. One or more may be included, and one or two may be included.
  • the third substituent may contain fluorine, it is preferably a substituent that does not contain other heteroatoms such as oxygen, sulfur and nitrogen.
  • R 3 preferably does not contain an ether bond or an ester bond in the bonding portion between the aryl group and any substituent, and preferably R 3 does not contain an ether bond or an ester bond.
  • a fluorinated alkyl group that the third substituent may comprise can be a fluoroalkyl group, wherein the alkyl group is substituted with one or more fluorine atoms.
  • the fluorinated alkyl group may have a substituent other than a fluorine atom.
  • the fluorinated alkyl group can also be an alkyl group having no substituents other than fluorine atoms.
  • the fluorinated alkyl group is preferably a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.
  • the fluorinated alkyl group preferably has 1 or 2 carbon atoms.
  • the fluorinated alkyl group is preferably a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, and a pentafluoroethyl group. , a trifluoromethyl group, or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.
  • the alkyl group optionally having one or more substituents that may be contained in the third substituent includes linear or branched alkyl groups optionally having one or more substituents.
  • Alkyl groups may be mentioned.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Alkyl groups can also be unsubstituted. Examples of the alkyl group that the third substituent may contain include the alkyl groups listed as the alkyl groups that the first substituent may contain.
  • the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the aralkyl group that the third substituent may contain include the aralkyl groups listed as the aralkyl groups that the first substituent may contain.
  • R 2 and R 3 represents an aryl group optionally having one or more substituents.
  • one of R 2 and R 3 is an alkyl group optionally having one or more substituents, or an aralkyl group optionally having one or more substituents group, the other is preferably an aryl group in which the second (or third) substituent is a fluorine-containing group.
  • R 1 , R 2 and R 3 in formula (1), at least one of R 1 , R 2 and R 3 is an aryl group having an electron donating group at the meta position, and/or R 2 and/or R 3 can be an aryl group having an electron-withdrawing group at the ortho and/or para position.
  • R 1 , R 2 and R 3 in formula (1), only one of R 1 , R 2 and R 3 is an aryl group having an electron donating group at the meta position.
  • two of R 1 , R 2 and R 3 may be aryl groups having an electron donating group at the meta position, or R 1 , R 2 and R 3 may have an electron donating group at the meta position.
  • R 2 or R 3 may be an aryl group having an electron withdrawing group at the ortho and/or para position, or R 2 and R 3 may have an electron withdrawing group at the ortho and/or para position.
  • R 2 and R 3 may have an electron withdrawing group at the ortho and/or para position.
  • Examples of the electron-donating group that at least one of R 1 , R 2 , and R 3 may have at the meta position include alkyl groups optionally having one or more substituents, and aralkyl groups. is preferably an alkyl group optionally having one or more substituents. Examples of the alkyl group optionally having one or more substituents include linear or branched alkyl groups optionally having one or more substituents. In addition, the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group. The number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Alkyl groups can also be unsubstituted. As the alkyl group, specific examples of the alkyl group listed as the first substituent can be given.
  • Examples of the electron-withdrawing group that at least one of R 2 and R 3 may have at the ortho-position and/or para-position include a fluorine atom and a fluorinated alkyl group.
  • a fluorinated alkyl group can be a fluoroalkyl group, wherein the alkyl group is substituted with one or more fluorine atoms.
  • the fluorinated alkyl group may have a substituent other than a fluorine atom.
  • the fluorinated alkyl group can also be an alkyl group having no substituents other than fluorine atoms.
  • the fluorinated alkyl group is preferably a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.
  • the fluorinated alkyl group preferably has 1 or 2 carbon atoms.
  • the fluorinated alkyl group is preferably a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, and a pentafluoroethyl group. , a trifluoromethyl group, or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.
  • At least one of R 1 , R 2 and R 3 may contain an alkyl group optionally having one or more substituents.
  • the alkyl group that at least one of R 1 , R 2 , and R 3 may contain may be a linear or branched alkyl group having 4 or more and 12 or less carbon atoms.
  • R 1 , R 2 and R 3 contains an alkyl group optionally having one or more substituents
  • R 1 , R 2 or , R 3 is an aryl group optionally having one or more substituents
  • R 1 , R 2 or R 3 is the first, second or third substituent, This includes cases where an alkyl group optionally having one or more substituents is included.
  • alkyl group that at least one of R 1 , R 2 and R 3 may contain does not contain a fluorinated alkyl group. Alkyl groups can also be unsubstituted. The number of carbon atoms in the alkyl group can be 4-12, preferably 4-10. The number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here. Examples of the alkyl group that at least one of R 1 , R 2 and R 3 may contain include the alkyl groups listed as the alkyl group that the first substituent may contain.
  • At least one of R 2 and R 3 may contain any one of a fluorine atom and a fluorinated alkyl group having 1 or 2 carbon atoms.
