WO2023022233A1 - 縮合環化合物、撮像素子用光電変換素子用電荷輸送材料および撮像素子用光電変換素子 - Google Patents

縮合環化合物、撮像素子用光電変換素子用電荷輸送材料および撮像素子用光電変換素子 Download PDF

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WO2023022233A1
WO2023022233A1 PCT/JP2022/031420 JP2022031420W WO2023022233A1 WO 2023022233 A1 WO2023022233 A1 WO 2023022233A1 JP 2022031420 W JP2022031420 W JP 2022031420W WO 2023022233 A1 WO2023022233 A1 WO 2023022233A1
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photoelectric conversion
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ring compound
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裕太 森中
雅也 平野
智宏 荘野
直樹 内田
泰裕 高橋
桂甫 野村
洋平 小野
剛 田中
信道 新井
史成 上原
一希 服部
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東ソー株式会社
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
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    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
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    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
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    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07—ORGANIC CHEMISTRY
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    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
    • H10F39/10—Integrated devices
    • H10F39/12—Image sensors
    • 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 condensed ring compound, a charge transport material for a photoelectric conversion device for an image pickup device, and a photoelectric conversion device for an image pickup device.
  • the monosubstituted dibenzo[g,p]chrysene substituted with a naphthyl group or a biphenylyl group as the aromatic hydrocarbon group has the problem of a low glass transition temperature. It turns out there is.
  • a compound having a low glass transition temperature is deposited, the quality of the film may become unstable.
  • it is conceivable to introduce a plurality of substituents but the introduction of a plurality of substituents increases the molecular weight of the compound, and there is concern about thermal decomposition during sublimation during film formation.
  • dibenzo[g,p]chrysene compounds have excellent properties as charge transport materials, particularly hole transport materials or electron blocking materials for organic semiconductor devices.
  • the present invention has been made in view of the above circumstances, and provides a condensed ring compound having a high glass transition temperature, a charge transport material for a photoelectric conversion device for an image pickup device containing the compound, and a charge blocking device for a photoelectric conversion device for an image pickup device.
  • An object of the present invention is to provide a material and a photoelectric conversion element for an imaging device using the material.
  • the present inventors have found that the above problems can be solved by using a specific condensed ring compound, and completed the present invention.
  • aspects of the present disclosure include the following condensed ring compound, a charge transport material for a photoelectric conversion device for an imaging device containing the compound, a charge blocking material for a photoelectric conversion device for an imaging device, and a photoelectric conversion device for an imaging device using the material Regarding.
  • the condensed ring compound is any of the following formulas (A1-1) to (A4-58) described below, or the following formulas (B1-1) to (B1-58), (B3-1) to ( B3-58), the condensed ring compound according to [2].
  • the condensed ring compound has the following formulas (A1-1) to (A1-58), (A2-1) to (A2-58), (A3-2) to (A3-58), and The condensed ring compound according to [4], represented by any one of (A4-1) to (A4-58).
  • the condensed ring compound is represented by the following formulas (A1-1) to (A1-58), (A2-1) to (A2-58), and (A4-1) to (A4-58) described later.
  • the condensed ring compound according to [4] represented by any one.
  • R 1 to R 16 each independently represent a hydrogen atom or a substituent;
  • L represents a phenylene group optionally having a substituent, a biphenylene group optionally having a substituent, or a terphenylene group optionally having a substituent;
  • Ar is an adamantyl group optionally having substituents, a carbazolyl group optionally having substituents, a fluoranthenyl group optionally having substituents, optionally having substituents represents a triphenylenyl group, an optionally substituted dibenzofuranyl group, or an optionally substituted dibenzothiophenyl group;
  • R 1 to R 16 have the same structure as L—Ar.
  • the condensed ring compound has the following formula (2A-III), formula (2B-III) or formula (2C-III): wherein Ar 1 and Ar 2 are groups shown in Tables A-1 and A-2 below, (2A-1) to (2A-65), (2B- 1)
  • the condensed ring compound according to [12] represented by any one of to (2B-65) or (2C-1) to (2C-65).
  • a charge-transporting material for a photoelectric conversion device for an imaging device or a charge blocking material for a photoelectric conversion device for an imaging device comprising the condensed ring compound according to any one of [1] to [6].
  • a photoelectric conversion element for an imaging device comprising the charge transport material for a photoelectric conversion device for an imaging device or the charge blocking material for a photoelectric conversion device for an imaging device according to [9].
  • a condensed ring compound having a high glass transition temperature, a charge-transporting material for a photoelectric conversion device for an imaging device containing the compound, a charge blocking material for a photoelectric conversion device for an imaging device, and an imaging device using the material can provide a photoelectric conversion element for
  • An example of a layered structure of a photoelectric conversion element for an image pickup element containing a charge transport material for an image pickup element photoelectric conversion element or a charge blocking material for an image pickup element photoelectric conversion element containing the condensed ring compound-I according to an embodiment of the present invention is and a schematic cross-sectional view showing the lamination structure of Element Example B-1.
  • Schematic cross-sectional view showing an example of the lamination structure of a hole-only device containing a charge-transporting material for a photoelectric conversion device for an imaging device containing the condensed ring compound-I according to one embodiment of the present invention, and lamination of device example A-1 It is a schematic sectional drawing which shows a structure.
  • FIG. 1 is a schematic cross-sectional view showing an example of a lamination structure of a photoelectric conversion element for an image pickup device containing a charge-transporting material for a photoelectric conversion device for an image pickup device containing a condensed ring compound-II according to an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing the lamination structure of a hole-only device (Device Example A-1) containing a condensed ring compound-II according to an embodiment of the present invention.
  • 1 is a schematic cross-sectional view showing an example of a lamination structure of a photoelectric conversion element for an imaging element containing a photoelectric conversion element material for an imaging element containing a condensed ring compound-III according to an embodiment of the present invention.
  • FIG. FIG. 3 is a schematic cross-sectional view showing the lamination structure of a hole-only device (Device Example A-1) containing a condensed ring compound-III according to an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing a layered structure (device example-A) of a hole-only device containing a condensed ring compound-IV according to one embodiment of the present invention.
  • 1 is a schematic cross-sectional view showing an example of a lamination structure of an organic electroluminescence device containing a condensed ring compound-IV according to one embodiment of the present invention.
  • FIG. 1 is a schematic cross-sectional view showing an example of the lamination structure of a photoelectric conversion element for an image pickup device containing a charge-transporting material for a photoelectric conversion device for an image pickup device containing a condensed ring compound-IV according to an embodiment of the present invention.
  • a condensed ring compound, a charge transport material for a photoelectric conversion device for an image pickup device, and a photoelectric conversion device for an image pickup device will be described in detail below.
  • the condensed ring compound of this embodiment is a condensed ring compound represented by the following formula (1).
  • R 1 to R 16 each independently represent a hydrogen atom or a substituent;
  • L 1 and L 2 are each independently a single bond or a substituted or unsubstituted divalent linking group; L 1 is substituted at either the R 2 or R 3 position in formula (1); L 2 is substituted at either the R 6 or R 7 position in formula (1);
  • n is an integer of 0 or 1;
  • Ar 1 is an optionally substituted carbazolyl group, an optionally substituted adamantyl group, an optionally substituted fluoranthenyl group, a substituent
  • a triphenylenyl group optionally having a substituent, a dibenzofuranyl group optionally having a substituent, a dibenzothiophenyl group optionally having a substituent, or a dibenzo optionally having a substituent
  • [ g, p] represents a chrysenyl group;
  • the substituents represented by R 1 to R 16 are preferably alkyl groups, aromatic hydrocarbon groups or heteroaromatic groups, and are aromatic hydrocarbon groups or heteroaromatic groups. is more preferable.
  • the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. Examples of such alkyl groups include methyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, cyclopropyl, cyclohexyl and 1-adamantyl groups.
  • the aromatic hydrocarbon group is preferably a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms.
  • heteroaromatic group is preferably a monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms.
  • heteroaromatic groups include, for example, a dibenzofuranyl group, a dibenzothiophenyl group, and the like.
  • R 1 to R 16 are preferably hydrogen atoms from the viewpoint of having a high glass transition temperature and a wide bandgap.
  • the divalent linking groups represented by L 1 and L 2 are preferably monocyclic, linking or condensed aromatic hydrocarbon groups having 6 to 30 carbon atoms.
  • aromatic hydrocarbon groups include phenylene groups, biphenylene groups, terphenylene groups, naphthylene groups, fluorenylene groups, triphenylenylene groups, phenanthrenylene groups, anthracenylene groups, and pyrenylene groups. These aromatic hydrocarbon groups may have a substituent.
  • the substituent on the aromatic hydrocarbon group is preferably, for example, an alkyl group, an aromatic hydrocarbon group, or a heteroaromatic group, more preferably an aromatic hydrocarbon group or a heteroaromatic group.
  • the alkyl group as a substituent is preferably a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. Examples of such alkyl groups include methyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, cyclopropyl and cyclohexyl groups.
  • the aromatic hydrocarbon group as a substituent is preferably a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms.
  • heteroaromatic group as a substituent is preferably a monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms.
  • heteroaromatic groups include, for example, a dibenzofuranyl group, a dibenzothiophenyl group, and the like.
  • the divalent linking group represented by L 1 and L 2 is preferably a monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms.
  • heteroaromatic groups include, for example, a dibenzofuranylene group, a dibenzothiophenylene group, a pyridylene group, a pyrimidylene group, and the like. These heteroaromatic groups may have a substituent.
  • substituents in the heteroaromatic group include the same substituents as those described above in the aromatic hydrocarbon group.
  • the aromatic hydrocarbon group represented by Ar 1 and Ar 2 is preferably a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms.
  • aromatic hydrocarbon groups include phenyl, biphenylyl, terphenylyl, naphthyl, fluorenyl, anthryl, phenanthryl, benzofluorenyl, triphenylenyl, spirobifluorenyl, diphenylfluorenyl group, dibenzo[g,p]chrysenyl group and the like.
  • These aromatic hydrocarbon groups may have a substituent.
  • substituents on the aromatic hydrocarbon group include alkyl groups, aromatic hydrocarbon groups, and heteroaromatic groups, with aromatic hydrocarbon groups and heteroaromatic groups being more preferred.
  • the alkyl group as a substituent is preferably a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. Examples of such alkyl groups include methyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, cyclopropyl and cyclohexyl groups.
  • the aromatic hydrocarbon group as a substituent is preferably a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms.
  • heteroaromatic group as a substituent is preferably a monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms.
  • heteroaromatic groups include, for example, a dibenzofuranyl group, a dibenzothiophenyl group, and the like.
  • the heteroaromatic group represented by Ar 1 and Ar 2 is preferably a monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms.
  • heteroaromatic groups include pyrrolyl, thienyl, furyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, pyridyl, phenylpyridyl, pyridylphenyl, pyrimidyl group, pyrazyl group, 1,3,5-triazyl group, 1,3,5-triazylphenyl group, 1,3,5-triazylbiphenylyl group, 4,6-diphenyl-1,3,5- triazyl group, indolyl group, benzothienyl group, benzofuranyl group, benzimidazolyl group, indazolyl group, benzothiazolyl group, benzo
  • substituents in the heteroaromatic group include the same substituents as those described above in the aromatic hydrocarbon group.
  • condensed ring compound the following condensed ring compounds-I to IV are preferred.
  • the condensed ring compound-I of the present embodiment is a condensed ring compound represented by the following formula (1A-I) or formula (1B-I).
  • R 1 to R 16 and R a to R i each independently represent a hydrogen atom or a substituent; any one of R a to R i One is linked to the dibenzo[g,p]chrysene skeleton as a single bond.
  • Both of the condensed ring compounds represented by formulas (1A-I) and (1B-I) have a high glass transition temperature and a wide bandgap. Therefore, these condensed ring compounds are suitable for charge transport materials or charge blocking materials for organic semiconductor elements that require transparency, such as display members.
  • R 1 to R 16 are preferably alkyl groups, aromatic hydrocarbon groups or heteroaromatic groups, and aromatic hydrocarbon groups.
  • a hydrogen group or a heteroaromatic group is more preferred.
  • the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. Examples of such alkyl groups include methyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, cyclopropyl, cyclohexyl and 1-adamantyl groups.
  • the aromatic hydrocarbon group is preferably a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms.
