WO2024071042A1 - Composé, matériau de transport de trous et élément de conversion photoélectrique utilisant ledit composé - Google Patents

Composé, matériau de transport de trous et élément de conversion photoélectrique utilisant ledit composé Download PDF

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WO2024071042A1
WO2024071042A1 PCT/JP2023/034740 JP2023034740W WO2024071042A1 WO 2024071042 A1 WO2024071042 A1 WO 2024071042A1 JP 2023034740 W JP2023034740 W JP 2023034740W WO 2024071042 A1 WO2024071042 A1 WO 2024071042A1
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group
substituent
carbon atoms
compound
photoelectric conversion
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Japanese (ja)
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泰彰 宮崎
秀聡 高橋
敦史 櫻井
洋 佐藤
俊昭 伊東
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保土谷化学工業株式会社
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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
    • H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
    • 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
    • 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
    • H10K30/80—Constructional details
    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/86—Layers having high hole mobility, e.g. hole-transporting layers or electron-blocking layers
    • 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 compound useful as a hole transport material and a photoelectric conversion element using the compound.
  • perovskite solar cells have attracted attention as a next-generation solar cell that can be manufactured at low cost by a solution process (for example, Patent Document 1, Non-Patent Documents 1 and 2).
  • a layer formed of a hole transport material is often provided in the element.
  • the purpose of using a hole transport material is (1) to improve the photoelectric conversion efficiency, and (2) to protect the perovskite material that is easily affected by moisture and oxygen (for example, Non-Patent Documents 3-4).
  • Spiro-OMeTAD has often been used as a standard organic hole transport material, and there have been few reports of organic hole transport materials that contribute more to photoelectric conversion properties than this material.
  • Non-Patent Document 5 When an organic compound is used as a hole transport material, a dopant is conventionally added to the hole transport layer to reduce the electrical resistance of the hole transport material.
  • a dopant as an additive not only complicates the manufacturing process but also leads to an increase in manufacturing costs.
  • the use of a dopant promotes the deterioration of the hole transport layer due to moisture absorption by the dopant, corrosion of the photoelectric conversion layer, and volatilization, which leads to a decrease in the durability of the element (for example, Non-Patent Document 5).
  • the problem to be solved by the present invention is to provide an organic compound useful as a hole transport material, and also to provide a photoelectric conversion element and a solar cell exhibiting excellent photoelectric conversion characteristics.
  • the inventors conducted extensive research and discovered that by using a compound having a structure in which a sulfonate group is linked to a phenoxazine skeleton as a hole transport material, it is possible to obtain a photoelectric conversion element or solar cell with good photoelectric conversion efficiency and high durability.
  • the present invention has been proposed based on this knowledge and specifically has the following configuration.
  • R 1 represents a linear or branched alkylene group having 1 to 18 carbon atoms which may have a substituent, a linear or branched alkenylene group having 2 to 20 carbon atoms which may have a substituent, a linear or branched alkynylene group having 2 to 20 carbon atoms which may have a substituent, a cycloalkylene group having 3 to 12 carbon atoms which may have a substituent, an arylene group having 6 to 36 carbon atoms which may have a substituent, or a divalent heterocyclic group having 5 to 36 ring atoms which may have a substituent, and X represents a monovalent cation other than a hydrogen ion.
  • R 2 to R 9 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms which may have a substituent, a linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent, a linear or branched alkynyl group having 2 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, a linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent, a cycloalkoxy group having 3 to 10 carbon atoms which may have a substituent, an aryloxy group having 6 to 36 carbon atoms which may have a substituent, a linear or branched alkoxycarbonyl group having 1 to 18 carbon atoms which may have a substituent, a thio group having 0 to 18 carbon atoms which may have a substituent, an amino group having
  • the compound of the present invention is useful as a hole transport material.
  • a hole transport material By using the compound of the present invention as a hole transport material in a photoelectric conversion element, it is possible to obtain a photoelectric conversion element and a solar cell having good photoelectric conversion efficiency and high durability.
  • FIG. 1 is a schematic cross-sectional view showing a configuration example of a photoelectric conversion element of the present invention.
  • a numerical range expressed using “to” means a range including the numerical values before and after "to” as the lower and upper limits.
  • some or all of the hydrogen atoms present in the compound represented by general formula (1) and the groups represented by R 1 to R 9 may be substituted with deuterium atoms.
  • “transparent” and “light-transmitting” refer to a transmittance of light to be used for photoelectric conversion of 50% or more, for example, 80% or more, for example, 90% or more, for example, 99% or more. The transmittance of light can be measured by an ultraviolet-visible spectrophotometer.
  • R 1 represents a linear or branched alkylene group having 1 to 18 carbon atoms which may have a substituent, a linear or branched alkenylene group having 2 to 20 carbon atoms which may have a substituent, a linear or branched alkynylene group having 2 to 20 carbon atoms which may have a substituent, a cycloalkylene group having 3 to 12 carbon atoms which may have a substituent, an arylene group having 6 to 36 carbon atoms which may have a substituent, or a divalent heterocyclic group having 5 to 36 ring atoms which may have a substituent.
  • the number of carbon atoms in the "straight-chain or branched alkylene group having 1 to 18 carbon atoms" in the "straight-chain or branched alkylene group having 1 to 18 carbon atoms which may have a substituent" represented by R 1 is selected from integers of 1 to 18, and may be selected from the range of, for example, 1 to 12, and may be selected from the range of, for example, 1 to 6.
  • the "straight-chain or branched alkylene group having 1 to 18 carbon atoms which may have a substituent" include divalent groups obtained by removing one hydrogen atom from an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, a 2-ethylhexyl group, a heptyl group, an octyl group, an isooctyl group, a nonyl group, or a decyl group, and a divalent group obtained by removing one hydrogen atom from a substituted alkyl group in which at least one hydrogen atom of the alkyl group is substituted with a substituent (the former divalent group obtained
  • the number of carbon atoms in the "straight-chain or branched alkenylene group having 2 to 20 carbon atoms" in the "straight-chain or branched alkenylene group having 2 to 20 carbon atoms which may have a substituent" represented by R 1 is selected from integers of 2 to 20, and may be selected from the range of, for example, 2 to 12, or may be selected from the range of, for example, 2 to 6.
  • the "straight-chain or branched alkenylene group having 2 to 20 carbon atoms which may have a substituent” include a vinyl group, a 1-propenyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, a 1-hexenyl group, an isopropenyl group, an isobutenyl group, or a divalent group obtained by removing one hydrogen atom from a straight-chain or branched alkenyl group having 2 to 20 carbon atoms to which a plurality of these alkenyl groups are bonded, and a divalent group obtained by removing one hydrogen atom from a substituted alkenyl group in which at least one hydrogen atom of the alkenyl group is substituted with a substituent (the first divalent group is preferred).