  • "at least one of R 2 and R 3 contains any one of a fluorine atom and a fluorinated alkyl group having 1 or 2 carbon atoms” means, for example, R 2 and/or R 3 is an aryl group optionally having one or more substituents, wherein R 2 and/or R 3 are, as the second or third substituents, a fluorine atom and 1 or 2 carbon atoms It includes the case of containing any one of fluorinated alkyl groups.
  • the fluorinated alkyl group that at least one of R 2 and R 3 may have can be a fluoroalkyl group in which the alkyl group is substituted with one or more fluorine atoms.
  • the fluorinated alkyl group may have a substituent other than a fluorine atom.
  • the fluorinated alkyl group can also be an alkyl group having no substituents other than fluorine atoms.
  • the fluorinated alkyl group is preferably a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.
  • the fluorinated alkyl group preferably has 1 or 2 carbon atoms. Specific examples of the fluorinated alkyl group include the fluorinated alkyl groups listed as the fluorinated alkyl groups that the second substituent and the third substituent may contain.
  • Ring A is preferably C60 fullerene or C70 fullerene, more preferably C60 fullerene.
  • the fullerene derivative of formula (1) includes a fullerene derivative in which ring A is C60 fullerene (hereinafter also referred to as C60 fullerene derivative) and a fullerene derivative in which ring A is C70 fullerene (hereinafter also referred to as C70 fullerene derivative). It may be a mixture.
  • the content of the C60 fullerene derivative in the mixture is, for example, 0.001, 0.01, 0.1, 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100% by mass. , within a range between any two of the numerical values exemplified herein.
  • the fullerene derivative represented by Formula (1) according to the present invention satisfies at least one of the following two conditions. i) R 1 , R 2 and R 3 are aryl groups optionally having one or more substituents, and at least one of R 1 , R 2 and R 3 is substituted is an aryl group having a group. ii) R2 and/or R3 are aryl groups with fluorine-containing substituents;
  • the fullerene derivative represented by formula (1) according to the present invention satisfies at least one of the above conditions i) and ii), and more preferably satisfies the above conditions i) and ii). An embodiment that is particularly preferred when condition i) is satisfied will be described in detail below.
  • R 1 , R 2 and R 3 are aryl groups optionally having one or more substituents, and at least one of R 1 , R 2 and R 3 is Especially preferred embodiment when the aryl group has a substituent>
  • R 1 , R 2 and R 3 are aryl groups optionally having one or more substituents, and , R 1 , R 2 , and R 3 can be a substituted aryl group. That is, in this case, all of R 1 , R 2 and R 3 are aryl groups optionally having one or more substituents, and R 1 , R 2 and R 3 At least one of them can be an aryl group having a substituent.
  • R 1 , R 2 and R 3 can be substituted aryl groups.
  • R 1 , R 2 and R 3 are preferably substituted aryl groups.
  • at least R 1 is preferably an aryl group having a substituent.
  • R 1 represents an aryl group optionally having one or more substituents. That is, R 1 can be an unsubstituted aryl group or an aryl group with one or more substituents.
  • Aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl groups, with phenyl groups being preferred.
  • R 1 is an aryl group having one or more substituents
  • the substituent of the aryl group included in R 1 is referred to as a first substituent.
  • R 1 can consist of the first substituent and an aryl group.
  • the first substituent is at least one selected from the group consisting of an alkyl group optionally having one or more substituents and an aralkyl group optionally having one or more substituents and may include one or more, and may include one or two.
  • the first substituent can be an alkyl group optionally having one or more substituents.
  • the first substituent is preferably constructed with hydrocarbon groups that do not contain heteroatoms such as oxygen, sulfur and nitrogen. That is, R 1 preferably does not contain an ether bond or an ester bond in the bonding portion between the aryl group and any substituent, and preferably does not contain an ether bond or an ester bond.
  • alkyl group optionally having one or more substituents that the first substituent may contain a linear or branched alkyl group optionally having one or more substituents Alkyl groups may be mentioned.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • Alkyl groups can also be unsubstituted.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Alkyl groups include n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, isobutyl, sec-butyl and isopentyl groups.
  • the aralkyl group can have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of aralkyl groups include benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 3-phenylpropyl, 4-phenylbutyl and 5-phenylpentyl groups.
  • R 1 is preferably a substituted aryl group, more preferably a substituted phenyl group.
  • R 1 preferably has, as the first substituent, an alkyl group optionally substituted with one or more substituents. Preferred forms of alkyl groups optionally substituted with one or more substituents are as described above.
  • R 1 preferably has an alkyl group optionally substituted with one or more substituents at the meta position.
  • R2 represents an aryl group optionally having one or more substituents.
  • R 2 can be an unsubstituted aryl group or an aryl group with one or more substituents.
  • Aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl groups, with phenyl groups being preferred.
  • R 2 is an aryl group having one or more substituents
  • the substituent of the aryl group included in R 2 is referred to as a second substituent.
  • R2 can consist of a second substituent and an aryl group.