  • aromatic hydrocarbon groups include phenyl, biphenyl and naphthyl groups.
  • the heteroaromatic group is preferably a monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms.
  • Such heteroaromatic groups include, for example, a dibenzofuranyl group, a dibenzothiophenyl group, and the like.
  • R 1 to R 16 are preferably hydrogen atoms from the viewpoint of having a high glass transition temperature and a wide bandgap.
  • R a to R i are: (i) a monocyclic ring having 6 to 30 carbon atoms which may be substituted; , or a condensed aromatic hydrocarbon group, (ii) an optionally substituted monocyclic, linked, or condensed heteroaromatic group having 3 to 36 carbon atoms, or (iii) 1 carbon atom A linear, branched or cyclic alkyl group of 1 to 18 is preferable, and (i) or (ii) described above is more preferable.
  • a substituent such as phenyl group, biphenylyl group, terphenylyl group, naphthyl group and fluorenyl group, anthryl group, phenanthryl group, benzofluorenyl group, triphenylenyl group, spirobifluorenyl group, diphenylfluorenyl group, dibenzo[g,p]chrysenyl group and the like.
  • the substituent is each independently a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a substituted a phosphine oxide group optionally having a group, a silyl group optionally having a substituent, a boronyl group optionally having a saturated hydrocarbon group having 2 to 10 carbon atoms, a A linear or branched alkyl group, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a trifluoromethylsulfonyloxy group is preferred.
  • the phosphine oxide group includes an unsubstituted phosphine oxide group and a phosphine oxide group having a substituent.
  • a phosphine oxide group having a substituent is preferred.
  • the phosphine oxide group having a substituent is preferably a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 18 carbon atoms, or a phosphine oxide group having a condensed heteroaromatic group. Specific examples include groups substituted with two aryl groups such as diphenylphosphine oxide.
  • Silyl groups include unsubstituted silyl groups and substituted silyl groups.
  • a silyl group having a substituent is preferred.
  • the silyl group having a substituent is preferably a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 18 carbon atoms, or a silyl group having a condensed heteroaromatic group. Specific examples thereof include groups substituted with three aryl groups such as a triphenylsilyl group.
  • Examples of the boronyl group optionally having a saturated hydrocarbon group having 2 to 10 carbon atoms include a dihydroxyboryl group (—B(OH) 2 ), 4,4,5,5-tetramethyl-[1, 3,2]-dioxaborolanyl group, 5,5-dimethyl-[1,3,2]-dioxaborinane group and the like.
  • Linear or branched alkyl groups having 1 to 18 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, n-hexyl group, cyclohexyl group, octyl group, decyl group, dodecyl group, octadecyl group and the like.
  • Linear or branched alkoxy groups having 1 to 18 carbon atoms include, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyl oxy group, n-hexyloxy group, cyclohexyloxy group, octyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group and the like.
  • the substituent is each independently a cyano group, a fluorine atom, a trifluoromethyl group, or a linear or branched alkyl group having 1 to 18 carbon atoms. , a linear or branched alkoxy group having 1 to 18 carbon atoms, or a trifluoromethylsulfonyloxy group.
  • Examples of the linear or branched alkyl group having 1 to 18 carbon atoms include the same linear or branched alkyl groups having 1 to 18 carbon atoms exemplified in (i) above.
  • Examples of the linear or branched alkoxy group having 1 to 18 carbon atoms include the same linear or branched alkoxy groups having 1 to 18 carbon atoms exemplified in (i) above.
  • Examples of linear, branched or cyclic alkyl groups having 1 to 18 carbon atoms include: methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, n-hexyl group, cyclohexyl group, octyl group, decyl group, dodecyl group , octadecyl group, and the like.
  • R a to R i have a high glass transition temperature and a wide bandgap, and are hydrogen atoms or single bonds with a dibenzo[g,p]chrysene skeleton. It is preferable that they are connected.
  • R i is an aromatic hydrocarbon group corresponding to (i) above or corresponding to (ii) above, from the viewpoint of having a high glass transition temperature and a wide bandgap. It is preferred to have a heteroaromatic group that
  • the condensed ring compound represented by formula (1A-I) is preferable in that it has a wide bandgap.
  • a compound having a wide bandgap has the advantage that the light absorption of the compound itself in a solid state tends toward the short wavelength side, so that the light absorption in a photoelectric conversion element for an imaging device, which will be described later, is less likely to be hindered.
  • condensed ring compound represented by formula (1A-I) include condensed ring compounds represented by the following formulas (A1-1) to (A4-58).
  • condensed ring compound represented by formula (1B) include condensed ring compounds represented by the following formulas (B1-1) to (B4-58).
  • the formula (A1-1 ) ⁇ (A4-58) is preferably a condensed ring compound represented by any one of the above formulas (A1-1) ⁇ (A1-58), (A2-1) ⁇ (A2-58), ( A3-2) to (A3-58), and (A4-1) to (A4-58) are more preferably condensed ring compounds represented by any of the above formulas (A1-1) to (A1 -58), (A2-1) to (A2-58), and (A4-1) to (A4-58).
  • the condensed ring compound represented by formula (1A-I) or formula (1B-I) can be produced by a known method, for example, by the method shown in the synthetic route below.
  • X and Y are a halogen atom (chlorine, bromine, or iodine) or a boronyl group optionally having a saturated hydrocarbon group having 2 to 10 carbon atoms. show. However, when X is a halogen atom, Y is a boronyl group optionally having a saturated hydrocarbon group having 2 to 10 carbon atoms, and X has a saturated hydrocarbon group having 2 to 10 carbon atoms. In the case of boronyl groups, Y is a halogen atom.
  • the condensed ring compound represented by formula (1A-I) or formula (1B-I) can be used as a charge-transporting material for a photoelectric conversion device for an imaging device or a charge blocking material for a photoelectric conversion device for an imaging device. That is, the charge transport material for a photoelectric conversion device for an image pickup device or the charge blocking material for a photoelectric conversion device for an image pickup device of the present embodiment is represented by formula (1A-I) or formula (1B-I) of the present embodiment. Including fused ring compounds.
  • the charge transport material for photoelectric conversion elements for imaging devices or the charge blocking material for photoelectric conversion devices for imaging devices for example, hole transport materials for photoelectric conversion devices for imaging devices or electron blocking materials for photoelectric conversion devices for imaging devices are preferable.
  • a charge-transporting material for a photoelectric conversion device for an imaging device or a charge blocking material for a photoelectric conversion device for an imaging device containing a condensed ring compound represented by formula (1A-I) or formula (1B-I) the film quality is improved. It is possible to manufacture a photoelectric conversion element for an imaging device that is stable, has excellent charge transport properties, sufficiently suppresses dark current, and exhibits high external quantum efficiency.
  • the photoelectric conversion element for an image pickup device of the present embodiment includes the charge transport material for a photoelectric conversion device for an image pickup device or the charge blocking material for a photoelectric conversion device for an image pickup device described above.
  • the configuration of the photoelectric conversion element for the imaging device is not particularly limited, but includes, for example, the following configurations (i) to (v).
  • the buffer layer may be replaced with a layer having another name or function as needed.
  • Layers having other names or functions include, for example, a hole injection layer and a work function adjusting layer.
  • the photoelectric conversion element for an imaging device includes at least one layer selected from the group consisting of an electron transport layer (hole blocking layer), a photoelectric conversion layer, a hole transport layer (electron blocking layer) and a buffer layer.
  • a charge transport material for devices or a charge blocking material for photoelectric conversion devices for imaging devices may be included.
  • the photoelectric conversion element for an image pickup device contains a charge transport material for a photoelectric conversion device for an image pickup device or a charge blocking material for a photoelectric conversion device for an image pickup device in the photoelectric conversion layer and/or the hole transport layer (electron blocking layer). is preferred, and it is more preferred that the hole transport layer (electron blocking layer) contains a charge transport material for a photoelectric conversion device for an imaging device or a charge blocking material for a photoelectric conversion device for an imaging device.
  • the charge-transporting material for a photoelectric conversion element for an image pickup device or the charge blocking material for a photoelectric conversion device for an image pickup device may be included in a plurality of layers provided in the photoelectric conversion device for an image pickup device.
  • FIG. 1 is a schematic cross-sectional view showing an example of a lamination structure of a photoelectric conversion element for an image pickup device containing a charge transport material for a photoelectric conversion device for an image pickup device or a charge blocking material for a photoelectric conversion device for an image pickup device according to the present embodiment.
  • Photoelectric conversion element 100-I for an imaging device in FIG. 1 includes substrate 1-I, lower electrode 2-I, electron transport layer (hole blocking layer) 3-I, photoelectric conversion layer 4-I, hole transport layer ( An electron blocking layer) 5-I, a buffer layer 6-I, and an upper electrode 7-I are provided in this order.
  • some of these layers may be omitted, or other layers may be added.
  • the photoelectric conversion element 100-I for an imaging device In the photoelectric conversion element 100-I for an imaging device, light enters from below the transparent lower electrode 2-I. Further, in the photoelectric conversion element 100-I for an imaging device, among charges (holes and electrons) generated in the photoelectric conversion layer 4-I, electrons move to the lower electrode 2-I, and holes move to the upper electrode 7-I. A voltage is applied to move to I. That is, the photoelectric conversion element 100-I for an imaging device uses the lower electrode 2-I as an electron collection electrode and the upper electrode 7-I as a hole collection electrode.
  • the photoelectric conversion element 100-I for an imaging device includes an electron transport layer (hole blocking layer) 3-I, a photoelectric conversion layer 4-I, a hole transport layer (electron blocking layer) 5-I and a buffer layer 6-I. At least one layer selected from the group consisting of a photoelectric conversion element material for an imaging element is included.
  • the photoelectric conversion element 100-I for an imaging element includes a charge transport material for a photoelectric conversion element for an imaging element or a photoelectric conversion element for an imaging element in the photoelectric conversion layer 4-I and/or the hole transport layer (electron blocking layer) 5-I.
  • the hole-transporting layer (electron blocking layer) 5-I contains a charge-transporting material for a photoelectric conversion device or a charge-blocking material for a photoelectric conversion device for an imaging device.
  • the charge transporting material for the photoelectric conversion element for the imaging element or the charge blocking material for the photoelectric conversion element for the imaging element may be included in a plurality of layers included in the photoelectric conversion element for the imaging element 100-I.
  • the hole transport layer (electron blocking layer) 5-I contains a charge transport material for an image pickup device photoelectric conversion device or a charge blocking material for an image pickup device photoelectric conversion device will be described.
  • the substrate is not particularly limited, and examples thereof include a glass plate, a quartz plate, a plastic plate and the like.
  • the substrate 1-I preferably has high transmittance (for example, transmittance of 80% or more, preferably transmittance of 90% or more) with respect to the wavelength of light. .
  • a lower electrode 2-I is provided on the substrate 1-I.
  • the lower electrode 2-I has high transmittance (for example, transmittance) with respect to the wavelength of incident light. transmittance of 80% or higher, preferably 90% or higher).
  • the transparent material used for the lower electrode 2-I is not particularly limited.
  • materials constituting the lower electrode 2 include, for example, indium-tin oxide (ITO; Indium Tin Oxide), indium-zinc oxide (IZO; Indium Zinc Oxide), tin oxide, and aluminum. ⁇ Doped tin oxide, magnesium-indium oxide, nickel-tungsten oxide, other metal oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, metal sulfides such as zinc sulfide, etc. It's okay.
  • the transmission characteristics of the lower electrode 2-I are not important. Accordingly, examples of materials used for the lower electrode 2-I in this case may be gold, iridium, molybdenum, palladium, platinum, and the like.
  • An electron transport layer (hole blocking layer) 3-I is provided between the lower electrode 2-I and the photoelectric conversion layer 4-I.
  • the electron transport layer (hole blocking layer) 3-I has a role of transporting electrons generated in the photoelectric conversion layer 4-I to the lower electrode 2-I, and a role of transporting holes generated in the photoelectric conversion layer 4-I to the lower electrode.
  • 2-I has a role of blocking movement.
  • the electron-transporting layer (hole-blocking layer) 3-I may have a single-layer structure composed of one or more materials, or may have a laminated structure composed of multiple layers having the same composition or different compositions.
  • the electron transport layer (hole blocking layer) 3-I includes, for example, a layer adjacent to the photoelectric conversion layer 4-I made of a material specialized for hole blocking and a lower layer made of a material specialized for electron transport. and a layer adjacent to the electrode 2-I.