  • the number of carbon atoms in the "linear or branched alkynylene group having 2 to 20 carbon atoms which may have a substituent" represented by R 1 is selected from integers of 2 to 20, and may be selected from the range of, for example, 2 to 12, or may be selected from the range of, for example, 2 to 6.
  • linear or branched alkynylene group having 2 to 20 carbon atoms which may have a substituent include divalent groups obtained by removing one hydrogen atom from an alkynyl group, such as an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 1-methyl-2-propynyl group, a 1-pentynyl group, a 2-pentynyl group, a 1-methyl-n-butynyl group, a 2-methyl-n-butynyl group, a 3-methyl-n-butynyl group, or a 1-hexynyl group, and divalent groups obtained by removing one hydrogen atom from a substituted alkynyl group in which at least one hydrogen atom of the alkynyl group is substituted with a substituent (the former divalent group is preferred).
  • the number of carbon atoms in the "cycloalkylene group having 3 to 12 carbon atoms" in the "cycloalkylene group having 3 to 12 carbon atoms which may have a substituent" represented by R 1 is selected from integers of 3 to 12, and may be selected from the range of, for example, 3 to 6.
  • cycloalkylene group having 3 to 12 carbon atoms which may have a substituent include divalent groups obtained by removing one hydrogen atom from a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a cyclododecyl group, and divalent groups obtained by removing one hydrogen atom from a substituted cycloalkyl group in which at least one hydrogen atom of the cycloalkyl group is substituted with a substituent (the former divalent group is preferred).
  • the aromatic ring constituting the "arylene group having 6 to 36 carbon atoms" in the "arylene group having 6 to 36 carbon atoms which may have a substituent" represented by R 1 may be a single ring, a fused ring in which two or more rings are fused, or a linked ring in which two or more rings are linked by a single bond.
  • the number of fused rings is, for example, 2 to 6, for example, 2 to 4.
  • the number of linked rings is, for example, 2 to 6, for example, 2 to 4.
  • the number of carbon atoms in the aromatic ring is selected from integers of 6 to 36, and may be selected from the range of, for example, 6 to 22 or 6 to 18, or may be selected from the range of, for example, 6 to 14 or 6 to 10.
  • Specific examples of the "arylene group having 6 to 36 carbon atoms which may have a substituent" include divalent groups obtained by removing one hydrogen atom from a monovalent aromatic hydrocarbon group (aryl group), such as a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a biphenyl group, an anthracenyl group (anthryl group), a phenanthryl group, a fluorenyl group, an indenyl group, a pyrenyl group, a perylenyl group, a fluoranthenyl group, or a triphenylenyl group, and divalent groups obtained by removing one hydrogen atom from a substituted ary
  • the heterocycle constituting the "divalent heterocyclic group having 5 to 36 ring atoms" in the "divalent heterocyclic group having 5 to 36 ring atoms which may have a substituent" represented by R 1 may be a monocycle or a condensed ring in which two or more rings are condensed. In the case of a condensed ring, the number of condensed rings is, for example, 2 to 6, for example, 2 to 4.
  • the heterocycle may be an aromatic heterocycle or an aliphatic heterocycle. Examples of heteroatoms constituting the heterocycle include a nitrogen atom, an oxygen atom, and a sulfur atom.
  • the number of carbon atoms in the aromatic heterocycle is selected from integers of 5 to 36, and may be selected from the range of, for example, 5 to 30 or 5 to 18.
  • Specific examples of the "divalent heterocyclic group having 5 to 36 ring atoms" include divalent groups obtained by removing one hydrogen atom from a monovalent heterocyclic group such as a pyridyl group, a pyrimidinyl group, a triazinyl group, a thienyl group, a furyl group (a furanyl group), a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a triazolyl group, a quinolyl group, an isoquinolyl group, a naphthyldinyl group, an acridinyl group, a phenanthrolinyl group, a benzofuranyl group, a benzothienyl group, an oxazolyl group, an indoly
  • examples of the "substituent" in the "linear or branched alkylene group having 1 to 18 carbon atoms which may have a substituent”, “linear or branched alkenylene group having 2 to 20 carbon atoms which may have a substituent”, “linear or branched alkynylene group having 2 to 20 carbon atoms which may have a substituent”, “cycloalkylene group having 3 to 12 carbon atoms which may have a substituent”, “arylene group having 6 to 36 carbon atoms which may have a substituent” or "divalent heterocyclic group having 5 to 36 ring atoms which may have a substituent” represented by R 1 include, Specifically, halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; cyano groups; hydroxyl groups; nitro groups; nitroso groups; carboxyl groups; phosphoric acid groups; carboxylate groups such as methyl ester groups and ethyl
  • Each group represented by R1 may contain only one or more substituents selected from the substituent group A, and when more than one is contained, the substituents may be the same or different.
  • the hydrogen atom of each of the substituents constituting the substituent group A may be further substituted with a substituent selected from the substituent group A.
  • R 1 in the general formula (1) is preferably a linear or branched alkylene group having 1 to 18 carbon atoms (preferably 1 to 12, for example 1 to 6) which may have a substituent, for example an unsubstituted alkylene group, for example an alkylene group substituted with an alkenyl group, an alkynyl group, a cycloalkyl group or an aryl group.
  • R 1 in the general formula (1) is also preferably an arylene group having 6 to 36 carbon atoms (preferably 6 to 14, for example 6 to 10) which may have a substituent.
  • the atom of R 1 bonded to SO 3 X is preferably a secondary carbon atom or a carbon atom constituting the backbone of a benzene ring.
  • X in the sulfonate group (-SO 3 X) in general formula (1) represents a monovalent cation other than a hydrogen ion.
  • the monovalent cation is preferably an alkali metal ion, an ammonium ion which may have a substituent, or a phosphonium ion which may have a substituent, but is not limited to these.
  • alkali metal ions include lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions, and francium ions, with sodium ions, potassium ions, rubidium ions, and cesium ions being preferred.
  • Examples of phosphonium ions which may have a substituent include ethyl phosphonium ion, isopropyl phosphonium ion, n-propyl phosphonium ion, isobutyl phosphonium ion, n-butyl phosphonium ion, t-butyl phosphonium ion, dimethyl phosphonium ion, diethyl phosphonium ion, phenyl phosphonium ion, benzyl phosphonium ion, and the above ammonium ions in which the nitrogen atom is replaced with a phosphorus atom.
  • R 2 to R 9 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms which may have a substituent, a linear or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent, a linear or branched alkynyl group having 2 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 10 carbon atoms which may have a substituent, a linear or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent, a cycloalkoxy group having 3 to 10 carbon atoms which may have a substituent, an aryloxy group having 6 to 36 carbon atoms which may have a substituent, a linear or branched alkoxycarbonyl group having 1 to 18 carbon atoms which may have a substituent, a thio group having 0 to 18 carbon atoms which may have a substituent,
  • the number of carbon atoms in the "linear or branched alkyl group having 1 to 18 carbon atoms" in the "linear or branched alkyl group having 1 to 18 carbon atoms which may have a substituent" represented by R 2 to R 9 is selected from integers of 1 to 18, and may be selected from the range of, for example, 1 to 12, or may be selected from the range of, for example, 1 to 6.