  • the second substituent consists of a fluorine atom, a fluorinated alkyl group, an alkyl group optionally having one or more substituents, and an aralkyl group optionally having one or more substituents It is preferable to include at least one selected from the group, one or more of these may be included, and one or two may be included.
  • the second substituent further preferably contains at least one selected from the group consisting of a fluorine atom, a fluorinated alkyl group, and an alkyl group optionally having one or more substituents. One or more may be included, and one or two may be included.
  • the second substituent may contain fluorine, but is preferably a substituent that does not contain other heteroatoms such as oxygen, sulfur, and nitrogen.
  • R 2 preferably does not contain an ether bond or an ester bond, for example, in the bonding portion between the aryl group and any substituent, and preferably R 2 does not contain an ether bond or an ester bond.
  • a fluorinated alkyl group that the second substituent may comprise can be a fluoroalkyl group, wherein the alkyl group is substituted with one or more fluorine atoms.
  • the fluorinated alkyl group may have a substituent other than a fluorine atom.
  • the fluorinated alkyl group can also be an alkyl group having no substituents other than fluorine atoms.
  • the fluorinated alkyl group is preferably a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.
  • the fluorinated alkyl group preferably has 1 or 2 carbon atoms.
  • the fluorinated alkyl group is preferably a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, and a pentafluoroethyl group. , a trifluoromethyl group, or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.
  • alkyl group optionally having one or more substituents that the second substituent may contain a linear or branched alkyl group optionally having one or more substituents Alkyl groups may be mentioned.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • Alkyl groups can also be unsubstituted.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the alkyl group that the second substituent may contain include the alkyl groups listed as the alkyl group that the first substituent may contain.
  • the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the aralkyl group that the second substituent may contain include the aralkyl groups listed as the aralkyl groups that the first substituent may contain.
  • R 3 in formula (1) represents an aryl group optionally having one or more substituents. That is, R 3 can be an unsubstituted aryl group or an aryl group with one or more substituents.
  • R3 is an aryl group having one or more substituents
  • the substituent of the aryl group contained in R3 is referred to as the third substituent.
  • R3 can consist of a third substituent and an aryl group.
  • the third substituent consists of a fluorine atom, a fluorinated alkyl group, an alkyl group optionally having one or more substituents, and an aralkyl group optionally having one or more substituents It is preferable to include at least one selected from the group, one or more of these may be included, and one or two may be included.
  • the third substituent preferably contains at least one selected from the group consisting of a fluorine atom, a fluorinated alkyl group, and an alkyl group optionally having one or more substituents. One or more may be included, and one or two may be included.
  • the third substituent may contain fluorine, it is preferably a substituent that does not contain other heteroatoms such as oxygen, sulfur and nitrogen.
  • R 3 preferably does not contain an ether bond or an ester bond in the bonding portion between the aryl group and any substituent, and preferably R 3 does not contain an ether bond or an ester bond.
  • a fluorinated alkyl group that the third substituent may comprise can be a fluoroalkyl group, wherein the alkyl group is substituted with one or more fluorine atoms.
  • the fluorinated alkyl group may have a substituent other than a fluorine atom.
  • the fluorinated alkyl group can also be an alkyl group having no substituents other than fluorine atoms.
  • the fluorinated alkyl group is preferably a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.
  • the fluorinated alkyl group preferably has 1 or 2 carbon atoms.
  • the fluorinated alkyl group is preferably a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, and a pentafluoroethyl group. , a trifluoromethyl group, or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.
  • the alkyl group optionally having one or more substituents that may be contained in the third substituent includes linear or branched alkyl groups optionally having one or more substituents.
  • Alkyl groups may be mentioned.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Alkyl groups can also be unsubstituted. Examples of the alkyl group that the third substituent may contain include the alkyl groups listed as the alkyl groups that the first substituent may contain.
  • the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the aralkyl group that the third substituent may contain include the aralkyl groups listed as the aralkyl groups that the first substituent may contain.
  • At least one of R 2 and R 3 is preferably a substituted aryl group, more preferably a substituted phenyl group.
  • Ring A is preferably C60 fullerene or C70 fullerene, more preferably C60 fullerene.
  • the fullerene derivative of formula (1) includes a fullerene derivative in which ring A is C60 fullerene (hereinafter also referred to as C60 fullerene derivative) and a fullerene derivative in which ring A is C70 fullerene (hereinafter also referred to as C70 fullerene derivative). It may be a mixture.
  • the content of the C60 fullerene derivative in the mixture is, for example, 0.001, 0.01, 0.1, 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100% by mass. , within a range between any two of the numerical values exemplified herein.
  • condition ii) is satisfied
  • R 2 and/or R 3 is an aryl group having a fluorine-containing substituent>
  • at least one of R 2 and R 3 can be an aryl group having a fluorine-containing substituent.
  • R 2 and R 3 may be aryl groups having fluorine-containing substituents, or R 2 and R 3 may be aryl groups having fluorine-containing substituents.