  • the electron transport layer (hole blocking layer) 3-I may be a layer containing a conventionally known electron transport material.
  • Conventionally known electron transport materials include, for example, bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, BCP ( 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis(2-methyl-8-quinolinolate)-4-( phenylphenolate)aluminum), 4,6-bis(3,5-di(pyridin-4-yl)phenyl)-2-methylpyrimidine, N,N'-diphenyl-1,4,5,8-naphthalenetetra carboxylic acid diimide, N,N'-di(4-pyridyl)-1,4,5,8-naphthalenetetracarbox
  • a photoelectric conversion layer 4-I is provided between the electron transport layer (hole blocking layer) 3-I and the hole transport layer (electron blocking layer) 5-I described later.
  • the photoelectric conversion layer 4-I contains a material having a photoelectric conversion function.
  • the photoelectric conversion layer 4-I may have a single layer structure composed of one or more materials, or may have a multilayer structure composed of multiple layers having the same composition or different compositions.
  • single-layer photoelectric conversion layers made of one type of material include photoelectric conversion layers made of materials such as coumarin and its derivatives, quinacridone and its derivatives, and phthalocyanine and its derivatives.
  • a photoelectric conversion layer having a single layer structure made of two materials for example, (i) a first material selected from the group consisting of coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, ( ii) a photoelectric conversion layer containing a second material selected from the group consisting of fullerenes and derivatives thereof;
  • the photoelectric conversion layer may further contain (iii) a hole transport material.
  • the photoelectric conversion layer 4-I made of these materials may be formed, for example, by vapor deposition using a mixed powder in which powders of each material are mixed, or by co-depositing each material at an arbitrary ratio. good too.
  • coumarin derivatives include coumarin 6 and coumarin 30.
  • quinacridone derivatives include N,N-dimethylquinacridone and the like.
  • phthalocyanine derivative include boron-subphthalocyanine chloride, boron-subnaphthalocyanine chloride (SubNC), and the like.
  • fullerene and derivatives thereof include [60] fullerene, [70] fullerene, [6,6]-phenyl-C61-methylbutyrate ([60]PCBM), and the like.
  • the hole-transporting material may be any known hole-transporting material;
  • hole transport materials include aromatic tertiary amine compounds, naphthalene compounds, anthracene compounds, tetracene compounds, pentacene compounds, phenanthrene compounds, pyrene compounds, perylene compounds, fluorene compounds, carbazole compounds, indole compounds, pyrrole compounds, picene compounds, thiophene compounds, benzotrifuran compounds, benzotrithiophene compounds, naphthodithiophene compounds, naphthothienothiophene compounds, benzodifuran compounds, benzodithiophene compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, chrysenodithiophene compounds, benzothienobenzothiophene compounds, indolocarbazole compounds, and the like.
  • fluorene compounds preferred are fluorene compounds, naphthodithiophene compounds, naphthothienothiophene compounds, benzodifuran compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, chrysenodithiophene compounds, benzothienobenzothiophene compounds, indolocarbazole compounds, and the like.
  • Fluorene compounds, chrysenodithiophene compounds, benzothienobenzothiophene compounds, and indolocarbazole compounds are more preferred.
  • hole transport materials include 9,9′-(9,9′-spirobi[9H-fluorene]-2,7′-diyl)bis[9H-carbazole], 2,7-diphenyl[1] benzothieno[3,2-b][1]benzothiophene (DiPh-BTBT), benzo[1,2-b:3,4-b′:5,6-b′′]trifuran compounds, benzo[1,2 -b:3,4-b':5,6-b'']trithiophene compound, naphtho[1,2-b:5,6-b']dithiophene, naphtho[2,3-b]naphtho[2 ',3':4,5]thieno[2,3-d]thiophene, benzo[1,2-b:4,5-b']difuran, benzo[1,2-b:4,5-b' ] dithiophene, benzo[1,2-b:4,5-b′]bis[1]benz
  • the material having the photoelectric conversion function described above may be contained only in the photoelectric conversion layer 4-I, or may be contained in layers other than the photoelectric conversion layer 4-I.
  • layers adjacent to the photoelectric conversion layer 4-I (electron transport layer (hole blocking layer) 3-I, hole transport layer (electron blocking layer) 5-I) contain a material having a photoelectric conversion function. may be
  • a hole transport layer (electron blocking layer) 5-I is provided between the photoelectric conversion layer 4-I and a buffer layer 6-I described later.
  • the hole transport layer (electron blocking layer) 5-I has the role of transporting holes generated in the photoelectric conversion layer 4-I to the upper electrode 7-I side, and the electrons generated in the photoelectric conversion layer 4-I It has a role of blocking movement to the electrode 7-I side.
  • the hole-transporting layer (electron-blocking layer) 5-I preferably contains the charge-transporting material for a photoelectric conversion device for an imaging device or the charge-blocking material for a photoelectric conversion device for an imaging device.
  • the hole-transporting layer (electron-blocking layer) 5-I may have a single-layer structure composed of one or more materials, or may have a laminated structure composed of multiple layers having the same composition or different compositions.
  • the hole transport layer (electron blocking layer) 5-I includes, for example, a layer adjacent to the photoelectric conversion layer 4-I made of a material specialized for electron blocking and a buffer made of a material specialized for hole transport. and a layer adjacent to layer 6-I.
  • the hole-transporting layer (electron-blocking layer) 5-I may further contain a conventionally known hole-transporting material in addition to the above-described materials for photoelectric conversion elements for imaging elements.
  • a conventionally known hole-transporting material in addition to the above-described materials for photoelectric conversion elements for imaging elements.
  • Preferable compounds and specific examples of conventionally known hole-transporting materials are the same as the hole-transporting materials described in the item of photoelectric conversion layer 4-I.
  • a buffer layer 6-I is provided between the hole transport layer (electron blocking layer) 5-I and an upper electrode 7-I, which will be described later.
  • the buffer layer 6-I serves to reduce damage to the organic layer (for example, the hole transport layer (electron blocking layer) 5-I) during sputtering.
  • the work function of the buffer layer 6-I it also plays a role of efficiently accepting holes from the hole transport layer (electron blocking layer) 5-I, and is also called a hole injection layer or a work function adjustment layer. Called.
  • Materials constituting the buffer layer 6-I may be known materials such as naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA), 2,3,6,7,10, 11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN) and the like.
  • NTCDA naphthalene-1,4,5,8-tetracarboxylic dianhydride
  • HTCN 2,3,6,7,10, 11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene
  • An upper electrode 7-I is provided on the buffer layer 6-I.
  • the material of the upper electrode 7-I is not particularly limited, and examples include sodium, sodium-potassium alloy, magnesium, lithium, magnesium/copper mixture, silver, magnesium/silver mixture, aluminum, magnesium/aluminum mixture, magnesium/indium mixture, It may be aluminum/aluminum oxide (Al 2 O 3 ) mixtures, indium, lithium/aluminum mixtures, rare earth metals, and the like.
  • each layer other than the lower electrode 2-I and the upper electrode 7-I the material of each layer (and, if necessary, a material such as a binder resin, a solvent, etc.) is applied by, for example, a vacuum evaporation method, a spin coating method, or a casting method. , LB (Langmuir-Blodgett method), or the like.
  • the thickness of each layer other than the lower electrode 2-I and the upper electrode 7-I is not particularly limited, and can be appropriately selected depending on the situation.
  • the thickness of each layer other than the lower electrode 2-I and the upper electrode 7-I is usually in the range of 5 nm or more and 5 ⁇ m or less.
  • the lower electrode 2-I and the upper electrode 7-I can be formed by thinning an electrode material by a method such as vapor deposition or sputtering.
  • the pattern can be formed through a mask having a desired shape, for example.
  • a pattern having a desired shape may be formed by photolithography.
  • the film thickness of the lower electrode 2-I and the upper electrode 7-I may be 1 ⁇ m or less, preferably 10 nm or more and 200 nm or less.
  • the materials constituting the lower electrode 2-I and the upper electrode 7-I may be exchanged if necessary (also called an inverted structure).
  • the photoelectric conversion element for an imaging device is configured such that light passes through the upper electrode 7-I and is incident on the photoelectric conversion layer 4-I.
  • An imaging device equipped with a photoelectric conversion device can be applied to, for example, imaging devices such as digital cameras and digital video cameras, and imaging devices built in mobile phones and the like.
  • imaging devices such as digital cameras and digital video cameras, and imaging devices built in mobile phones and the like.
  • the present invention may relate to a hole-only device containing the charge-transporting material for a photoelectric conversion device for an imaging device described above.
  • the device configuration of the hole-only device is not particularly limited, the following configurations (a) to (c) can be mentioned, for example.
  • (a) lower electrode/hole transport layer/upper electrode (b) lower electrode/hole injection layer/hole transport layer/upper electrode
  • buffer layer may be replaced with a layer having another name or function as necessary.
  • Layers having other names or functions include, for example, a work function adjusting layer.
  • At least one layer selected from the group consisting of a hole injection layer, a hole transport layer and a buffer layer may contain a charge transport material for a photoelectric conversion device for an imaging device, and the hole transport layer may contain an imaging material. It preferably contains a charge transport material for photoelectric conversion devices.
  • the charge-transporting material for the photoelectric conversion device for the imaging device may be included in a plurality of layers included in the hole-only device.
  • FIG. 2 is a schematic cross-sectional view showing an example of a layered structure of a hole-only element.
  • the hole-only device 1000-I of FIG. 2 includes a substrate 101-I, a lower electrode 102-I, a hole injection layer 103-I, a hole transport layer 104-I, a buffer layer 105-I and an upper electrode 106-I. Prepare in this order. Note that the hole-only element may omit some of these layers, or may have other layers added.
  • At least one layer selected from the group consisting of a hole injection layer 103-I, a hole transport layer 104-I, and a buffer layer 105-I contains a charge transport material for a photoelectric conversion device for an imaging device. and it is preferable that the hole transport layer 104-I contains a charge transport material for a photoelectric conversion element for an imaging device. Note that the charge-transporting material for the photoelectric conversion element for the imaging element may be included in a plurality of layers included in the hole-only element 1000-I.
  • each layer will be described below, taking as an example a hole-only device 1000-I in which the hole-transport layer 104-I contains a charge-transport material for a photoelectric conversion device for an imaging device.
  • the substrate 101-I is not particularly limited, and can be exemplified by the same substrate as in the above photoelectric conversion element for imaging device.
  • a lower electrode 102-I is provided on the substrate 101-I.
  • the same one as the lower electrode in the above-described photoelectric conversion element for imaging device can be exemplified.
  • a hole injection layer 103-I is provided between the lower electrode 102-I and the hole transport layer 104-I.
  • the hole injection layer 103-I has a role of promoting the injection of holes from the lower electrode 102-I to the hole transport layer 104-I.
  • the hole injection layer 103-I may have a single layer structure composed of one or more materials, or may have a laminated structure composed of multiple layers of the same composition or different compositions.
  • the hole injection layer 103-I may be, for example, a layer containing a conventionally known hole injection material.
  • Conventionally known hole injection materials include, for example, molybdenum oxide and 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN). be done.
  • a hole transport layer 104-I is provided between the hole injection layer 103-I and the buffer layer 105-I.
  • the hole transport layer 104-I has a role of transporting holes carried from the hole injection layer 103-I to the upper electrode 106-I side.
  • the hole-transporting layer 104-I preferably contains the charge-transporting material for photoelectric conversion elements for imaging elements described above.
  • the hole-transporting layer 104-I may have a single-layer structure composed of one or more materials, or may have a laminated structure composed of multiple layers of the same composition or different compositions.
  • the hole-transporting layer 104-I may further contain a conventionally known hole-transporting material in addition to the above charge-transporting material for photoelectric conversion elements for imaging devices.
  • a conventionally known hole-transporting material in addition to the above charge-transporting material for photoelectric conversion elements for imaging devices.
  • Preferable compounds and specific examples of conventionally known hole-transporting materials include the same hole-transporting materials described in the item of the photoelectric conversion layer 4-I in the photoelectric conversion element 100-I for an imaging device.
  • a buffer layer 105-I is provided between the hole transport layer 104-I and the upper electrode 106-I.