  • linear or branched alkyl group having 1 to 18 carbon atoms For specific examples of the "linear or branched alkyl group having 1 to 18 carbon atoms", reference may be made to the specific examples of the alkyl group (the alkyl group before removal of one hydrogen atom) given in the explanation of the "linear or branched alkylene group having 1 to 18 carbon atoms which may have a substituent" represented by R 1 above.
  • the number of carbon atoms in the "straight- chain or branched alkenyl group having 2 to 20 carbon atoms" in the "straight-chain or branched alkenyl group having 2 to 20 carbon atoms which may have a substituent" represented by R 2 to R 9 is selected from integers from 2 to 20, and may be selected from the range of, for example, 2 to 12, or may be selected from the range of, for example, 2 to 6.
  • the number of carbon atoms in the "straight- chain or branched alkynyl group having 2 to 20 carbon atoms" in the "straight-chain or branched alkynyl group having 2 to 20 carbon atoms which may have a substituent" represented by R 2 to R 9 is selected from integers from 2 to 20, and may be selected from the range of, for example, 2 to 12, or may be selected from the range of, for example, 2 to 6.
  • the number of carbon atoms in the "cycloalkyl group having 3 to 10 carbon atoms" in the "cycloalkyl group having 3 to 10 carbon atoms which may have a substituent" represented by R 2 to R 9 is selected from integers of 3 to 10, and may be selected, for example, from the range of 3 to 6.
  • R 2 to R 9 the number of carbon atoms in the "cycloalkyl group having 3 to 10 carbon atoms" in the "cycloalkyl group having 3 to 10 carbon atoms which may have a substituent" represented by R 2 to R 9 is selected from integers of 3 to 10, and may be selected, for example, from the range of 3 to 6.
  • the cycloalkyl group having 3 to 10 carbon atoms reference can be made to the specific examples of the cycloalkyl group (cycloalkyl group before removal of one hydrogen atom) given in the explanation of the "cycloalkylene group having 3 to 12 carbon atoms" in R 1 above.
  • the number of carbon atoms in the "straight-chain or branched alkoxy group having 1 to 20 carbon atoms" in the "straight-chain or branched alkoxy group having 1 to 20 carbon atoms which may have a substituent" represented by R 2 to R 9 is selected from an integer of 1 to 20, and may be selected from the range of, for example, 1 to 12, or may be selected from the range of, for example, 1 to 6.
  • the "straight-chain or branched alkoxy group having 1 to 20 carbon atoms" include a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an isopropoxy group, an isobutoxy group, an s-butoxy group, a t-butoxy group, an isooctyloxy group, a t-octyloxy group, and the like.
  • the number of carbon atoms in the "straight - chain or branched cycloalkoxy group having 3 to 10 carbon atoms" in the "straight-chain or branched cycloalkoxy group having 3 to 10 carbon atoms which may have a substituent" represented by R 2 to R 9 is selected from integers of 3 to 10, and may be selected, for example, from the range of 3 to 6.
  • Specific examples of the "straight-chain or branched cycloalkoxy group having 3 to 10 carbon atoms" include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.
  • aryloxy group having 6 to 36 carbon atoms include a phenoxy group, a tolyloxy group, a biphenylyloxy group, a terphenylyloxy group, a naphthyloxy group, an anthryloxy group, a phenanthryloxy group, a fluorenyloxy group, and an indenyloxy group.
  • the number of carbon atoms in the "straight-chain or branched alkoxycarbonyl group having 1 to 18 carbon atoms which may have a substituent" represented by R 2 to R 9 is selected from integers of 1 to 18, and may be selected from the range of, for example, 1 to 12, or may be selected from the range of, for example, 1 to 6.
  • Specific examples of the "alkoxycarbonyl group having 1 to 18 carbon atoms" include a methoxycarbonyl group, an ethoxycarbonyl group, etc.
  • the "thio group having 0 to 18 carbon atoms which may have a substituent" represented by R 2 to R 9 may be an unsubstituted thio group (thiol group: -SH) or a substituted thio group in which the hydrogen atom of the thiol group is substituted with a substituent.
  • substituent of the substituted thio group include an alkyl group and an aryl group, and the hydrogen atom of each of these groups may be substituted with a substituent selected from the above-mentioned substituent group A.
  • alkyl group which is a substituent of the thio group the description of the "linear or branched alkyl group having 1 to 18 carbon atoms" and the “cycloalkyl group having 3 to 10 carbon atoms" in the above-mentioned R 2 to R 9 can be referred to, and for an explanation and specific examples of the aryl group, the description of the "monovalent aromatic hydrocarbon group having 6 to 36 carbon atoms" in the below-mentioned R 2 to R 9 can be referred to.
  • the number of carbon atoms of the substituted thio group is preferably in the range of 1 to 18, and may be, for example, in the range of 1 to 12, or may be, for example, in the range of 1 to 6.
  • Specific examples of the "substituted thio group having 1 to 18 carbon atoms" include a methylthio group, an ethylthio group, a propylthio group, a phenylthio group, and a biphenylthio group.
  • the "amino group having 0 to 20 carbon atoms which may have a substituent" represented by R 2 to R 9 may be an unsubstituted amino group, a mono-substituted amino group, or a di-substituted amino group.
  • substituent of each substituted amino group include an alkyl group, an aryl group, and an acyl group, and the hydrogen atom of each of these groups may be substituted with a substituent selected from the above-mentioned substituent group A.
  • the above description of the "linear or branched alkyl group having 1 to 18 carbon atoms” and the “cycloalkyl group having 3 to 10 carbon atoms" in R 2 to R 9 can be referred to, and for the explanation and specific examples of the aryl group, the description of the "monovalent aromatic hydrocarbon group having 6 to 36 carbon atoms" in R 2 to R 9 can be referred to below.
  • the number of carbon atoms of the mono-substituted amino group and the di-substituted amino group is preferably 1 to 20, and may be, for example, in the range of 1 to 12.
  • the mono-substituted amino group examples include an alkylamino group (e.g., an ethylamino group), an acetylamino group, and an arylamino group (e.g., a phenylamino group).
  • the disubstituted amino group examples include a dialkylamino group (eg, a diethylamino group), a diarylamino group (eg, a diphenylamino group), and an acetylphenylamino group.
  • substituted group A such as "a linear or branched alkylene group having 1 to 18 carbon atoms which may have a substituent” represented by formula ( 1)
  • substituent of the "monovalent aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent” is preferably an amino group substituted with a monovalent aromatic hydrocarbon group (aryl group), more preferably a diarylamino group.
  • the monovalent aromatic hydrocarbon group which is the substituent of the amino group may be substituted with a substituent selected from the above substituent group A.
  • R 2 to R 9 is a monovalent aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent or an amino group having 0 to 20 carbon atoms which may have a substituent.