  • R 2 or R 3 is preferably an aryl group having a fluorine-containing substituent.
  • R 1 represents an aryl group optionally having one or more substituents. That is, R 1 can be an unsubstituted aryl group or an aryl group with one or more substituents.
  • Aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl groups, with phenyl groups being preferred.
  • R 1 is an aryl group having one or more substituents
  • the substituent of the aryl group included in R 1 is referred to as a first substituent.
  • R 1 can consist of the first substituent and an aryl group.
  • the first substituent is at least one selected from the group consisting of an alkyl group optionally having one or more substituents and an aralkyl group optionally having one or more substituents and may include one or more, and may include one or two.
  • the first substituent can be an alkyl group optionally having one or more substituents.
  • the first substituent is preferably constructed with hydrocarbon groups that do not contain heteroatoms such as oxygen, sulfur and nitrogen. That is, R 1 preferably does not contain an ether bond or an ester bond in the bonding portion between the aryl group and any substituent, and preferably does not contain an ether bond or an ester bond.
  • alkyl group optionally having one or more substituents that the first substituent may contain a linear or branched alkyl group optionally having one or more substituents Alkyl groups may be mentioned.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • Alkyl groups can also be unsubstituted.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Alkyl groups include n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, isobutyl, sec-butyl and isopentyl groups.
  • the aralkyl group can have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of aralkyl groups include benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 3-phenylpropyl, 4-phenylbutyl and 5-phenylpentyl groups.
  • R 1 is preferably an unsubstituted aryl group, preferably a phenyl group.
  • R 1 is preferably an aryl group having an alkyl group optionally substituted with one or more substituents as the first substituent, and one or more substituents as the first substituent A phenyl group having an optionally substituted alkyl group is more preferred. Preferred forms of alkyl groups optionally substituted with one or more substituents are as described above.
  • R 1 preferably has an alkyl group optionally substituted with one or more substituents at the meta position.
  • R2 represents an organic group.
  • an organic group means a group containing one or more carbon atoms (or a group formed by removing a hydrogen atom from an organic compound).
  • the organic group can be a hydrocarbon group optionally having one or more substituents.
  • Hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, and aralkyl groups, and groups in which two or more of these are linked. be able to.
  • R 2 is an alkyl group optionally having one or more substituents, an aralkyl group optionally having one or more substituents, or having one or more substituents
  • An aryl group optionally having one or more substituents is preferable, and an alkyl group optionally having one or more substituents or an aryl group optionally having one or more substituents is more preferable.
  • R 2 is an alkyl group optionally having one or more substituents
  • R 2 is a linear or branched alkyl group optionally having one or more substituents It can be an alkyl group.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • Alkyl groups can also be unsubstituted.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the alkyl group include the alkyl groups listed as the alkyl group that the first substituent may contain.
  • the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the aralkyl group include the aralkyl groups listed as the aralkyl group that the first substituent may contain.
  • R 2 When R 2 represents an aryl group optionally having one or more substituents, R 2 can be an unsubstituted aryl group or an aryl group having one or more substituents.
  • Aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl groups, with phenyl groups being preferred.
  • R 2 is an aryl group having one or more substituents
  • the substituent of the aryl group included in R 2 is referred to as a second substituent.
  • R2 can consist of a second substituent and an aryl group.
  • the second substituent consists of a fluorine atom, a fluorinated alkyl group, an alkyl group optionally having one or more substituents, and an aralkyl group optionally having one or more substituents It is preferable to include at least one selected from the group, one or more of these may be included, and one or two may be included.
  • the second substituent further preferably contains at least one selected from the group consisting of a fluorine atom, a fluorinated alkyl group, and an alkyl group optionally having one or more substituents. One or more may be included, and one or two may be included.
  • the second substituent may contain fluorine, but is preferably a substituent that does not contain other heteroatoms such as oxygen, sulfur, and nitrogen.
  • R 2 preferably does not contain an ether bond or an ester bond, for example, in the bonding portion between the aryl group and any substituent, and preferably R 2 does not contain an ether bond or an ester bond.
  • a fluorinated alkyl group that the second substituent may comprise can be a fluoroalkyl group, wherein the alkyl group is substituted with one or more fluorine atoms.
  • the fluorinated alkyl group may have a substituent other than a fluorine atom.
  • the fluorinated alkyl group can also be an alkyl group having no substituents other than fluorine atoms.
  • the fluorinated alkyl group is preferably a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.
  • the fluorinated alkyl group preferably has 1 or 2 carbon atoms.
  • the fluorinated alkyl group is preferably a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, and a pentafluoroethyl group. , a trifluoromethyl group, or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.
  • alkyl group optionally having one or more substituents that the second substituent may contain a linear or branched alkyl group optionally having one or more substituents Alkyl groups may be mentioned.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • Alkyl groups can also be unsubstituted.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the alkyl group that the second substituent may contain include the alkyl groups listed as the alkyl group that the first substituent may contain.