  • the role of the buffer layer 105-I is not particularly limited, but includes the role of improving interface contact between the adjacent hole transport layer 104-I and the upper electrode 106-I, the role of adjusting the work function, and the like. be done.
  • the material constituting the buffer layer 105-I may be a known material, such as HATCN described above.
  • An upper electrode 106-I is provided on the buffer layer 105-I.
  • the same one as the upper electrode in the above-described photoelectric conversion element for imaging device can be exemplified.
  • each layer other than the lower electrode 102-I and the upper electrode 106-I the material of each layer (and, if necessary, a binder resin, solvent, etc.) is applied, for example, by vacuum deposition, spin coating, casting, LB (Langmuir-Blodgett method) method or the like to form a thin film.
  • LB Liuir-Blodgett method
  • each layer other than the lower electrode 102-I and the upper electrode 106-I is not particularly limited, and can be appropriately selected depending on the situation.
  • the thickness of each layer other than the lower electrode 102-I and the upper electrode 106-I is usually in the range of 5 nm or more and 5 ⁇ m or less.
  • the lower electrode 102-I and the upper electrode 106-I can be formed by thinning an electrode material by a method such as vapor deposition or sputtering.
  • the pattern can be formed, for example, by vapor deposition, sputtering, or the like through a mask of desired shape.
  • a pattern having a desired shape may be formed by photolithography.
  • the thickness of the lower electrode 102-I and the upper electrode 106-I may be, for example, 1 ⁇ m or less, preferably 10 nm or more and 200 nm or less.
  • Materials constituting the lower electrode 102-I and the upper electrode 106-I may be exchanged as necessary.
  • the condensed ring compound-II of this embodiment is a condensed ring compound represented by the following formula (1A-II) or formula (1B-II).
  • R 1 to R 16 each independently represent a hydrogen atom or a substituent;
  • L represents a phenylene group optionally having a substituent, a biphenylene group optionally having a substituent, or a terphenylene group optionally having a substituent;
  • Ar is an adamantyl group optionally having substituents, a carbazolyl group optionally having substituents, a fluoranthenyl group optionally having substituents, optionally having substituents represents a triphenylenyl group, an optionally substituted dibenzofuranyl group, or an optionally substituted dibenzothiophenyl group;
  • none of R 1 to R 16 have the same structure as L—Ar.
  • Both of the condensed ring compounds represented by formulas (1A-II) and (1B-II) have a high glass transition temperature and a wide bandgap. Therefore, these condensed ring compounds are suitable as charge transport materials for organic semiconductor elements that require transparency, such as display members.
  • R 1 to R 16 are preferably alkyl groups, aromatic hydrocarbon groups or heteroaromatic groups, and aromatic hydrocarbon groups.
  • a hydrogen group or a heteroaromatic group is more preferred.
  • the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. Examples of such alkyl groups include methyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, cyclopropyl and cyclohexyl groups.
  • the aromatic hydrocarbon group is preferably a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms.
  • aromatic hydrocarbon groups include phenyl, biphenyl and naphthyl groups.
  • the heteroaromatic group is preferably a monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms.
  • Such heteroaromatic groups include, for example, a dibenzofuranyl group, a dibenzothiophenyl group, and the like. None of R 1 to R 16 are the same as the structure represented by L-Ar described below.
  • R 1 to R 16 are preferably hydrogen atoms from the viewpoint that the condensed ring compound has a high glass transition temperature and a wide bandgap.
  • L is a phenylene group optionally having a substituent, a biphenylene group optionally having a substituent, or having a substituent represents a terphenylene group.
  • L is a divalent group connecting the dibenzo[g,p]chrysene skeleton in formula (1A-II) or formula (1B-II) and Ar described later.
  • the phenylene group include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group and the like.
  • the biphenylene group includes, for example, 4,4'-biphenylene group, 4,3'-biphenylene group, 4,2'-biphenylene group, 3,3'-biphenylene group, 3,2'-biphenylene group, 2,2 '-biphenylene group and the like.
  • Terphenylene groups include, for example, 4,4''-p-terphenylene group, 4,3''-p-terphenylene group, 4,2''-p-terphenylene group, 3,3''- p-terphenylene group, 3,2''-p-terphenylene group, 2,2''-p-terphenylene group, 4,2'-p-terphenylene group, 4,3'-p-terphenylene group, 3,2′-p-terphenylene group, 3,3′-p-terphenylene group, 2,3′-p-terphenylene group, 2,2′-p-terphenylene group, 4,4′ '-m-terphenylene group, 4,3''-m-terphenylene group, 4,2''-m-terphenylene group, 3,3''-m-terphenylene group, 3,2''-m-terphenylene group, 2,2''-m-terphenylene group, 4,2'-m-terphenylene group, 4,2
  • the substituent for L is preferably an alkyl group, an aromatic hydrocarbon group or a heteroaromatic group, more preferably an aromatic hydrocarbon group or a heteroaromatic group.
  • the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. Examples of such alkyl groups include methyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, cyclopropyl and cyclohexyl groups.
  • the aromatic hydrocarbon group is preferably a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms. Examples of such aromatic hydrocarbon groups include phenyl, biphenyl and naphthyl groups.
  • the heteroaromatic group is preferably a monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms.
  • Such heteroaromatic groups include, for example, a dibenzofuranyl group, a dibenzothiophenyl group, and the like.
  • L is preferably an unsubstituted phenylene group or an unsubstituted biphenylene group.
  • Ar is an adamantyl group which may have a substituent, a carbazolyl group which may have a substituent, a carbazolyl group which may have a substituent, optionally substituted fluoranthenyl group, optionally substituted triphenylenyl group, optionally substituted dibenzofuranyl group, or optionally substituted dibenzothiophenyl group;
  • an adamantyl group which may have a substituent, a carbazolyl group which may have a substituent, and a triphenylenyl group which may have a substituent are preferable.
  • All of the substituents on Ar are preferably alkyl groups, aromatic hydrocarbon groups or heteroaromatic groups, more preferably aromatic hydrocarbon groups or heteroaromatic groups.
  • the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. Examples of such alkyl groups include methyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, cyclopropyl and cyclohexyl groups.
  • the aromatic hydrocarbon group is preferably a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms. Examples of such aromatic hydrocarbon groups include phenyl, biphenyl and naphthyl groups.
  • the heteroaromatic group is preferably a monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms.
  • Such heteroaromatic groups include, for example, a dibenzofuranyl group, a dibenzothiophenyl group, and the like.
  • the condensed ring compound represented by formula (1A-II) is preferable in that it has a wide bandgap.
  • a compound having a wide bandgap has the advantage that the light absorption of the compound itself in a solid state tends toward the short wavelength side, so that the light absorption in a photoelectric conversion element for an imaging device, which will be described later, is less likely to be hindered.
  • condensed ring compound represented by formula (1A-II) include the following formulas (AA-1) to (AA-20), (AC-1) to (AC-28), and (AF-1) ⁇ (AF-20), (AT-1) ⁇ (AT-20), (AO-1) ⁇ (AO-40), (AS-1) ⁇ (AS-40) condensed ring compounds represented by mentioned.
  • condensed ring compound represented by formula (1B-II) include the following formulas (BA-1) to (BA-20), (BC-1) to (BC36), (BF-1) to ( BF-20), (BT-1) to (BT-20), (BO-1) to (BO-40), and condensed ring compounds represented by (BS-1) to (BS-40).
  • (AA-1) ⁇ (AA-20), (AC-1) ⁇ (AC-28), (AT-1) ⁇ (AT-20), (BA- 1) ⁇ (BA-20), (BC-1) ⁇ (BC36), (BT-1) ⁇ (BT-20) are more preferably condensed ring compounds represented by (AA-1) ⁇ ( AA-20), (AC-1) to (AC-28), and (AT-1) to (AT-20) are more preferred condensed ring compounds.
  • the condensed ring compound represented by formula (1A-II) or formula (1B-II) can be produced by a known method, for example, by the method shown in the synthetic route below.
  • X and Y are a halogen atom (chlorine, bromine, or iodine), a boronyl group optionally having a saturated hydrocarbon group having 2 to 10 carbon atoms , or represents a trifluoromethanesulfonyl group (triflyl group).
  • X is a halogen atom or a triflyl group
  • Y is a boronyl group
  • Y is a halogen atom or a triflyl group.
  • R 1 to R 16 The definitions of R 1 to R 16 and the preferred ranges of substituents in the above formulas (AX), (BX), (C), (1A-II) and (1B-II) are the same as described above.
  • a compound represented by the formula (AX) or (BX) and a compound represented by the formula (C) are subjected to a coupling reaction in the presence of a palladium catalyst, optionally using a base, to obtain the formula (1A-II).
  • a dibenzo[g,p]chrysene compound represented by (1B-II) is obtained.
  • a condensed ring compound represented by formula (1A-II) or formula (1B-II) can be used as a charge transport material for a photoelectric conversion device for an imaging device. That is, the charge-transporting material for a photoelectric conversion device for an imaging device of the present embodiment contains the condensed ring compound represented by Formula (1A-II) or Formula (1B-II) of the present embodiment.
  • the charge-transporting material for photoelectric conversion elements for imaging devices for example, hole-transporting materials for photoelectric conversion devices for imaging devices are preferable.
  • An image pickup device having stable film quality and excellent charge transport properties by using a charge transport material for a photoelectric conversion device for an image pickup device containing a condensed ring compound represented by formula (1A-II) or formula (1B-II). can produce a photoelectric conversion element for
  • the photoelectric conversion element for an image pickup device of the present embodiment includes the charge transport material for a photoelectric conversion device for an image pickup device or the charge blocking material for a photoelectric conversion device for an image pickup device described above.
  • the configuration of the photoelectric conversion element for the imaging device is not particularly limited, but includes, for example, the following configurations (i) to (v).
  • the buffer layer may be replaced with a layer having another name or function as needed.
  • Layers having other names or functions include, for example, a hole injection layer and a work function adjusting layer.
  • the photoelectric conversion element for an imaging device includes at least one layer selected from the group consisting of an electron transport layer (hole blocking layer), a photoelectric conversion layer, a hole transport layer (electron blocking layer) and a buffer layer.
  • a charge transport material for devices or a charge blocking material for photoelectric conversion devices for imaging devices may be included.
  • the photoelectric conversion element for an image pickup device contains a charge transport material for a photoelectric conversion device for an image pickup device or a charge blocking material for a photoelectric conversion device for an image pickup device in the photoelectric conversion layer and/or the hole transport layer (electron blocking layer). is preferred, and it is more preferred that the hole transport layer (electron blocking layer) contains a charge transport material for a photoelectric conversion device for an imaging device or a charge blocking material for a photoelectric conversion device for an imaging device.
  • the charge-transporting material for a photoelectric conversion element for an image pickup device or the charge blocking material for a photoelectric conversion device for an image pickup device may be included in a plurality of layers provided in the photoelectric conversion device for an image pickup device.
  • FIG. 3 is a schematic cross-sectional view showing an example of a lamination structure of a photoelectric conversion element for an image pickup device containing the charge transport material for the photoelectric conversion device for the image pickup device or the charge blocking material for the photoelectric conversion device for the image pickup device according to the present embodiment. .
  • the photoelectric conversion element 100-II for an imaging device in FIG. 3 includes a substrate 1-II, a lower electrode 2-II, an electron transport layer (hole blocking layer) 3-II, a photoelectric conversion layer 4-II, a hole transport layer ( An electron blocking layer) 5-II, a buffer layer 6-II, and an upper electrode 7-II are provided in this order.
  • some of these layers may be omitted, or other layers may be added.
  • the photoelectric conversion element 100-II for an image sensor light enters from below the transparent lower electrode 2-II. Further, in the photoelectric conversion element 100-II for an imaging device, among charges (holes and electrons) generated in the photoelectric conversion layer 4-II, electrons move to the lower electrode 2-II, and holes move to the upper electrode 7- A voltage is applied to move to II. That is, the photoelectric conversion element 100-II for an imaging device uses the lower electrode 2-II as an electron collection electrode and the upper electrode 7-II as a hole collection electrode.
  • the photoelectric conversion element 100-II for an imaging device includes an electron transport layer (hole blocking layer) 3-II, a photoelectric conversion layer 4-II, a hole transport layer (electron blocking layer) 5-II and a buffer layer 6-II. At least one layer selected from the group consisting of a photoelectric conversion element material for an imaging element is included.