  • R 3 , R 4 , R 7 and R 8 is a monovalent aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent or an amino group having 0 to 20 carbon atoms which may have a substituent
  • at least one of R 4 and R 7 is a monovalent aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent or an amino group having 0 to 20 carbon atoms which may have a substituent.
  • the amino group has a substituent, the number of carbon atoms is 1 to 20.
  • At least one of R 2 to R 9 in the general formula (1) is a group having a diarylamino group, and it is more preferable that at least one of R 3 , R 4 , R 7 and R 8 is a group having a diarylamino group. It is also preferable that at least one of R 2 to R 5 and at least one of R 6 to R 9 in the general formula (1) is a group having a diarylamino group, it is more preferable that at least one of R 3 and R 4 and at least one of R 7 and R 8 are a group having a diarylamino group, and it is even more preferable that R 4 and R 7 are groups having a diarylamino group.
  • the group having a diarylamino group is, for example, a diarylamino group, for example, a diarylaminoaryl group, for example, a diarylaminocarbazol-9-yl group.
  • a diarylamino group for example, a diarylaminoaryl group, for example, a diarylaminocarbazol-9-yl group.
  • the description of the "monovalent aromatic hydrocarbon group having 6 to 36 carbon atoms" in R 2 to R 9 above can be referred to.
  • At least one hydrogen atom of the diarylamino group, diarylaminoaryl group, and diarylaminocarbazol-9-yl group may be substituted with a substituent selected from the above-mentioned Substituent Group A.
  • the substituent include a substituent bonded via a heteroatom, such as an alkoxy group (e.g., a methoxy group) or a diarylamino group (e.g., a di(methoxyphenyl)amino group).
  • a heteroatom such as an alkoxy group (e.g., a methoxy group) or a diarylamino group (e.g., a di(methoxyphenyl)amino group).
  • a heteroaryl group containing a nitrogen atom as a ring skeleton-constituting atom (e.g., a pyridyl group).
  • Compound group 1 includes compound group 1a in which R 4 is a diarylamino group which may have a substituent, compound group 1b in which R 4 is a diarylaminoaryl group which may have a substituent (preferably a diarylaminophenyl group which may have a substituent), compound group 1c in which R 4 is a diarylaminocarbazol-9-yl group which may have a substituent, and compound group 1d in which R 4 is a linear or branched alkyl group having 1 to 18 carbon atoms which may have a substituent.
  • R 2 , R 3 , and R 5 to R 9 in each group may be hydrogen atoms.
  • R 7 in each group may not be a hydrogen atom, and for example, R 4 and R 7 may be the same group, and for example, R 2 , R 3 , R 5 , R 6 , R 8 , and R 9 may be hydrogen atoms.
  • Each of the compound groups 1a to 1d can further satisfy at least one of the following additional conditions.
  • One additional condition is when the "diarylamino" has an alkoxy group (e.g., an alkoxy group having 1 to 6 carbon atoms) as a substituent.
  • One additional condition is when the "diarylamino" has a heteroaryl group (e.g., a pyridyl group) containing a nitrogen atom as a ring skeleton constituent atom as a substituent.
  • R 1 is a linear or branched alkylene group having 1 to 18 carbon atoms (preferably 1 to 12, e.g., 1 to 6) that may have a substituent, for example, an unsubstituted alkylene group, for example, an alkylene group substituted with an alkenyl group, an alkynyl group, a cycloalkyl group, or an aryl group.
  • R 1 is an arylene group having 6 to 36 carbon atoms (preferably 6 to 14, e.g., 6 to 10) that may have a substituent.
  • R 1 bonded to SO 3 X is a secondary carbon atom.
  • X is Li, Na, K, Rb or Cs, such as Li, such as Na, such as K, such as Rb, such as Cs.
  • Compound group 2 includes compound group 2a in which R 3 is a diarylamino group which may have a substituent, compound group 2b in which R 3 is a diarylaminoaryl group which may have a substituent (preferably a diarylaminophenyl group which may have a substituent), compound group 2c in which R 3 is a diarylaminocarbazol-9-yl group which may have a substituent, and compound group 2d in which R 3 is a linear or branched alkyl group having 1 to 18 carbon atoms which may have a substituent.
  • R 2 and R 4 to R 9 in each group may be hydrogen atoms.
  • R 8 in each group may not be a hydrogen atom, for example, R 3 and R 8 may be the same group, for example, R 2 , R 4 to R 7 , and R 9 may be hydrogen atoms.
  • Compound groups 2a to 2d each can satisfy at least one of the additional conditions described in compound group 1.
  • Compound group 3 includes compound group 3a in which R 2 is a diarylamino group which may have a substituent, compound group 3b in which R 2 is a diarylaminoaryl group which may have a substituent (preferably a diarylaminophenyl group which may have a substituent), compound group 3c in which R 2 is a diarylaminocarbazol-9-yl group which may have a substituent, and compound group 3d in which R 2 is a linear or branched alkyl group having 1 to 18 carbon atoms which may have a substituent.
  • R 3 to R 9 in each group may be a hydrogen atom.
  • R 9 in each group may not be a hydrogen atom, for example, R 2 and R 9 may be the same group, and for example, R 3 to R 8 may be a hydrogen atom.
  • Compound groups 3a to 3d each can satisfy at least one of the additional conditions described in compound group 1.
  • Compound group 4 includes compound group 4a in which R 5 is a diarylamino group which may have a substituent, compound group 4b in which R 5 is a diarylaminoaryl group which may have a substituent (preferably a diarylaminophenyl group which may have a substituent), compound group 4c in which R 5 is a diarylaminocarbazol-9-yl group which may have a substituent, and compound group 4d in which R 5 is a linear or branched alkyl group having 1 to 18 carbon atoms which may have a substituent.
  • R 2 to R 4 and R 6 to R 9 in each group may be hydrogen atoms.
  • R 6 in each group may not be a hydrogen atom, for example, R 5 and R 6 may be the same group, for example, R 2 to R 4 and R 7 to R 9 may be hydrogen atoms.
  • Compound groups 4a to 4d each can satisfy at least one of the additional conditions described in compound group 1.
  • the compound represented by the general formula (1) of the present invention can be synthesized by known methods such as those described in JP 2020-013898 A.
  • the corresponding substituent is introduced into 3,7-dibromophenoxazine by Suzuki-Miyaura coupling reaction or Buchwald reaction, and then the corresponding sultone is reacted to obtain compound (A-1).
  • the compound represented by the general formula (1) can be obtained by known methods using a halogenated phenothiazine derivative as a precursor.
  • Methods for purifying the compound represented by general formula (1) of the present invention include purification by column chromatography, adsorption purification using silica gel, activated carbon, activated clay, etc., recrystallization or crystallization using a solvent, etc. Alternatively, these methods may be used in combination to increase the purity of the compound. Furthermore, these compounds can be identified by nuclear magnetic resonance analysis (NMR).