  • the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the aralkyl group that the second substituent may contain include the aralkyl groups listed as the aralkyl groups that the first substituent may contain.
  • R 3 in formula (1) represents an organic group.
  • an organic group means a group containing one or more carbon atoms (or a group formed by removing a hydrogen atom from an organic compound).
  • the organic group can be a hydrocarbon group optionally having one or more substituents.
  • Hydrocarbon groups include alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, cycloalkadienyl groups, aryl groups, and aralkyl groups, and groups in which two or more of these are linked. be able to.
  • R 3 is an alkyl group optionally having one or more substituents, an aralkyl group optionally having one or more substituents, or having one or more substituents
  • An aryl group optionally having one or more substituents is preferred, and an alkyl group optionally having one or more substituents or an aryl group optionally having one or more substituents is more preferred.
  • R 3 is an alkyl group optionally having one or more substituents
  • R 3 is a linear or branched alkyl group optionally having one or more substituents It can be an alkyl group.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • Alkyl groups can also be unsubstituted.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the alkyl group include the alkyl groups listed as the alkyl group that the first substituent may contain.
  • the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the aralkyl group include the aralkyl groups listed as the aralkyl group that the first substituent may contain.
  • R 3 When R 3 is an aryl group optionally having one or more substituents, R 3 can be an unsubstituted aryl group or an aryl group having one or more substituents.
  • Aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, and 2-anthryl groups, with phenyl groups being preferred.
  • R3 is an aryl group having one or more substituents
  • the substituent of the aryl group contained in R3 is referred to as the third substituent.
  • R3 can consist of a third substituent and an aryl group.
  • the third substituent consists of a fluorine atom, a fluorinated alkyl group, an alkyl group optionally having one or more substituents, and an aralkyl group optionally having one or more substituents It is preferable to include at least one selected from the group, one or more of these may be included, and one or two may be included.
  • the third substituent preferably contains at least one selected from the group consisting of a fluorine atom, a fluorinated alkyl group, and an alkyl group optionally having one or more substituents. One or more may be included, and one or two may be included.
  • the third substituent may contain fluorine, it is preferably a substituent that does not contain other heteroatoms such as oxygen, sulfur and nitrogen.
  • R 3 preferably does not contain an ether bond or an ester bond in the bonding portion between the aryl group and any substituent, and preferably R 3 does not contain an ether bond or an ester bond.
  • a fluorinated alkyl group that the third substituent may comprise can be a fluoroalkyl group, wherein the alkyl group is substituted with one or more fluorine atoms.
  • the fluorinated alkyl group may have a substituent other than a fluorine atom.
  • the fluorinated alkyl group can also be an alkyl group having no substituents other than fluorine atoms.
  • the fluorinated alkyl group is preferably a perfluoroalkyl group in which all hydrogen atoms in the alkyl group are substituted with fluorine atoms.
  • the fluorinated alkyl group preferably has 1 or 2 carbon atoms.
  • the fluorinated alkyl group is preferably a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, and a pentafluoroethyl group. , a trifluoromethyl group, or a pentafluoroethyl group, and even more preferably a trifluoromethyl group.
  • the alkyl group optionally having one or more substituents that may be contained in the third substituent includes linear or branched alkyl groups optionally having one or more substituents.
  • Alkyl groups may be mentioned.
  • the alkyl group which may have one or more substituents may not contain a fluorinated alkyl group.
  • the number of carbon atoms in the alkyl group can be 4-12, preferably 4-10.
  • the number of carbon atoms in the alkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Alkyl groups can also be unsubstituted. Examples of the alkyl group that the third substituent may contain include the alkyl groups listed as the alkyl groups that the first substituent may contain.
  • the aralkyl group may have 4 to 12 carbon atoms, preferably 4 to 10 carbon atoms.
  • the number of carbon atoms in the aralkyl group is, for example, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the aralkyl group that the third substituent may contain include the aralkyl groups listed as the aralkyl groups that the first substituent may contain.
  • At least one of R 2 and R 3 is preferably an aryl group having a fluorine-containing substituent, and at least one is preferably a phenyl group having a fluorine-containing substituent.
  • R 2 or R 3 is an alkyl group optionally having one or more substituents
  • the other is an aryl having a fluorine-containing substituent
  • the fluorine-containing group is fluorine or perfluoro It can contain an alkyl group.
  • Ring A is preferably C60 fullerene or C70 fullerene, more preferably C60 fullerene.
  • the fullerene derivative of formula (1) includes a fullerene derivative in which ring A is C60 fullerene (hereinafter also referred to as C60 fullerene derivative) and a fullerene derivative in which ring A is C70 fullerene (hereinafter also referred to as C70 fullerene derivative). It may be a mixture.
  • the content of the C60 fullerene derivative in the mixture is, for example, 0.001, 0.01, 0.1, 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100% by mass. , within a range between any two of the numerical values exemplified herein.