  • the photoelectric conversion element 100-II for an imaging element includes a charge transport material for a photoelectric conversion element for an imaging element or a photoelectric conversion element for an imaging element in the photoelectric conversion layer 4-II and/or the hole transport layer (electron blocking layer) 5-II.
  • the hole-transporting layer (electron blocking layer) 5-II contains a charge-transporting material for a photoelectric conversion device for an imaging device or a charge-blocking material for a photoelectric conversion device for an imaging device.
  • the charge transport material for the photoelectric conversion element for the imaging element or the charge blocking material for the photoelectric conversion element for the imaging element may be included in a plurality of layers included in the photoelectric conversion element for the imaging element 100-II.
  • the hole transport layer (electron blocking layer) 5-II contains a charge transport material for an image pickup device photoelectric conversion device or a charge blocking material for an image pickup device photoelectric conversion device will be described.
  • the substrate is not particularly limited, and examples thereof include a glass plate, a quartz plate, a plastic plate and the like.
  • the substrate 1-II preferably has high transmittance (for example, transmittance of 80% or more, preferably transmittance of 90% or more) with respect to the wavelength of light. .
  • a lower electrode 2-II is provided on the substrate 1-II.
  • the lower electrode 2-II has high transmittance (for example, transmittance) with respect to the wavelength of incident light. transmittance of 80% or higher, preferably 90% or higher).
  • the transparent material used for the lower electrode 2-II is not particularly limited.
  • materials constituting the lower electrode 2 include, for example, indium-tin oxide (ITO; Indium Tin Oxide), indium-zinc oxide (IZO; Indium Zinc Oxide), tin oxide, and aluminum. ⁇ Doped tin oxide, magnesium-indium oxide, nickel-tungsten oxide, other metal oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, metal sulfides such as zinc sulfide, etc. It's okay.
  • the transmission characteristics of the lower electrode 2-II are not important. Accordingly, examples of materials used for the lower electrode 2-II in this case may be gold, iridium, molybdenum, palladium, platinum, and the like.
  • An electron transport layer (hole blocking layer) 3-II is provided between the lower electrode 2-II and the photoelectric conversion layer 4-II.
  • the electron transport layer (hole blocking layer) 3-II has the role of transporting electrons generated in the photoelectric conversion layer 4-II to the lower electrode 2-II and the role of transporting the holes generated in the photoelectric conversion layer 4-II to the lower electrode. It has a role of blocking migration to 2-II.
  • the electron-transporting layer (hole-blocking layer) 3-II may have a single-layer structure composed of one or more materials, or may have a laminated structure composed of multiple layers having the same composition or different compositions.
  • the electron transport layer (hole blocking layer) 3-II includes, for example, a layer adjacent to the photoelectric conversion layer 4-II made of a material specialized for hole blocking, and a lower layer made of a material specialized for electron transport. and a layer adjacent to electrode 2-II.
  • the electron transport layer (hole blocking layer) 3-II may be a layer containing a conventionally known electron transport material.
  • Conventionally known electron transport materials include, for example, bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, BCP ( 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis(2-methyl-8-quinolinolate)-4-( phenylphenolate)aluminum), 4,6-bis(3,5-di(pyridin-4-yl)phenyl)-2-methylpyrimidine, N,N'-diphenyl-1,4,5,8-naphthalenetetra carboxylic acid diimide, N,N'-di(4-pyridyl)-1,4,5,8-naphthalenetetracar
  • a photoelectric conversion layer 4-II is provided between the electron transport layer (hole blocking layer) 3-II and the hole transport layer (electron blocking layer) 5-II described later.
  • the photoelectric conversion layer 4-II contains a material having a photoelectric conversion function.
  • the photoelectric conversion layer 4-II may have a single layer structure composed of one or more materials, or may have a laminated structure composed of multiple layers having the same composition or different compositions.
  • Examples of single-layer photoelectric conversion layers made of one type of material include photoelectric conversion layers made of materials such as coumarin and its derivatives, quinacridone and its derivatives, and phthalocyanine and its derivatives.
  • a photoelectric conversion layer having a single layer structure made of two materials for example, (i) a first material selected from the group consisting of coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, ( ii) a photoelectric conversion layer containing a second material selected from the group consisting of fullerenes and derivatives thereof;
  • the photoelectric conversion layer may further contain (iii) a hole transport material.
  • the photoelectric conversion layer 4-II made of these materials may be formed, for example, by vapor deposition using a mixed powder in which powders of each material are mixed, or by co-depositing each material at an arbitrary ratio. good too.
  • coumarin derivatives include coumarin 6 and coumarin 30.
  • quinacridone derivatives include N,N-dimethylquinacridone and the like.
  • phthalocyanine derivative include boron-subphthalocyanine chloride, boron-subnaphthalocyanine chloride (SubNC), and the like.
  • fullerene and derivatives thereof include [60] fullerene, [70] fullerene, [6,6]-phenyl-C61-methylbutyrate ([60]PCBM), and the like.
  • the hole transport material may be any known hole transport material;
  • hole transport materials include aromatic tertiary amine compounds, naphthalene compounds, anthracene compounds, tetracene compounds, pentacene compounds, phenanthrene compounds, pyrene compounds, perylene compounds, fluorene compounds, carbazole compounds, indole compounds, pyrrole compounds, picene compounds, thiophene compounds, benzotrifuran compounds, benzotrithiophene compounds, naphthodithiophene compounds, naphthothienothiophene compounds, benzodifuran compounds, benzodithiophene compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, chrysenodithiophene compounds, benzothienobenzothiophene compounds, indolocarbazole compounds, and the like.
  • fluorene compounds preferred are fluorene compounds, naphthodithiophene compounds, naphthothienothiophene compounds, benzodifuran compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, chrysenodithiophene compounds, benzothienobenzothiophene compounds, indolocarbazole compounds, and the like.
  • Fluorene compounds, chrysenodithiophene compounds, benzothienobenzothiophene compounds, and indolocarbazole compounds are more preferred.
  • hole transport materials include 9,9′-(9,9′-spirobi[9H-fluorene]-2,7′-diyl)bis[9H-carbazole], 2,7-diphenyl[1] benzothieno[3,2-b][1]benzothiophene (DiPh-BTBT), benzo[1,2-b:3,4-b′:5,6-b′′]trifuran compounds, benzo[1,2 -b:3,4-b':5,6-b'']trithiophene compound, naphtho[1,2-b:5,6-b']dithiophene, naphtho[2,3-b]naphtho[2 ',3':4,5]thieno[2,3-d]thiophene, benzo[1,2-b:4,5-b']difuran, benzo[1,2-b:4,5-b' ] dithiophene, benzo[1,2-b:4,5-b′]bis[1]benz
  • the material having the photoelectric conversion function described above may be contained only in the photoelectric conversion layer 4-II, or may be contained in layers other than the photoelectric conversion layer 4-II.
  • layers adjacent to photoelectric conversion layer 4-II (electron transport layer (hole blocking layer) 3-II, hole transport layer (electron blocking layer) 5-II) contain a material having a photoelectric conversion function. may be
  • a hole transport layer (electron blocking layer) 5-II is provided between the photoelectric conversion layer 4-II and a buffer layer 6-II described later.
  • the hole transport layer (electron blocking layer) 5-II has the role of transporting holes generated in the photoelectric conversion layer 4-II to the upper electrode 7-II side, and the electrons generated in the photoelectric conversion layer 4-II It has a role of blocking movement to the electrode 7-II side.
  • the hole-transporting layer (electron-blocking layer) 5-II preferably contains the charge-transporting material for photoelectric conversion elements for imaging devices or the charge-blocking material for photoelectric conversion devices for imaging devices described above.
  • the hole-transporting layer (electron-blocking layer) 5-II may have a single-layer structure composed of one or more materials, or may have a laminated structure composed of multiple layers having the same composition or different compositions.
  • the hole transport layer (electron blocking layer) 5-II includes, for example, a layer adjacent to the photoelectric conversion layer 4-II made of a material specialized for electron blocking and a buffer made of a material specialized for hole transport. and a layer adjacent to layer 6-II.
  • the hole-transporting layer (electron-blocking layer) 5-II may further contain a conventionally known hole-transporting material in addition to the above-described photoelectric conversion element materials for imaging elements.
  • a conventionally known hole-transporting material in addition to the above-described photoelectric conversion element materials for imaging elements.
  • Preferable compounds and specific examples of conventionally known hole-transporting materials are the same as the hole-transporting materials described in the item of photoelectric conversion layer 4-II.
  • a buffer layer 6-II is provided between the hole transport layer (electron blocking layer) 5-II and an upper electrode 7-II described later.
  • the buffer layer 6-II serves to reduce damage to the organic layer (for example, the hole transport layer (electron blocking layer) 5-II) during sputtering.
  • the work function of the buffer layer 6-II it also plays a role of efficiently accepting holes from the hole transport layer (electron blocking layer) 5-II, and is also called a hole injection layer or a work function adjustment layer. Called.
  • Materials constituting the buffer layer 6-II may be known materials such as naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA), 2,3,6,7,10, 11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN) and the like.
  • NTCDA naphthalene-1,4,5,8-tetracarboxylic dianhydride
  • HTCN 2,3,6,7,10, 11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene
  • An upper electrode 7-II is provided on the buffer layer 6-II.
  • the material of the upper electrode 7-II is not particularly limited, and examples include sodium, sodium-potassium alloy, magnesium, lithium, magnesium/copper mixture, silver, magnesium/silver mixture, aluminum, magnesium/aluminum mixture, magnesium/indium mixture, It may be aluminum/aluminum oxide (Al 2 O 3 ) mixtures, indium, lithium/aluminum mixtures, rare earth metals, and the like.
  • each layer other than the lower electrode 2-II and the upper electrode 7-II the material of each layer (and, if necessary, a material such as a binder resin, a solvent, etc.) is applied, for example, by a vacuum vapor deposition method, a spin coating method, a casting method, or the like. , LB (Langmuir-Blodgett method), or the like.
  • the thickness of each layer other than the lower electrode 2-II and the upper electrode 7-II is not particularly limited, and can be appropriately selected depending on the situation.
  • the thickness of each layer other than the lower electrode 2-II and the upper electrode 7-II is usually in the range of 5 nm or more and 5 ⁇ m or less.
  • the lower electrode 2-II and the upper electrode 7-II can be formed by thinning an electrode material by a method such as vapor deposition or sputtering.
  • the pattern can be formed through a mask having a desired shape, for example.
  • a pattern having a desired shape may be formed by photolithography.
  • the film thickness of the lower electrode 2-II and the upper electrode 7-II may be 1 ⁇ m or less, preferably 10 nm or more and 200 nm or less.
  • the materials constituting the lower electrode 2-II and the upper electrode 7-II may be exchanged if necessary (also called an inverted structure).
  • the photoelectric conversion element for an imaging device is configured such that light passes through the upper electrode 7-II and is incident on the photoelectric conversion layer 4-II.
  • An imaging device equipped with a photoelectric conversion device can be applied to, for example, imaging devices such as digital cameras and digital video cameras, and imaging devices built in mobile phones and the like.
  • imaging devices such as digital cameras and digital video cameras, and imaging devices built in mobile phones and the like.
  • the condensed ring compound-III of the present embodiment is a condensed ring compound represented by the following formula (1-III).
  • R 1 to R 16 each independently represent a hydrogen atom or a substituent; either R 2 or R 3 is Ar 1 ; either R 6 or R 7 is Ar 2 ; Ar 1 and Ar 2 are the same and represent an aromatic hydrocarbon group or a heteroaromatic group.
  • R 1 to R 16 each independently represent a hydrogen atom or a substituent.
  • the substituent is preferably an alkyl group, an aromatic hydrocarbon group or a heteroaromatic group, more preferably an aromatic hydrocarbon group or a heteroaromatic group.
  • the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. Examples of such alkyl groups include methyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, cyclopropyl and cyclohexyl groups.
  • the aromatic hydrocarbon group is preferably a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms.
  • aromatic hydrocarbon groups include phenyl, biphenyl and naphthyl groups.
  • the heteroaromatic group is preferably a monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms.
  • Such heteroaromatic groups include, for example, a dibenzofuranyl group, a dibenzothiophenyl group, and the like.
  • R 1 to R 16 do not correspond to Ar 1 or Ar 2 described later, they are preferably hydrogen atoms from the viewpoint that the condensed ring compound has a high glass transition temperature and a wide bandgap.