  • NMR nuclear magnetic resonance analysis
  • the compound represented by the general formula (1) of the present invention is useful as a hole transport material, and can be effectively used as a hole transport material in a hole transport layer of an organic electronics device such as a photoelectric conversion element or an organic electroluminescence element.
  • the "hole transport material” means a material having a function of transporting holes.
  • the hole transport material used in the present invention may be composed of a compound represented by the general formula (1), or may contain a hole transport material other than the compound represented by the general formula (1) in addition to the compound represented by the general formula (1).
  • the photoelectric conversion element of the present invention is characterized in that it contains a hole transport material containing a compound represented by general formula (1).
  • a compound represented by general formula (1) the description in the above column "Compound represented by general formula (1)" can be referred to.
  • the compound represented by general formula (1) has excellent hole transport properties, so it can be effectively used as a material for the hole transport layer of the photoelectric conversion element.
  • Preferred embodiments of the photoelectric conversion element will be described below, but the embodiments of the photoelectric conversion element of the present invention should not be construed as being limited to the embodiments described below. In one embodiment of the present invention, as shown in FIG.
  • the photoelectric conversion element has a conductive support 1, an electron transport layer 2, a photoelectric conversion layer 3, a hole transport layer 4, and a counter electrode 5 in this order, and the hole transport layer 4 contains a compound represented by general formula (1).
  • the photoelectric conversion element has a conductive support, a hole transport layer, a photoelectric conversion layer, an electron transport layer, and a counter electrode in this order, and the hole transport layer contains a compound represented by general formula (1).
  • the photoelectric conversion layer contains, for example, a perovskite compound.
  • the photoelectric conversion element is, for example, a photoelectric conversion element used in a solar cell.
  • the conductive support 1 functions as a cathode that extracts electrons transported from the photoelectric conversion layer 3 via the electron transport layer 2.
  • the conductive support 1 is a conductive support having translucency that allows light to pass through the conductive support, and is, for example, a conductive substrate in which a film of a conductive material is formed on a translucent substrate.
  • conductive materials used for the conductive support include conductive transparent oxide semiconductors such as tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), tungsten-doped indium oxide (IWO), zinc aluminum oxide (AZO), fluorine-doped tin oxide (FTO), indium oxide (In 2 O 3 ), and indium-tin composite oxide, and it is preferable to use tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), etc.
  • ITO tin-doped indium oxide
  • IZO zinc-doped indium oxide
  • IWO tungsten-doped indium oxide
  • AZO zinc aluminum oxide
  • FTO fluorine-doped tin oxide
  • ITO indium oxide
  • FTO fluorine-doped tin oxide
  • the electron transport layer 2 is a layer containing a material (electron transport material) having a function of transporting electrons, and is disposed between the conductive support 1 and the photoelectric conversion layer 3, and has a function of transporting electrons generated in the photoelectric conversion layer 3 to the conductive support 1 side. This can improve the efficiency of electron migration from the photoelectric conversion layer to the conductive support.
  • the electron transport layer may have a function of suppressing hole injection from the conductive support.
  • the electron transport layer 2 may be formed adjacent to the conductive support 1, or another layer may be interposed between the conductive support 1 and the electron transport layer 2.
  • semiconductor materials used in the electron transport layer include metal oxides such as tin oxide (SnO, SnO2 , SnO3 , etc.), titanium oxide ( TiO2 , etc.), tungsten oxide ( WO2 , WO3 , W2O3 , etc.), zinc oxide (ZnO), niobium oxide ( Nb2O5 , etc.), tantalum oxide ( Ta2O5 , etc.), yttrium oxide ( Y2O3 , etc.), and strontium titanate ( SrTiO3 , etc.); metal sulfides such as titanium sulfide, zinc sulfide, zirconium sulfide, copper sulfide, tin sulfide, indium sulfide, tungsten sulfide, cadmium sulfide, and silver sulfide; metal selenides such as titanium selenide, zirconium selenide, indium selenide,
  • a paste containing fine particles of the semiconductor material can be mentioned.
  • the semiconductor paste may be a commercially available product, or may be a preparation prepared by dispersing fine powder of the semiconductor material in a solvent.
  • solvents used in preparing the semiconductor paste include, but are not limited to, water; alcohol-based solvents such as methanol, ethanol, and isopropyl alcohol; ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and hydrocarbon-based solvents such as n-hexane, cyclohexane, benzene, and toluene. These solvents may be used alone or as a mixed solvent of two or more types.
  • Methods for dispersing semiconductor fine powder in a solvent include grinding the powder in a mortar or the like as necessary, and then dispersing it in the solvent using a dispersing machine such as a ball mill, paint conditioner, vertical bead mill, horizontal bead mill, or attritor.
  • a dispersing machine such as a ball mill, paint conditioner, vertical bead mill, horizontal bead mill, or attritor.
  • a surfactant or the like to prevent the semiconductor fine particles from agglomerating
  • a thickener such as polyethylene glycol
  • the electron transport layer can be formed using a known film-forming method. That is, the electron transport layer can be formed using a coating method or a gas-phase process using a coating liquid containing a semiconductor material (for example, a coating liquid for the electron transport layer such as a semiconductor paste).
  • a method of forming a film by applying a coating liquid for the electron transport layer to a conductive substrate by a wet coating method such as a spin coating method, an inkjet method, a doctor blade method, a drop casting method, a squeegee method, a screen printing method, a reverse roll coating method, a gravure coating method, a kiss coating method, a roll brush method, a spray coating method, an air knife coating method, a wire barber coating method, a pipe doctor method, an impregnation/coating method, or a curtain coating method, and then removing the solvent or additives by baking, or a method of forming a film of a semiconductor material by a gas-phase film-forming method such as a sputtering method, a vapor deposition method, an electrodeposition method, an electrodeposition method, or a microwave irradiation method.
  • a gas-phase film-forming method such as a sputtering method, a vapor deposition method, an electrode
  • a coating method in which the prepared coating liquid for the electron transport layer is applied by a spin coating method it is preferable to use a coating method in which the prepared coating liquid for the electron transport layer is applied by a spin coating method, but this is not limited to this.
  • the conditions for spin coating can be set appropriately.
  • the atmosphere in which the film is formed is not particularly limited, and may be air or an inert atmosphere.
  • the thickness of the electron transport layer is, for example, 5 nm to 200 nm, and preferably 10 nm to 150 nm. Furthermore, when a dense electron transport layer is used, for example from the viewpoint of further improving photoelectric conversion efficiency, the thickness of the electron transport layer is usually preferably 5 nm to 100 nm, and more preferably 10 nm to 50 nm. In the present invention, when a porous (mesoporous) metal oxide is used in addition to the dense layer, the thickness is usually preferably 20 nm to 200 nm, and more preferably 50 nm to 150 nm.
  • the photoelectric conversion layer 3 is a layer for converting light energy into electricity, more specifically, a layer in which a charge separation state occurs due to light energy to generate holes and electrons.