  • R 1 is a phenyl group or a phenyl group having an alkyl group
  • R 2 is a phenyl group having a fluorine atom or a fluorinated alkyl group
  • R 3 is a phenyl group
  • R 1 is a phenyl group or a phenyl group having an alkyl group
  • R 2 is a phenyl group having an alkyl group
  • R 3 is a phenyl group
  • R 1 is a phenyl group or a phenyl group having an alkyl group
  • R 2 is a phenyl group having a fluorine atom or a fluorinated alkyl group
  • R 3 is an alkyl group
  • the fullerene derivative according to one embodiment of the present invention preferably has a LUMO level value of less than -3.67 eV.
  • the values of the LUMO levels are, for example, ⁇ 3.75, ⁇ 3.74, ⁇ 3.73, ⁇ 3.72, ⁇ 3.71, ⁇ 3.7, ⁇ 3.69, ⁇ 3.68 eV. , within a range between any two of the numerical values exemplified herein.
  • a fullerene derivative according to one embodiment of the present invention has a structure represented by formula (1), and R 1 , R 2 , and/or R 3 have specific substituents, so that the LUMO level can be adjusted lower, which is considered to contribute to the improvement of conversion efficiency.
  • the LUMO level can be measured by the method described in Karakawa et al., Journal of Materials Chemistry A, 2014, 2, 20889 pages.
  • the fullerene derivative according to one embodiment of the present invention preferably has a toluene solubility of 0.5% by mass or more at room temperature, more preferably 1.0% by mass or more.
  • the toluene solubility may be, for example, about 0.5, 1.0, 1.5, 2.0, 2.5, 3.0% by mass, or between any two of the numerical values exemplified here. may be within the range.
  • the toluene solubility means the mass of a fullerene derivative soluble in 100 g of toluene.
  • a fullerene derivative according to an embodiment of the present invention has a structure represented by formula (1), and R 1 , R 2 and/or R 3 have specific substituents such as toluene. It is presumed to have moderate solubility in an organic solvent, so that the organic power generation layer forming solution can be easily prepared, and the organic power generation layer can be easily formed.
  • the solubility in toluene at room temperature can be determined from the absorbance using the Beer-Lambert law.
  • a molar extinction coefficient is obtained using a toluene solution of a fullerene derivative with a known concentration.
  • a certain amount of the supernatant solution of the supersaturated toluene solution of the fullerene derivative is weighed, and the absorbance thereof is measured.
  • the concentration can be calculated according to the following formula.
  • C A/ ⁇ d [In the formula, C: concentration, A: absorbance, ⁇ : molar extinction coefficient, d: cell length for absorbance measurement (1 cm)]
  • the method for producing the fullerene derivative according to the present invention is not particularly limited, and it can be produced by a known method for producing a fullerene derivative or a method analogous thereto.
  • a fullerene derivative according to one embodiment of the present invention can be synthesized by the following scheme known as the plateau reaction.
  • the amount ratio of the aldehyde compound, the amino acid compound, and the fullerene is not particularly limited, but from the viewpoint of increasing the yield, for example, 0.1 to 10 mol each of the aldehyde compound and the amino acid compound can be used per 1 mol of the fullerene. can be used, preferably in an amount of 0.5 to 2 mol.
  • the reaction can be carried out in the absence of solvent or in a solvent.
  • solvents include carbon disulfide, chloroform, dichloroethane, toluene, xylene, chlorobenzene, dichlorobenzene and the like. Among these, chloroform, toluene, xylene, chlorobenzene, and the like are preferable. These solvents may be mixed in an appropriate ratio and used.
  • the reaction temperature can be, for example, room temperature to 150°C, preferably 80 to 120°C. In this specification, room temperature is 15 to 30°C.
  • the reaction time is, for example, 1 hour to 4 days, preferably 10 to 48 hours.
  • the obtained compound can be purified by a known purification method, if necessary.
  • the obtained compound is purified by silica gel column chromatography (developing solvent is preferably hexane-chloroform, hexane-toluene, or hexane-carbon disulfide), and then further HPLC (preparative GPC ) (preferable developing solvent is, for example, chloroform or toluene).
  • Aldehyde compounds, amino acid compounds, and fullerenes used in the reaction may be synthesized by known methods or methods based thereon, or may be commercially available.
  • an aldehyde compound and an amino acid compound can be synthesized, for example, by the method of Examples.
  • the n-type semiconductor material according to one embodiment of the present invention can contain the fullerene derivative.
  • the n-type semiconductor material according to one embodiment of the present invention can also be made of the above fullerene derivative.
  • An organic power generation layer according to an embodiment of the present invention can contain the n-type semiconductor material and the p-type semiconductor material.
  • An organic power generation layer according to an embodiment of the present invention can be made of the n-type semiconductor material of the present invention and the organic p-type semiconductor.