  • the condensed ring compound represented by formula (1-III) is preferably a condensed ring compound represented by the following formula (1A-III), formula (1B-III), or formula (1C-III), A condensed ring compound represented by the following formula (2A-III), formula (2B-III), or formula (2C-III) is more preferable.
  • R 1 to R 16 each independently represent a hydrogen atom or a substituent; Ar 1 and Ar 2 are are the same as each other and represent an aromatic hydrocarbon group or a heteroaromatic group.
  • the substituents for R 1 to R 16 are the same as the substituents for R 1 to R 16 in formula (1) above.
  • Ar 1 and Ar 2 are the same and represent an aromatic hydrocarbon group or a heteroaromatic group.
  • Ar 1 and Ar 2 > Formula (1-III) above, Formula (1A-III), Formula (1B-III), and Formula (1C-III) above, and Formula (2A-III) and Formula (2B-III) above, and in formula (2C-III), Ar 1 and Ar 2 are the same and represent an aromatic hydrocarbon group or a heteroaromatic group.
  • the aromatic hydrocarbon group represented by Ar 1 and Ar 2 is preferably a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms.
  • aromatic hydrocarbon groups include phenyl, biphenylyl, terphenylyl, naphthyl, fluorenyl, anthryl, phenanthryl, benzofluorenyl, triphenylenyl, spirobifluorenyl, diphenylfluorenyl group, dibenzo[g,p]chrysenyl group and the like.
  • aromatic hydrocarbon groups may have a substituent.
  • substituents on the aromatic hydrocarbon group include alkyl groups, aromatic hydrocarbon groups, and heteroaromatic groups, with aromatic hydrocarbon groups and heteroaromatic groups being more preferred.
  • the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. Examples of such alkyl groups include methyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, cyclopropyl and cyclohexyl groups.
  • the aromatic hydrocarbon group is preferably a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms. Examples of such aromatic hydrocarbon groups include phenyl, biphenyl and naphthyl groups.
  • the heteroaromatic group is preferably a monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms.
  • Such heteroaromatic groups include, for example, a dibenzofuranyl group, a dibenzothiophenyl group, and the like.
  • the heteroaromatic group represented by Ar 1 and Ar 2 is preferably a monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms.
  • heteroaromatic groups include pyrrolyl, thienyl, furyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, pyridyl, phenylpyridyl, pyridylphenyl, pyrimidyl group, pyrazyl group, 1,3,5-triazyl group, 1,3,5-triazylphenyl group, 1,3,5-triazylbiphenylyl group, 4,6-diphenyl-1,3,5- triazyl group, indolyl group, benzothienyl group, benzofuranyl group, benzimidazolyl group, indazolyl group, benzothiazolyl group, benzoisothiazo
  • substituents in the heteroaromatic group include the same substituents as those described above in the aromatic hydrocarbon group.
  • Specific examples of the fused ring compound represented by formula (1-III) include Ar 1 and Ar 2 represented by formulas (2A-III), (2B-III), and (2C-III). , (2A-1) to (2A-65), (2B-1) to (2B-65), and (2C-1), which are the groups shown in Tables A-1 and A-2 below. and condensed ring compounds represented by (2C-65).
  • Tables A-1 and A-2 m represents an integer from 1 to 65. Therefore, for example, in the case of a compound (2A-1), a compound (2A-1) having a skeleton of formula (2A-III), in which Ar 1 and Ar 2 of the skeleton are phenyl groups, is shown. there is In the table, dashed lines indicate bonding positions.
  • the condensed ring compound represented by formula (1-III) can be produced by a known method, for example, by the method shown in Synthetic Route 1 or 2 below.
  • Synthetic Route 1 or 2 definitions of R 1 to R 16 , Ar 1 and Ar 2 and preferred ranges of substituents are the same as described above.
  • X 1 and X 2 represent a halogen atom (chlorine, bromine, or iodine) or a trifluoromethylsulfonyloxy group
  • Y 1 and Y 2 represents a boronyl group optionally having a saturated hydrocarbon group having 2 to 10 carbon atoms.
  • X 1 and X 2 are the same as each other.
  • Y 1 and Y 2 are the same as each other.
  • Ar has the same structure as Ar 1 and Ar 2 , and the preferred range of substituents is the same as described above.
  • the condensed ring compound represented by formula (1-III) can be used as a material for photoelectric conversion elements for imaging devices. That is, the photoelectric conversion device material for an imaging device of the present embodiment contains the condensed ring compound represented by Formula (1-III) of the present embodiment.
  • the material for photoelectric conversion elements for imaging devices is preferably, for example, a charge transport material for photoelectric conversion devices for imaging devices or a charge blocking material for photoelectric conversion devices for imaging devices, and a hole transport material for photoelectric conversion devices for imaging devices or an imaging device. More preferably, it is an electron blocking material for a photoelectric conversion device for a device.
  • the charge transport material for photoelectric conversion elements for imaging devices and the charge blocking material for photoelectric conversion devices for imaging devices have different names, but mean the same material. Further, the hole-transporting material for the optical conversion element for the imaging element and the electron blocking material for the photoelectric conversion element for the imaging element have different names, but mean the same material.
  • a photoelectric conversion device material for an image pickup device containing a condensed ring compound represented by the formula (1-III) a photoelectric conversion device for an image pickup device having stable film quality, excellent charge transport properties, and high external quantum efficiency can be obtained.
  • a conversion element can be fabricated.
  • the photoelectric conversion element for an image pickup device of this embodiment includes the above-described material for a photoelectric conversion element for an image pickup device.
  • the configuration of the photoelectric conversion element for the imaging device is not particularly limited, but includes, for example, the configurations (i) to (ix) shown below.
  • the hole transport layer and the electron blocking layer have different names, but mean the same layer.
  • the buffer layer may be replaced with a layer having another name or function as needed.
  • Layers having other names or functions include, for example, a hole injection layer and a work function adjusting layer.
  • FIG. 5 is a schematic cross-sectional view showing an example of a lamination structure of a photoelectric conversion element for an image pickup device containing the charge transport material for the photoelectric conversion device for an image pickup device according to the present embodiment.
  • the photoelectric conversion element 100-III for an imaging device includes a substrate 1-III, a lower electrode 2-III, an electron transport layer (hole blocking layer) 3-III, a photoelectric conversion layer 4-III, a hole transport layer (electron blocking layer ) 5-III, a buffer layer 6-III, and an upper electrode 7-III in this order.
  • a substrate 1-III a lower electrode 2-III, an electron transport layer (hole blocking layer) 3-III, a photoelectric conversion layer 4-III, a hole transport layer (electron blocking layer ) 5-III, a buffer layer 6-III, and an upper electrode 7-III in this order.
  • some of these layers may be omitted, or conversely, other layers may be added.
  • the photoelectric conversion element for an imaging device shown in FIG. 5 light enters from below the transparent lower electrode 2-III. Further, the photoelectric conversion element for an imaging device moves electrons to the lower electrode 2-III and moves holes to the upper electrode 7-III among the charges (holes and electrons) generated in the photoelectric conversion layer 4-III. A voltage is applied to cause That is, the lower electrode 2-III is used as an electron collecting electrode, and the upper electrode 7-III is used as a hole collecting electrode.
  • the photoelectric conversion element for an imaging device contains a photoelectric conversion element material for an imaging device in one or more layers selected from the group consisting of layers between a lower electrode and an upper electrode. Therefore, in the configuration example shown in FIG. 5, the photoelectric conversion element 100-III for an imaging device includes an electron transport layer (hole blocking layer) 3-III, a photoelectric conversion layer 4-III, a hole transport layer (electron blocking layer) At least one layer selected from the group consisting of 5-III and buffer layer 6-III contains a photoelectric conversion element material for an imaging element.
  • the photoelectric conversion layer 4-III and the hole transport layer (electron blocking layer) 5-III contain a photoelectric conversion element material for an imaging device, and the hole transport layer (electron blocking layer) 5-III is used for imaging. It is particularly preferred to contain a photoelectric conversion element material for a device.
  • the material for the photoelectric conversion element for the imaging device may be included in a plurality of layers included in the photoelectric conversion element for the imaging device.
  • the photoelectric conversion layer 4-III and the hole transport layer (electron blocking layer) 5-III may contain a photoelectric conversion element material for an imaging element.
  • a photoelectric conversion element 100-III for an image pickup device in which the hole transport layer (electron blocking layer) 5-III contains a material for an image pickup device photoelectric conversion device will be described below.
  • the substrate is not particularly limited, and examples thereof include a glass plate, a quartz plate, a plastic plate and the like. Further, in the case of a configuration in which light is incident from the substrate 1 side, the substrate 1-III is transparent to the wavelength of light.
  • a lower electrode 2-III is provided on the substrate 1-III.
  • the lower electrode is made of a transparent material that allows the light to pass through or substantially pass through.
  • the transparent material used for the lower electrode 2-III is not particularly limited, but examples include indium-tin oxide (ITO; Indium Tin Oxide), indium-zinc oxide (IZO; Indium Zinc Oxide), Tin oxide, aluminum-doped tin oxide, magnesium-indium oxide, nickel-tungsten oxide, other metal oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, and zinc sulfide A metal sulfide etc. are mentioned.
  • ITO Indium-tin oxide
  • IZO Indium Zinc Oxide
  • Tin oxide aluminum-doped tin oxide
  • magnesium-indium oxide magnesium-indium oxide
  • nickel-tungsten oxide other metal oxides
  • metal nitrides such as gallium nitride
  • metal selenides such as zinc selenide
  • zinc sulfide A metal sulfide etc. are mentioned.
  • the transmission characteristics of the lower electrode are not important.
  • examples of materials used for the lower electrode in this case include gold, iridium, molybdenum, palladium, platinum, and the like.
  • Electrode transport layer (hole blocking layer) 3-III An electron transport layer (hole blocking layer) 3-III is provided between the lower electrode 2-III and a photoelectric conversion layer 4-III described later.
  • the electron transport layer (hole blocking layer) 3-III has a role of transporting electrons generated in the photoelectric conversion layer 4-III to the lower electrode 2-III, and a role of transporting holes generated in the photoelectric conversion layer 4-III to the lower electrode. It has a role of blocking migration to 2-III.
  • the electron-transporting layer (hole-blocking layer) 3-III may have a single-layer structure composed of one or more materials, or may have a laminated structure composed of multiple layers having the same composition or different compositions.
  • a layer made of a material specialized for hole blocking is formed, and between the forming layer and the lower electrode 2-III, specialized for electron transport.
  • a two-layer structure may be formed by forming a layer made of the same material.
  • the electron transport layer (hole blocking layer) 3-III can contain a conventionally known electron transport material.
  • Conventionally known electron transport materials include, for example, bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, BCP ( 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis(2-methyl-8-quinolinolate)-4-( phenylphenolate)aluminum), 4,6-bis(3,5-di(pyridin-4-yl)phenyl)-2-methylpyrimidine, N,N'-diphenyl-1,4,5,8-naphthalenetetra carboxylic acid diimide, N,N'-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxylic acid diimi
  • a photoelectric conversion layer 4-III is provided between the electron-transporting layer (hole-blocking layer) 3-III and the hole-transporting layer (electron-blocking layer) 5-III described later.
  • Examples of materials for the photoelectric conversion layer include materials having a photoelectric conversion function.
  • the photoelectric conversion layer 4-III may have a single-layer structure composed of one or more materials, or may have a laminated structure composed of multiple layers having the same composition or different compositions.
  • materials used for the photoelectric conversion layer 4-III, which is a single-layer structure made of one material include (i) coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, and the like.
  • materials used for the photoelectric conversion layer 4-III, which has a single-layer structure composed of two materials include (i) coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, and (ii) Combinations with fullerenes and derivatives thereof are included.
  • the photoelectric conversion layer 4-III made of these materials may be formed by vapor deposition in a state where powders are mixed in advance, or may be formed by co-evaporation in an arbitrary ratio.
  • Materials used for the photoelectric conversion layer 4-III, which has a single-layer structure composed of three materials include the above-mentioned (i) coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, and (ii) fullerene and its derivatives. and (iii) combinations with hole-transporting materials.
  • the photoelectric conversion layer 4-III made of these materials may be formed by vapor deposition in a state where powders are mixed in advance, or may be formed by co-evaporation in an arbitrary ratio.