  • the photoelectric conversion layer 3 is formed on the opposite side of the electron transport layer 2 to the conductive support 1.
  • the photoelectric conversion layer is a layer (perovskite layer) formed of a perovskite material.
  • the "perovskite material” means a material having a perovskite structure represented by the general formula ABX3 .
  • A represents a monovalent organic cation or a monovalent metal cation
  • B represents a divalent metal cation
  • X represents a halogen ion.
  • Examples of the divalent metal cation represented by B include Pb 2+ and Sn 2+ .
  • Examples of the halogen ion represented by X include I - and Br - .
  • perovskite materials include MAPbI 3 , FAPbI 3 , EAPbI 3 , CsPbI 3 , MASnI 3 , FASnI 3 , EASnI 3 , MAPbBr 3 , FAPbBr 3 , EAPbBr 3 , MASnBr 3 , FASnBr 3 , and EASnBr 3 .
  • mixed cation type and mixed anion type perovskite materials such as (FAMA)Pb(IBr) 3 , K(FAMA)Pb(IBr) 3 , Rb(FAMA)Pb(IBr) 3 , and Cs(FAMA)Pb(IBr) 3 can also be mentioned.
  • the photoelectric conversion layer may contain only one type selected from these perovskite materials, or may contain two or more types.
  • the photoelectric conversion layer may be composed of only the perovskite material, or may contain other materials in addition to the perovskite material. Examples of the other materials include a light absorbing agent.
  • the perovskite layer can be formed by applying a solution of halide AX and metal halide BX2 (perovskite precursor solution) to form a precursor coating film, and drying the precursor coating film.
  • AX and metal halide BX2 perovskite precursor solution
  • A, B, and X the description of each ion constituting ABX3 above can be referred to.
  • specific examples of the halide AX include methylammonium halide, formamidine halide, and cesium halide
  • specific examples of the metal halide BX2 include lead halide and tin halide.
  • examples of the solvent for the perovskite precursor solution include, but are not limited to, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), ⁇ -butyrolactone, etc. Furthermore, these solvents may be used alone or in combination of two or more.
  • a preferred example of the solvent is a mixed solvent of N,N-dimethylformamide and dimethyl sulfoxide.
  • the application process of the perovskite precursor solution is preferably carried out in a dry atmosphere, and more preferably in a dry inert gas atmosphere such as a glove box. This prevents moisture from being mixed into the perovskite layer, allowing highly efficient perovskite solar cells to be produced with good reproducibility.
  • a dry atmosphere such as a glove box.
  • the perovskite layer is formed by drying the precursor coating film thus formed.
  • the precursor coating film may be dried naturally or by heating using a hot plate or the like.
  • the temperature at which the precursor coating film is heated using a hot plate or the like is preferably 50 to 200°C, more preferably 70 to 150°C, from the viewpoint of producing a perovskite material from the precursor.
  • the heating time is preferably about 10 to 90 minutes, more preferably about 10 to 60 minutes.
  • the thickness of the photoelectric conversion layer is preferably 50 to 1000 nm, and more preferably 300 to 700 nm. This suppresses performance degradation due to defects or peeling in the photoelectric conversion layer, prevents the element resistance from becoming excessively high, and provides the photoelectric conversion layer with sufficient light absorption.
  • the hole transport layer 4 is a layer containing a material (hole transport material) having a function of transporting holes, and is disposed between the photoelectric conversion layer 3 and the counter electrode 5, and has a function of transporting holes generated in the photoelectric conversion layer 3 to the counter electrode 5. This can improve the efficiency of hole movement from the photoelectric conversion layer to the electrode.
  • the hole transport layer may have a function of suppressing electron injection from the counter electrode.
  • the hole transport layer contains a compound represented by general formula (1) as a hole transport material.
  • the compound represented by general formula (1) contained in the hole transport layer may be one type or two or more types selected from the group of compounds represented by general formula (1).
  • the hole transport layer may contain, in addition to the compound represented by general formula (1), a hole transport material other than the compound represented by general formula (1) (hereinafter referred to as a "second hole transport material") or an additive.
  • the second hole transport material may be an inorganic hole transport material or an organic hole transport material.
  • inorganic hole transport materials include compound semiconductors containing monovalent copper, such as CuI, CuInSe2 , and CuS, and compounds containing metals other than copper, such as GaP, NiO, CoO, FeO, Bi2O3 , MoO2 , and Cr2O3 .
  • organic hole transport material examples include polythiophene derivatives such as poly-3-hexylthiophene (P3HT) and polyethylenedioxythiophene (PEDOT); fluorene derivatives such as 2,2',7,7'-tetrakis-(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (Spiro-OMeTAD); carbazole derivatives such as polyvinylcarbazole; triphenylamine derivatives such as poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA); diphenylamine derivatives; polysilane derivatives; polyaniline derivatives, etc.
  • These second hole transport materials may be mixed in the hole transport layer, or a hole transport layer containing the second hole transport material may be laminated on a hole transport layer containing the compound represented by general formula (1).
  • the solvent used in the coating solution for the hole transport layer may be an aromatic organic solvent such as benzene, toluene, xylene, mesitylene, tetralin (1,2,3,4-tetrahydronaphthalene), monochlorobenzene (chlorobenzene), o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, or nitrobenzene; an alkyl halide organic solvent such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2-trichloroethane, or dichloromethane; a nitrile solvent such as benzonitrile or acetonitrile; or a tetrahydrofuran,
  • aromatic organic solvent such as benzene, toluene, xylene, mesitylene, tetralin (1,2,3,4-tetrahydronaphthalene), monochlorobenz
  • the solvent examples include, but are not limited to, ether solvents such as isopropyl ether, c-pentyl methyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol monomethyl ether; ester solvents such as ethyl acetate and propylene glycol monomethyl ether acetate; and alcohol solvents such as methanol, isopropanol, n-butanol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, cyclohexanol, and 2-n-butoxyethanol.
  • ether solvents such as isopropyl ether, c-pentyl methyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol monomethyl ether
  • ester solvents such as ethyl acetate and propy
  • the atmosphere during film formation of the hole transport layer is preferably a dry atmosphere.
  • a solvent that has been dehydrated so that the moisture content is 10 ppm or less in the coating solution.
  • the thickness of the hole transport layer is preferably 5 nm to 500 nm, and more preferably 10 nm to 250 nm.
  • additives that may be added to the hole transport layer include an oxidizing agent (dopant) and a basic compound (basic additive). By adding these additives to the hole transport layer, the carrier concentration of the hole transport layer is improved, and the photoelectric conversion efficiency of the photoelectric conversion element can be improved.
  • dopants include lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), silver bis(trifluoromethanesulfonyl)imide, tris(2-(1H-pyrazol-1-yl)-4-tert-butylpyridine)cobalt(III) tri[bis(trifluoromethane)sulfonimide] (FK209), NOSbF 6 , SbCl 5 , SbF 5 , and the like. Of these, it is preferable to use lithium bis(trifluoromethylsulfonyl)imide (LiTFSI).