  • Examples of p-type semiconductor materials include poly-p-phenylene vinylene, poly-alkoxy-p-phenylene vinylene, poly-9,9-dialkylfluorene, poly-p-phenylene vinylene, and the like.
  • a donor-acceptor type ⁇ -conjugated polymer can be used that enables absorption of long-wavelength light by narrowing the bandgap (low bandgap).
  • a donor-acceptor type ⁇ -conjugated polymer has a structure in which donor units and acceptor units are alternately arranged.
  • Donor units include benzodithiophene, dithienosilol, and N-alkylcarbazole, and acceptor units include benzothiadiazole, thienothiophene, thiophenepyrroledione, and the like.
  • poly(thieno[3,4-b]thiophene-co-benzo[1,2-b:4,5-b′]thiophene) (PTBx series)
  • poly( Dithieno[1,2-b:4,5-b′][3,2-b:2′,3′-d]silole-alt-(2,1,3-benzothiadiazole)s can be mentioned.
  • Examples include PTB7, PBDTTPD, PSBTBT, PBDTTT-CF, PDTP-DFBT, and the like.
  • the n-type semiconductor material containing the fullerene derivative according to the present invention mixes with good affinity even with a long-wavelength absorption p-type semiconductor material, which has relatively poor affinity with conventional n-type semiconductor materials, Since a bulk heterojunction structure having a large interface area and high stability can be constructed, a photoelectric conversion element having high conversion efficiency and high durability can be obtained.
  • the fullerene derivative according to the present invention can also be suitably used as an n-type semiconductor material for an organic power generation layer using a long wavelength absorption p-type semiconductor material.
  • the long-wave absorption p-type semiconductor material can be specifically a p-type semiconductor material having a maximum absorption wavelength of 700 nm or more.
  • PDTP-DFBT, PTB7-Th, PCDTBT, PCPDTBT, NT812, etc. can be mentioned as long-wavelength absorption p-type semiconductor materials.
  • the n-type semiconductor material containing the fullerene derivative according to the present invention and the p-type semiconductor material form a bulk heterojunction structure.
  • the organic power generation layer according to one embodiment of the present invention can be produced, for example, by a production method including an organic power generation layer forming solution preparation step and an organic power generation layer formation step.
  • the organic power generation layer forming solution preparation step the n-type semiconductor material and p-type semiconductor material containing the fullerene derivative according to the present invention can be dissolved in an organic solvent to obtain an organic power generation layer forming solution.
  • the obtained organic power generation layer forming solution is applied to a substrate by employing a known thin film forming method such as a spin coating method, a casting method, a dipping method, an ink jet method, and a screen printing method.
  • a known thin film forming method such as a spin coating method, a casting method, a dipping method, an ink jet method, and a screen printing method.
  • a thin film can be formed thereon.
  • a photoelectric conversion device can be provided with the organic power generation layer described above.
  • a photoelectric conversion element according to an embodiment of the present invention can be used as a photosensor.
  • the photoelectric conversion element which concerns on one Embodiment of this invention can be made into an organic thin-film solar cell.
  • An organic thin-film solar cell according to an embodiment of the present invention includes, for example, a transparent electrode (cathode), a cathode-side charge transport layer, an organic power-generating layer, an anode-side charge transport layer, and a counter electrode (anode) which are sequentially laminated on a substrate.
  • a solar cell having a structure can be obtained.
  • the organic power generation layer can be a semiconductor thin film layer (that is, a photoelectric conversion layer) in which an n-type semiconductor material containing the fullerene derivative according to the present invention and a p-type semiconductor material form a bulk heterojunction structure.
  • Electrode materials include aluminum, gold, silver, copper, and indium oxide (ITO).
  • Materials for the charge transport layer include, for example, PFN (poly[9,9-bis(3′-(N,N-dimethylamino)propyl-2,7-fluorene)-alt-2,7-(9,9 -dioctylfluorene)]) and MoO 3 (molybdenum oxide).
  • a photoelectric conversion device and an organic thin film solar cell according to an embodiment of the present invention have an initial energy conversion efficiency of 7.0% or more when PTB7 or PDTP-DFBT is used as the p-type semiconductor material. Furthermore, the energy conversion efficiency after heating the photoelectric conversion element and the organic thin film solar cell at 85° C. for 2 hours can maintain 95% or more of the initial energy conversion efficiency. That is, the decrease in energy conversion efficiency after heating at 85° C. for 2 hours with respect to the initial energy conversion efficiency is within 5%.
  • a photoelectric conversion device and an organic thin film solar cell provided with an organic power generation layer containing an n-type semiconductor material containing a fullerene derivative according to the present invention according to the present invention are such that an n-type semiconductor material and a p-type semiconductor material are mixed with good affinity, Since a bulk heterojunction structure having a large interface area and high stability can be constructed, a photoelectric conversion element and an organic thin-film solar cell having high conversion efficiency and high durability can be obtained.