  • coumarin derivatives include coumarin 6 and coumarin 30.
  • quinacridone derivatives include N,N-dimethylquinacridone.
  • phthalocyanine derivatives include boron-subphthalocyanine chloride and boron-subnaphthalocyanine chloride (SubNC).
  • fullerene and derivatives thereof include [60]fullerene, [70]fullerene, and [6,6]-phenyl-C61-methylbutyrate ([60]PCBM).
  • hole-transporting materials include aromatic tertiary amine compounds, naphthalene compounds, anthracene compounds, tetracene compounds, pentacene compounds, phenanthrene compounds, pyrene compounds, perylene compounds, fluorene compounds, carbazole compounds, indole compounds, and pyrrole compounds , picene compounds, thiophene compounds, benzotrifuran compounds, benzotrithiophene compounds, naphthodithiophene compounds, naphthothienothiophene compounds, benzodifuran compounds, benzodithiophene compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, chrysenodithiophene compounds , benzothienobenzothiophene compounds, and indolocarbazole compounds.
  • fluorene compounds preferred are fluorene compounds, naphthodithiophene compounds, naphthothienothiophene compounds, benzodifuran compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, chrysenodithiophene compounds, benzothienobenzothiophene compounds, indolocarbazole compounds, and the like.
  • Fluorene compounds, chrysenodithiophene compounds, benzothienobenzothiophene compounds, and indolocarbazole compounds are particularly preferred.
  • hole transport materials include 9,9′-(9,9′-spirobi[9H-fluorene]-2,7′-diyl)bis[9H-carbazole], 2,7-diphenyl[1] benzothieno[3,2-b][1]benzothiophene (DiPh-BTBT), benzo[1,2-b:3,4-b′:5,6-b′′]trifuran compound, benzo[1,2 -b:3,4-b':5,6-b'']trithiophene compound, naphtho[1,2-b:5,6-b']dithiophene, naphtho[2,3-b]naphtho[2 ',3':4,5]thieno[2,3-d]thiophene, benzo[1,2-b:4,5-b']difuran, benzo[1,2-b:4,5-b' ] dithiophene, benzo[1,2-b:4,5-b′]bis[1]benz
  • the material having a photoelectric conversion function is not limited to being contained only in the photoelectric conversion layer.
  • the material having a photoelectric conversion function is contained in layers adjacent to the photoelectric conversion layer 4-III (electron transport layer (hole blocking layer) 3-III, hole transport layer (electron blocking layer) 5-III). may be
  • a hole transport layer (electron blocking layer) 5-III is provided between the photoelectric conversion layer 4-III and a buffer layer 6-III described later.
  • the hole transport layer (electron blocking layer) 5-III has a role of transporting holes generated in the photoelectric conversion layer 4-III to the upper electrode 7-III side, and electrons generated in the photoelectric conversion layer 4-III It has a role of blocking movement to the electrode 7-III side.
  • the hole-transporting layer (electron-blocking layer) 5-III preferably contains a photoelectric conversion element material for an imaging element, as described above.
  • the hole-transporting layer (electron-blocking layer) 5-III may have a single-layer structure composed of one or more materials, or may have a laminated structure composed of multiple layers having the same composition or different compositions.
  • a layer made of a material specialized for electron blocking is formed, and between the forming layer and the buffer layer 6-III, hole transport is specialized.
  • a two-layer structure may be formed by forming a layer made of the same material.
  • the hole-transporting layer (electron-blocking layer) 5-III may further contain a conventionally known hole-transporting material in addition to the photoelectric conversion element material for an imaging device.
  • a conventionally known hole-transporting material in addition to the photoelectric conversion element material for an imaging device.
  • Preferable compounds and specific examples of conventionally known hole-transporting materials are the same as those described in the photoelectric conversion layer 4-III.
  • a buffer layer 6-III is provided between the hole transport layer (electron blocking layer) 5-III and an upper electrode 7-III described later.
  • the buffer layer 6-III serves to reduce damage to the organic film when the upper electrode 7-III is formed by sputtering. Further, by adjusting the work function of the buffer layer, it also plays a role of efficiently accepting holes from the hole transport layer (electron blocking layer) 5-III, and is also called a hole injection layer or a work function adjustment layer.
  • buffer layer 6-III examples include naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA), 2,3,6,7,10,11-hexacyano-1,4,5 , 8,9,12-hexaazatriphenylene (HATCN).
  • NTCDA naphthalene-1,4,5,8-tetracarboxylic dianhydride
  • HTCN 2,3,6,7,10,11-hexacyano-1,4,5 , 8,9,12-hexaazatriphenylene
  • An upper electrode 7-III is provided on the buffer layer 6-III.
  • Materials for the upper electrode 7-III include sodium, sodium-potassium alloy, magnesium, lithium, magnesium/copper mixture, silver, magnesium/silver mixture, aluminum, magnesium/aluminum mixture, magnesium/indium mixture, aluminum/aluminum oxide ( Al 2 O 3 ) mixtures, indium, lithium/aluminum mixtures, rare earth metals and the like.
  • Each layer except for the lower electrode 2-III and the upper electrode 7-III described above is formed by applying the material of each layer (with a material such as a binder resin and a solvent as necessary) by, for example, a vacuum deposition method, a spin coating method, a It can be formed by forming a thin film by a known method such as a casting method or an LB (Langmuir-Blodgett method) method.
  • the thickness of each layer thus formed is not particularly limited and can be appropriately selected depending on the situation, but is usually in the range of 5 nm or more and 5 ⁇ m or less.
  • the lower electrode 2-III and the upper electrode 7-III can be formed by thinning an electrode material by a method such as vapor deposition or sputtering.
  • a pattern may be formed through a mask of a desired shape during vapor deposition or sputtering, or a pattern of a desired shape may be formed by photolithography after forming a thin film by vapor deposition, sputtering, or the like.
  • the film thickness of the lower electrode 2-III and the upper electrode 7-III is preferably 1 ⁇ m or less, more preferably 10 nm or more and 200 nm or less.
  • the materials constituting the lower electrode 2-III and the upper electrode 7-III may be exchanged if necessary (also called an inverted structure).
  • the photoelectric conversion element for an imaging device is configured such that light passes through the upper electrode 7-III and is incident on the photoelectric conversion layer 4-III.
  • An imaging device equipped with a photoelectric conversion device can be applied to, for example, imaging devices of digital cameras and digital video cameras, and imaging devices built into mobile phones and the like.
  • the condensed ring compound-IV of the present embodiment is a condensed ring compound represented by the following formula (1-IV).
  • R 1 to R 16 each independently represent a hydrogen atom or a substituent; L is a single bond or a substituted or unsubstituted divalent linking group; L is substituted at either the R2 or R3 position; Ar represents an optionally substituted dibenzo[g,p]chrysenyl group;
  • the fused ring compound of formula (1-IV) does not have a 2,7-naphthylene group.
  • All of the condensed ring compounds represented by formula (1-IV) have a high glass transition temperature and a wide bandgap. Therefore, these condensed ring compounds are suitable as charge transport materials for organic semiconductor elements that require transparency, such as display members.
  • R 1 to R 16 each independently represent a hydrogen atom or a substituent.
  • the substituent is preferably an alkyl group, an aromatic hydrocarbon group or a heteroaromatic group, more preferably an aromatic hydrocarbon group or a heteroaromatic group.
  • the alkyl group among the substituents of R 1 to R 16 is preferably a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. Examples of such alkyl groups include methyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, cyclopropyl and cyclohexyl groups.
  • the aromatic hydrocarbon group is preferably a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms.
  • aromatic hydrocarbon groups include phenyl, biphenyl and naphthyl groups.
  • the heteroaromatic group is preferably a monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms.
  • Such heteroaromatic groups include, for example, a dibenzofuranyl group, a dibenzothiophenyl group, and the like. None of R 1 to R 16 are the same as the structure represented by L-Ar described below.
  • R 1 to R 16 are preferably hydrogen atoms from the viewpoint that the condensed ring compound has a high glass transition temperature and a wide bandgap.
  • L represents a single bond or a substituted or unsubstituted divalent linking group.
  • L is a divalent group connecting the dibenzo[g,p]chrysene skeleton in formula (1-IV) and Ar described later.
  • L is a single bond, an optionally substituted monocyclic, linked or condensed C6 to C30 aromatic hydrocarbon group, or an optionally substituted C3 to C36 is preferably a monocyclic, linked or condensed heteroaromatic group, and includes a single bond, optionally substituted phenylene group, biphenylene group, terphenylene group, naphthylene group, fluorenylene group, triphenylene group.
  • a rene group, a phenanthrenylene group, an anthracenylene group, a pyrenylene group, a dibenzofuranylene group, a dibenzothiophenylene group, a pyridylene group, or a pyrimidylene group is more preferable.
  • the substituent for L is preferably an alkyl group, an aromatic hydrocarbon group or a heteroaromatic group, more preferably an aromatic hydrocarbon group or a heteroaromatic group.
  • the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. Examples of such alkyl groups include methyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, cyclopropyl and cyclohexyl groups.
  • the aromatic hydrocarbon group is preferably a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms.
  • the heteroaromatic group is preferably a monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms.
  • Such heteroaromatic groups include, for example, a dibenzofuranyl group, a dibenzothiophenyl group, and the like.
  • L is preferably a single bond, an unsubstituted phenylene group, an unsubstituted biphenylene group, or an unsubstituted pyridylene group.
  • Ar represents an optionally substituted dibenzo[g,p]chrysenyl group.
  • an optionally substituted 2-dibenzo[g,p]chrysenyl group or an optionally substituted 3-dibenzo[g,p]chrysenyl group is preferable.
  • All of the substituents on Ar are preferably alkyl groups, aromatic hydrocarbon groups or heteroaromatic groups, more preferably aromatic hydrocarbon groups or heteroaromatic groups.
  • the alkyl group among the substituents of Ar is preferably a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms.
  • alkyl groups include methyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, cyclopropyl and cyclohexyl groups.
  • the aromatic hydrocarbon group is preferably a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms.
  • aromatic hydrocarbon groups include phenyl, biphenyl and naphthyl groups. Among these, a phenyl group is preferred.
  • the heteroaromatic group is preferably a monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms.
  • Such heteroaromatic groups include, for example, a dibenzofuranyl group, a dibenzothiophenyl group, and the like.
  • the condensed ring compound represented by formula (1-IV) is preferably any one of formula (2A-IV), formula (3A-IV), and formula (4A-IV) shown below.
  • L is a single bond or a substituted or unsubstituted divalent linking group; ), and the fused ring compound of formula (4A) do not have a 2,7-naphthylene group.
  • formula (2A-IV) and formula (3A-IV) are preferable, and the condensed ring compound represented by formula (2A-IV) is preferable in that it has a wide bandgap.
  • a compound having a wide bandgap has the advantage that the light absorption of the compound itself in a solid state tends toward the short wavelength side, so that the light absorption in a photoelectric conversion element for an imaging device, which will be described later, is less likely to be hindered.
  • condensed Ring Compound represented by formula (1-IV) include formula (2A-IV), formula (3A-IV) or formula (4A-IV) where L represented in the following table (2A-1) to (2A-60), (3A-1) to (3A-60) or (4A-1) to (4A), which are groups or single bonds shown in A-3 and A-4 -60), and condensed ring compounds represented by the following formulas (2B-1) to (2B-30) and (3B-1) to (3B-3).
  • m represents an integer from 1 to 60. Therefore, for example, the compound (2A-1) has a skeleton of formula (2A-IV) and L in the skeleton is a single bond. In the table, dashed lines indicate bonding positions.
  • the condensed ring compound represented by formula (1-IV) can be produced by a known method, for example, by any of the methods shown in Synthetic Routes 1 to 3 below.
  • Synthetic Routes 1 to 3 the definitions of R 1 to R 16 , L, and Ar and the preferred range of substituents are the same as described above.
  • X1, Y1 and Y2 are a halogen atom (chlorine, bromine or iodine), a boronyl group optionally having a saturated hydrocarbon group having 2 to 10 carbon atoms, or represents a trifluoromethylsulfonyloxy group, provided that when X1 is a halogen atom or a trifluoromethylsulfonyloxy group, Y1 and Y2 are a boronyl group optionally having a saturated hydrocarbon group having 2 to 10 carbon atoms and when X1 is a boronyl group optionally having a saturated hydrocarbon group with 2 to 10 carbon atoms, Y1 and Y2 are a halogen atom or a trifluoromethylsulfonyloxy group.