  • LiTFSI lithium bis(trifluoromethylsulfonyl)imide
  • LiTFSI lithium bis(trifluoromethylsulfonyl)imide
  • the concentration of the dopant in the hole transport layer is preferably 2.0 equivalents or less, more preferably 0.5 equivalents or less, relative to 1 equivalent of the hole transport material. While the inclusion of an additive in the hole transport layer leads to an improvement in the photoelectric conversion efficiency of the photoelectric conversion element, if the concentration of the dopant is too high, the durability of the photoelectric conversion element may be reduced.
  • Specific examples of the basic additive include 4-tert-butylpyridine (tBP), 2-picoline, and 2,6-lutidine, and among these, it is preferable to use 4-tert-butylpyridine.
  • the basic additive may be used in combination with a dopant.
  • the concentration of the basic additive in the hole transport layer is preferably 5 equivalents or less, more preferably 3.5 equivalents or less, relative to 1 equivalent of the hole transport material.
  • the counter electrode 5 is an electrode formed on the opposite side of the hole transport layer 4 to the photoelectric conversion layer 3, and is disposed opposite the conductive support 1 with the above-mentioned electron transport layer 2, photoelectric conversion layer 3, and hole transport layer 4 sandwiched therebetween.
  • the counter electrode functions as an anode that extracts holes transported from the photoelectric conversion layer via the hole transport layer.
  • the counter electrode 5 may be provided adjacent to the hole transport layer 4, or an electron blocking layer made of an organic material or an inorganic compound semiconductor may be interposed between the hole transport layer 4 and the counter electrode 5.
  • the counter electrode include metals such as platinum, titanium, stainless steel, aluminum, gold, silver, nickel, magnesium, chromium, cobalt, and copper, or alloys thereof. Among these, it is preferable to use gold, silver, or a silver alloy, since it exhibits high electrical conductivity even in a thin film.
  • silver alloys include silver-gold alloys, silver-copper alloys, silver-palladium alloys, silver-copper-palladium alloys, and silver-platinum alloys, since they are less susceptible to sulfurization or chlorination and have high stability as a thin film.
  • the counter electrode is a material that can be formed by a gas phase process such as deposition. When a metal electrode is used as the counter electrode, the thickness thereof is preferably 10 nm or more, and more preferably 50 nm or more, in order to obtain good electrical conductivity.
  • the conductive support 1 serves as the cathode
  • the counter electrode 5 serves as the anode. It is preferable to irradiate light such as sunlight (light used for photoelectric conversion) from the conductive support side.
  • the photoelectric conversion layer absorbs the light and enters an excited state, generating electrons and holes. These electrons move via the electron transport layer to the conductive support, and the holes move via the hole transport layer to the counter electrode, causing a current to flow and functioning as a photoelectric conversion element.
  • the photoelectric conversion element of the present invention may also have a conductive support, a hole transport layer, a photoelectric conversion layer, an electron transport layer, and a counter electrode, in that order.
  • the conductive support functions as an anode
  • the counter electrode functions as a cathode, with electrons generated in the photoelectric conversion layer moving to the counter electrode via the electron transport layer, and holes generated in the photoelectric conversion layer moving to the conductive support via the hole transport layer. This allows current to be extracted to the outside.
  • the corresponding description of the photoelectric conversion element shown in Figure 1 above can be referenced.
  • the short circuit current density represents the current per cm2 flowing between the output terminals when the terminals are shorted
  • the open circuit voltage represents the voltage between the output terminals when the terminals are open.
  • the fill factor is the maximum output (product of current and voltage) divided by the product of the short circuit current density and the open circuit voltage, and is mainly dependent on the internal resistance.
  • the photoelectric conversion efficiency is calculated as a percentage by multiplying the maximum output (W) divided by the light intensity (W) per cm2 by 100.
  • the photoelectric conversion element of the present invention can be applied to solar cells, various optical sensors, and the like.
  • the solar cell to which the photoelectric conversion element of the present invention is applied is preferably a perovskite solar cell.
  • a solar cell can be obtained by arranging the required number of photoelectric conversion elements, each of which contains a compound represented by general formula (1) in the hole transport layer, into a module and providing the required electrical wiring.
  • a compound (0.5 g) of the following formula (2), [4-[bis(4-methoxyphenyl)amino]phenyl]boronic acid (1.13 g, manufactured by Tokyo Chemical Industry Co., Ltd.), sodium carbonate (0.34 g), tetrahydrofuran (50 mL), and purified water (25 mL) were charged into a reaction vessel, and degassed under reduced pressure.
  • Tetrakistriphenylphosphinepalladium (0.08 g, manufactured by Kanto Chemical Co., Ltd.) was charged, and degassed under reduced pressure, and the mixture was stirred for 7 hours by heating and refluxing. After the aqueous layer of the reaction solution was separated and removed, the organic layer was distilled off the solvent under reduced pressure.
  • the compound of formula (3) (0.30 g), 55% sodium hydride (0.04 g, manufactured by Kanto Chemical Co., Ltd.), and DMF (10 mL) were added to a reaction vessel and stirred at room temperature for 1 hour. 2,4-butanesultone (0.063 mL, manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto and stirred at 90°C for 4 hours.
  • the solvent was distilled off from the reaction liquid under reduced pressure, and the obtained crude product was purified using a silica gel column (ethyl acetate:methanol).
  • the compound of formula (6) (0.251 g), 55% sodium hydride (0.03 g, manufactured by Kanto Chemical Co., Ltd.), and dimethylformamide (10 mL) were added to a reaction vessel and stirred at room temperature for 1 hour. 2,4-butanesultone (0.03 mL, manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto and stirred at 80° C. for 3 hours.
  • Synthesis Example 3 Synthesis of Compound (A-71)
  • the compound (0.251 g) of the above formula (6), potassium tert-butoxide (0.017 g, manufactured by Kanto Chemical Co., Ltd.), and dimethylformamide (10 mL) were added to a reaction vessel and stirred at room temperature for 1 hour.
  • 2,4-butanesultone (0.02 mL, manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto and stirred at 80° C. for 6 hours.
  • Synthesis Example 4 Synthesis of Compound (A-72) A compound (0.401 g) represented by the following formula (7), a compound (0.930 g) represented by the above formula (4), sodium tert-butoxide (0.200 g, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), toluene (5 mL), and tetrahydrofuran (5 mL) were added to a reaction vessel, and the mixture was degassed by bubbling with argon for 20 minutes.
  • the compound of formula (9) (0.233 g), 55% sodium hydride (0.05 g, manufactured by Kanto Chemical Co., Ltd.), and dimethylformamide (10 mL) were added to a reaction vessel and stirred at room temperature for 1 hour. 2,4-butanesultone (0.055 mL, manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto and stirred at 80° C. for 2 hours.