  • reaction vessel was immersed in an oil bath (bath temperature 100° C.) and heated with stirring for 48 hours. The reaction was followed by GLC and the reaction endpoint was determined by the disappearance of starting material. After cooling, the reaction liquid was subjected to extraction separation using ethyl acetate and water. The organic phase was concentrated by an evaporator to obtain intermediate 21 (oct-1-yn-1-yl)nitrobenzene).
  • reaction product was subjected to silica gel column chromatography (eluent n-heptane:toluene 100:1 to 50:1) and preparative HPLC (column: Buckyprep 28 mm x 250 mm, eluent: toluene, 10 mL/min, detector: RI) to obtain compound 4 (fullerene derivative (HPdFNP)) (32% yield).
  • the reactant obtained here was dissolved in 30 mL of 1,3-bis(trifluoromethyl)benzene, and NBS (N-bromosuccinimide) (1.78 g, 10.0 mmol), AIBN (azobisisobutyro nitrile) (200 mg) was added, and the mixture was heated and stirred at 90°C for 15 hours.
  • the reaction solution was diluted with heptane, washed with water and concentrated by evaporation. Aniline (1 mL), triethylamine (4 mL), and methanol (2 mL) were added to the obtained reaction product, and the mixture was stirred at room temperature for 18 hours.
  • the reaction solution was diluted with ethyl acetate, washed with water, and concentrated by evaporation.
  • Sodium hydroxide (1.8 g), 40 mL of methanol and 20 mL of water were added to the above ester, and the mixture was stirred at room temperature for 24 hours.
  • reaction solution was acidified to pH 3 with dilute hydrochloric acid and extracted with ethyl acetate. Concentration by evaporation gave 2.1 g of 2-(phenylamino)-2-[4-(trifluoromethyl)phenyl]acetic acid (93%).
  • test solar cells were prepared and their conversion efficiencies were evaluated.
  • PDTP-DFBT see the chemical formula below
  • charge transport layer material PFN (poly[9,9-bis(3′-(N,N-dimethylamino)propyl-2,7- fluorene)-alt-2,7-(9,9-dioctylfluorene)]) and MoO3 (molybdenum oxide), and ITO (indium tin oxide) (cathode) and aluminum (anode) as electrodes, respectively.
  • the solubility of the 1,2,5-triphenylpyrrolidine derivative is insufficient, and there is a problem in producing a coating-type photoelectric conversion element, but introduction of a long-chain alkyl group to the phenyl group here, or one carbon is sufficient. has improved solubility due to the introduction of CF3 groups with fluorine.
  • the LUMO level of a fullerene derivative in which R 1 , R 2 and R 3 are all phenyl groups is ⁇ 3.67 eV.
  • fullerene derivatives of compounds 2 to 6 having an electron donating group at the meta position or an electron withdrawing group at the ortho and/or para positions have a LUMO level of less than -3.67 eV.

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Abstract

La présente invention concerne un dérivé de fullerène permettant à un élément de conversion photoélectrique, qui comprend une couche organique de production d'énergie utilisant ce dérivé de fullerène comme matériau semi-conducteur de type n, d'atteindre un rendement de conversion élevé, tout en permettant à l'élément de conversion photoélectrique de maintenir le rendement de conversion élevé pendant une longue période de temps. La présente invention fournit un dérivé de fullerène de formule (1).
PCT/JP2022/043184 2021-11-30 2022-11-22 DÉRIVÉ DE FULLERÈNE, MATÉRIAU SEMI-CONDUCTEUR DE TYPE n, COUCHE DE GÉNÉRATION D'ÉNERGIE ORGANIQUE ET ÉLÉMENT DE CONVERSION PHOTOÉLECTRIQUE WO2023100719A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014218492A (ja) * 2012-07-17 2014-11-20 株式会社リコー フラーレン誘導体およびその製造方法
WO2014185536A1 (fr) * 2013-05-16 2014-11-20 ダイキン工業株式会社 Dérivé de fullerène et matériau semi-conducteur de type n
JP2015113301A (ja) * 2013-12-11 2015-06-22 株式会社リコー フラーレン誘導体およびその製造方法
WO2017061543A1 (fr) * 2015-10-06 2017-04-13 ダイキン工業株式会社 DÉRIVÉ DE FULLERÈNE ET MATÉRIAU DE SEMI-CONDUCTEUR DE TYPE n

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014218492A (ja) * 2012-07-17 2014-11-20 株式会社リコー フラーレン誘導体およびその製造方法
WO2014185536A1 (fr) * 2013-05-16 2014-11-20 ダイキン工業株式会社 Dérivé de fullerène et matériau semi-conducteur de type n
JP2015113301A (ja) * 2013-12-11 2015-06-22 株式会社リコー フラーレン誘導体およびその製造方法
WO2017061543A1 (fr) * 2015-10-06 2017-04-13 ダイキン工業株式会社 DÉRIVÉ DE FULLERÈNE ET MATÉRIAU DE SEMI-CONDUCTEUR DE TYPE n

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