  • Example 1 Preparation of photoelectric conversion element using compound (A-1) 1
  • a glass plate with an ITO film conductive support 1, manufactured by Geomatec Co., Ltd.
  • ITO film conductive support 1, manufactured by Geomatec Co., Ltd.
  • isopropyl alcohol conductive support 1, manufactured by Geomatec Co., Ltd.
  • the following layers were formed by a coating method.
  • a tin oxide colloidal solution tin(IV) oxide, 15% in H2O colloidal dispersion: manufactured by Alfa Aesar
  • purified water were mixed at a volume ratio of 1:9 to form a tin oxide dispersion (electron transport layer coating solution) on the ITO film.
  • the cesium iodide solution was added in an amount such that the amount of cesium charged was 5% in composition ratio.
  • This perovskite precursor solution was dropped onto the tin oxide layer, and spin-coated while dropping chlorobenzene (0.3 mL) to form a perovskite precursor coating film. Subsequently, the resultant was heated on a hot plate at 100° C. for 1 hour to form a perovskite layer (photoelectric conversion layer 3) of Cs(MAFA)Pb(IBr) 3 having a thickness of about 500 nm.
  • lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and 4-tert-butylpyridine as dopants were dissolved in chlorobenzene to prepare a solution, and compound (A-1) was dissolved in this solution at a concentration of 50 mM to prepare a hole transport layer coating solution.
  • concentrations of lithium bis(trifluoromethanesulfonyl)imide and 4-tert-butylpyridine in the hole transport coating solution were 0.5 equivalents and 3 equivalents relative to compound (A-1), respectively.
  • This hole transport layer coating solution was spin-coated on the Cs(MAFA)Pb(IBr) 3 layer and then dried to form a hole transport layer 4 with a film thickness of about 200 nm.
  • gold was evaporated to a thickness of 80 nm on the hole transport layer 4 by vacuum evaporation at a degree of vacuum of 1 ⁇ 10 ⁇ 4 Pa to form a gold electrode (counter electrode 5 ), thereby completing a photoelectric conversion element.
  • Example 2 Preparation of photoelectric conversion element using compound (A-1) 2
  • a photoelectric conversion element was produced in the same manner as in Example 1, except that lithium bis(trifluoromethanesulfonyl)imide and 4-tert-butylpyridine were not added when preparing the hole transport layer coating solution, and the prepared hole transport coating solution was spin-coated at room temperature.
  • Example 3 Preparation of photoelectric conversion element using compound (A-70) 1
  • a photoelectric conversion element was produced in the same manner as in Example 1, except that a solution prepared by the following procedure was used as the hole transport layer coating solution.
  • a dopant solution was prepared by dissolving lithium bis(trifluoromethanesulfonyl)imide in acetonitrile at a concentration of 1.8 M in a dry atmosphere with a relative humidity of 10% or less.
  • a chlorobenzene solution was prepared in which compound (A-70) was dissolved at a concentration of 28 mM, and the dopant solution was added to compound (A-70) so that the amount of lithium bis(trifluoromethanesulfonyl)imide was 0.5 equivalents.
  • 4-tert-butylpyridine was added to compound (A-70) so that the amount of lithium bis(trifluoromethanesulfonyl)imide was 3.3 equivalents to prepare a hole transport layer coating solution.
  • Example 4 Preparation of photoelectric conversion element using compound (A-70) 2 A photoelectric conversion element was produced in the same manner as in Example 3, except that the dopant solution and 4-tert-butylpyridine were not added when preparing the coating solution for the hole transport layer.
  • Example 5 Preparation of photoelectric conversion element using compound (A-71) 1 A photoelectric conversion element was prepared in the same manner as in Example 3, except that compound (A-71) was used instead of compound (A-70).
  • Example 6 Preparation of photoelectric conversion element using compound (A-71) 2 A photoelectric conversion element was prepared in the same manner as in Example 5, except that the dopant solution and 4-tert-butylpyridine were not added when preparing the coating solution for the hole transport layer.
  • the photoelectric conversion element of the Example in which the compound corresponding to the general formula (1) was used as the hole transport material exhibited superior photoelectric conversion efficiency compared to the photoelectric conversion element of Comparative Example 1 in which the compound (B-1), which is a conventional standard hole transport material, was used.
  • the compound represented by the general formula (1) when used as a hole transport material, higher photoelectric conversion characteristics were obtained than when the compound (B-1) was used, even without using a dopant. From the above results, it was found that the photoelectric conversion efficiency can be improved by using the compound represented by the general formula (1) as a hole transport material. It was also found that it is possible to eliminate the need for dopants and basic additives, thereby reducing the manufacturing cost and simplifying the manufacturing process.
  • the compound of the present invention As a hole transport material, a photoelectric conversion element and a solar cell with good photoelectric conversion efficiency can be realized. This makes it possible to efficiently provide electrical energy converted from solar energy as clean energy.
  • hole transport materials containing the compound of the present invention can also be used in organic EL elements, image sensors, and the like. Therefore, the present invention has a high industrial applicability.

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Abstract

Un composé représenté par la formule générale indiquée est utile en tant que matériau de transport de trous pour des éléments de conversion photoélectrique. Dans la formule générale, R 1 représente un groupe alkylène ou similaire ; et R2 à R9 représentent chacun un atome d'hydrogène, un groupe amino, un groupe hydrocarboné aromatique ou similaire.
PCT/JP2023/034740 2022-09-30 2023-09-25 Composé, matériau de transport de trous et élément de conversion photoélectrique utilisant ledit composé WO2024071042A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11511031A (ja) * 1996-04-15 1999-09-28 ピアース ケミカル カンパニー ペルオキシダーゼ活性のアッセイ
US20080176251A1 (en) * 2007-01-24 2008-07-24 Cyanagen Srl Preparation of high purity phenothiazine N-alkylsulfonates and their use in chemiluminescent assays for the measurement of peroxidase acitivity
JP2015503671A (ja) * 2012-01-16 2015-02-02 ケンブリッジ ディスプレイ テクノロジー リミテッド 非対称ジアリールアミンフルオレンユニットを含むポリマー
EP3855185A1 (fr) * 2020-01-23 2021-07-28 Cyanagen Srl Substrats chimiluminescents pour peroxydase à durée de conservation étendue

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11511031A (ja) * 1996-04-15 1999-09-28 ピアース ケミカル カンパニー ペルオキシダーゼ活性のアッセイ
US20080176251A1 (en) * 2007-01-24 2008-07-24 Cyanagen Srl Preparation of high purity phenothiazine N-alkylsulfonates and their use in chemiluminescent assays for the measurement of peroxidase acitivity
JP2015503671A (ja) * 2012-01-16 2015-02-02 ケンブリッジ ディスプレイ テクノロジー リミテッド 非対称ジアリールアミンフルオレンユニットを含むポリマー
EP3855185A1 (fr) * 2020-01-23 2021-07-28 Cyanagen Srl Substrats chimiluminescents pour peroxydase à durée de conservation étendue

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