  • X1, X2, Y1 and Y2 are halogen atoms (chlorine, bromine or iodine) and saturated hydrocarbon groups having 2 to 10 carbon atoms.
  • Y1 and Y2 represent a saturated hydrocarbon group having 2 to 10 carbon atoms; is an optionally substituted boronyl group, and when X1 is a boronyl group optionally containing a saturated hydrocarbon group having 2 to 10 carbon atoms, Y1 and Y2 are a halogen atom or a trifluoromethylsulfonyloxy group .
  • L1 and L2 are each independently a single bond, an optionally substituted monocyclic ring having 6 to 30 carbon atoms, a linked or condensed aromatic ring represents an optionally substituted monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms,
  • X1 and Y1 each represent a halogen atom (chlorine, bromine or iodine), a boronyl group optionally having a saturated hydrocarbon group having 2 to 10 carbon atoms, or a trifluoromethylsulfonyloxy group, provided that when X1 is a halogen atom or a trifluoromethylsulfonyloxy group, Y1 is a boronyl group optionally having a saturated hydrocarbon group having 2 to 10 carbon atoms, and when X1 is a boronyl group optionally having a saturated hydrocarbon group having 2 to 10 carbon atoms, Y1 is hal
  • a material for an organic semiconductor device according to one aspect of the present invention contains a condensed ring compound represented by formula (1-IV).
  • a charge transport material for an organic semiconductor device according to one aspect of the present invention contains a condensed ring compound (1-IV).
  • a charge transport material for an organic electroluminescent device according to one aspect of the present invention contains a condensed ring compound (1-IV).
  • a charge-transporting material for a photoelectric conversion device for an imaging device according to one aspect of the present invention contains a condensed ring compound (1-IV).
  • a charge-transporting material for an organic electroluminescence device containing the condensed ring compound (1) contributes to the production of an organic electroluminescence device excellent in current efficiency or life.
  • the condensed ring compound (1-IV) is not particularly limited, it can be used, for example, as a material for organic semiconductor devices. Also, the condensed ring compound (1-IV) can be used, for example, as a charge transport material for an organic semiconductor device.
  • a hole-only device comprises a condensed ring compound (1-IV).
  • the configuration of the hole-only device is not particularly limited, but includes, for example, the following configurations (Ai) to (Aiii).
  • FIG. 7 is a schematic cross-sectional view showing an example of a layered structure of a hole-only device containing a condensed ring compound according to one embodiment of the present invention.
  • the hole-only device 100-IV includes a substrate 1-IV, a lower electrode 2-IV, a hole injection layer 3-IV, a hole transport layer 4-IV, a buffer layer 5-IV, and an upper electrode 6-IV in this order. Prepare with. However, some of these layers may be omitted, or conversely, other layers may be added.
  • the hole transport layer may be a laminated structure consisting of two layers.
  • a hole-only device contains a condensed ring compound (1-IV) in one or more layers selected from the group consisting of layers between the lower electrode 2-IV and the upper electrode 6-IV. Therefore, in the configuration example shown in FIG. 7, the hole-only device 100-IV includes at least one layer selected from the group consisting of the hole injection layer 3-IV, the hole transport layer 4-IV, and the buffer layer 5-IV. contains the fused ring compound (1-IV). In particular, the hole transport layer 4-IV preferably contains the condensed ring compound (1-IV). Note that the organic electroluminescence device 100-IV in which the hole transport layer 4-IV contains the condensed ring compound (1-IV) will be described below.
  • the substrate 1-IV is not particularly limited, and examples thereof include a glass plate, a quartz plate, a plastic plate and the like.
  • the material used for the lower electrode 2-IV is not particularly limited, for example, indium-tin oxide (ITO; Indium Tin Oxide), indium-zinc oxide (IZO; Indium Zinc Oxide), oxide Tin, aluminum-doped tin oxide, magnesium-indium oxide, nickel-tungsten oxide, other metal oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, metal sulfides such as zinc sulfide metals, gold, iridium, molybdenum, palladium, and platinum.
  • ITO Indium-tin oxide
  • IZO Indium Zinc Oxide
  • oxide Tin aluminum-doped tin oxide
  • magnesium-indium oxide magnesium-indium oxide
  • nickel-tungsten oxide other metal oxides
  • metal nitrides such as gallium nitride
  • metal selenides such as zinc selenide
  • metal sulfides such as zinc sulfide metals
  • a hole injection layer 3-IV is provided between the lower electrode 2-IV and the hole transport layer 4-IV.
  • the hole injection layer 3-IV has a role of promoting the injection of holes from the lower electrode 2-IV to the hole transport layer 4-IV.
  • the hole injection layer 3-IV may consist of one or more materials.
  • the hole injection layer 3-IV may further contain conventionally known materials in addition to the condensed ring compound (1-IV).
  • Conventionally known hole injection materials include molybdenum oxide and 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN).
  • a hole transport layer 4-IV is provided between the hole injection layer 3-IV and the buffer layer 5-IV.
  • the hole transport layer 4-IV has a role of transporting holes carried from the hole injection layer 3-IV to the buffer layer 5-IV.
  • the hole transport layer 3-IV preferably contains the condensed ring compound (1-IV).
  • buffer layer 5-IV A buffer layer 5-IV is provided between the hole transport layer 4-IV and the upper electrode 6-IV.
  • the role of the buffer layer 5-IV is not particularly limited, but includes the role of improving contact at the interface between the adjacent hole transport layer 4-IV and the upper electrode 6-IV, and the role of adjusting the work function. mentioned.
  • Conventionally known buffer layers include HATCN and the like.
  • An upper electrode 6-IV is provided on the buffer layer 5-IV.
  • Materials for the upper electrode 6-IV include sodium, sodium-potassium alloy, magnesium, lithium, magnesium/copper mixture, silver, magnesium/silver mixture, aluminum, magnesium/aluminum mixture, magnesium/indium mixture, aluminum/aluminum oxide ( Al2O3) mixtures, indium, lithium/aluminum mixtures, gold, rare earth metals, and the like.
  • Each layer except for the lower electrode 2-IV and the upper electrode 6-IV described above is formed by applying the material of each layer (with a material such as a binder resin and a solvent as necessary), for example, by vacuum deposition, spin coating, It can be formed by forming a thin film by a known method such as a casting method or an LB (Langmuir-Blodgett method) method.
  • the thickness of each layer thus formed is not particularly limited and can be appropriately selected depending on the situation, but is usually in the range of 5 nm or more and 5 ⁇ m or less.
  • the lower electrode 2-IV and the upper electrode 6-IV can be formed by thinning an electrode material by a method such as vapor deposition or sputtering.
  • a pattern may be formed through a mask of a desired shape during vapor deposition or sputtering, or a pattern of a desired shape may be formed by photolithography after forming a thin film by vapor deposition, sputtering, or the like.
  • the film thickness of the lower electrode 2-IV and the upper electrode 6-IV is preferably 1 ⁇ m or less, more preferably 10 nm or more and 200 nm or less.
  • the condensed ring compound (1-IV) is not particularly limited, it can be used, for example, as a material for organic electroluminescence devices. Also, the condensed ring compound (1-IV) can be used, for example, as a charge transport material for an organic electroluminescence device.
  • a material for an organic electroluminescent device contains a condensed ring compound represented by Formula (1-IV). Further, the charge-transporting material for an organic electroluminescence device according to one aspect of the present invention contains a condensed ring compound (1-IV).
  • the organic electroluminescence device material and the charge transport material for organic electroluminescence device containing the condensed ring compound (1-IV) can transport both holes and electrons as needed, and are excellent in current efficiency and life. It contributes to the production of organic electroluminescence devices.
  • An organic electroluminescent device contains a condensed ring compound (1-IV).
  • the structure of the organic electroluminescence device is not particularly limited, but examples thereof include the structures (Bi) to (Bvi) shown below.
  • FIG. 8 is a schematic cross-sectional view showing an example of a lamination structure of an organic electroluminescence device containing the condensed ring compound (1-IV) according to one embodiment of the present invention.
  • the organic electroluminescence element shown in FIG. 8 has a so-called bottom emission type element configuration, but the organic electroluminescence element according to one aspect of the present invention is limited to the bottom emission type element configuration. isn't it. That is, the organic electroluminescence device according to one aspect of the present invention may have a top emission type device configuration, or may have another known device configuration.
  • the organic electroluminescent device 200-IV includes a substrate 101-IV, an anode 102-IV, a hole injection layer 103-IV, a charge generation layer 104-IV, a hole transport layer 105-IV, a light emitting layer 106-IV, and an electron transport layer.
  • Layer 107-IV and cathode 108-IV are provided in that order. However, some of these layers may be omitted, or conversely, other layers may be added.
  • an electron injection layer may be provided between electron transport layer 107-IV and cathode 108-IV, charge generation layer 104-IV may be omitted, and hole transport layer 103-IV may be provided on hole injection layer 103-IV.
  • Layer 105-IV may be applied directly.
  • a single layer having the functions of a plurality of layers such as an electron injection/transport layer having both the function of an electron injection layer and the function of an electron transport layer in a single layer. It may be a configuration provided instead of. Further, for example, the single-layer hole-transporting layer 105-IV and the single-layer electron-transporting layer 107-IV may each consist of a plurality of layers.
  • the organic electroluminescence element contains the condensed ring compound represented by the above formula (1-IV) in one or more layers selected from the group consisting of layers between the anode 102-IV and the cathode 108-IV. Therefore, in the configuration example shown in FIG. At least one layer selected from the group consisting of layers 107-IV contains the condensed ring compound (1-IV). In particular, the hole-transporting layer 105-IV or the electron-transporting layer 107-IV preferably contains the condensed ring compound (1-IV). Note that the condensed ring compound (1-IV) may be contained in a plurality of layers included in the organic electroluminescent device.
  • the hole-injection layer when a hole-injection layer is provided between the anode and the hole-transport layer, the hole-injection layer may contain a condensed ring compound (1-IV), and When an electron injection layer is provided therebetween, the electron injection layer may contain the condensed ring compound (1-IV).
  • the substrate is not particularly limited, and examples thereof include a glass plate, a quartz plate, a plastic plate and the like.
  • the substrate 101-IV is transparent to the wavelength of light.
  • light-transmitting plastic films include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate ( PC), cellulose triacetate (TAC), cellulose acetate propionate (CAP), and the like.
  • An anode 102-IV is provided on the substrate 101-IV (on the side of the hole injection layer 103-IV).
  • the anode is formed of a material that is transparent or substantially transparent to the emitted light.
  • the transparent material used for the anode 102-IV is not particularly limited. Tin, aluminum-doped tin oxide, magnesium-indium oxide, nickel-tungsten oxide, other metal oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, and metals such as zinc sulfide sulfide and the like.
  • the transmission characteristics of the anode are not important. Accordingly, examples of materials used for the anode in this case include gold, iridium, molybdenum, palladium, platinum, and the like.
  • a buffer layer electrode interface layer may be provided on the anode.
  • Hole injection layer 103-IV, hole transport layer 105-IV Between the anode 102-IV and the light-emitting layer 106-IV described later, from the anode 102-IV side, there are a hole injection layer 103-IV, a charge generation layer 104-IV described later, and a hole transport layer 105-IV. are provided in this order.
  • the hole injection layer and the hole transport layer have a function of transferring holes injected from the anode to the light emitting layer, and the hole injection layer and the hole transport layer are interposed between the anode and the light emitting layer. As a result, more holes are injected into the light-emitting layer at a lower electric field.
  • the hole injection layer and the hole transport layer also function as electron blocking layers. That is, electrons injected from the cathode and transported from the electron injection layer and/or the electron transport layer to the light-emitting layer are blocked by the electron barrier present at the interface between the light-emitting layer and the hole injection layer and/or the hole transport layer. , leakage into the hole injection layer and/or the hole transport layer is suppressed. As a result, the electrons are accumulated at the interface in the light-emitting layer, resulting in an effect such as an improvement in current efficiency, and an organic electroluminescence device with excellent light-emitting performance can be obtained.
  • the material for the hole injection layer and the hole transport layer has at least one of hole injection, hole transport, and electron barrier properties.
  • Materials for the hole injection layer and the hole transport layer may be either organic or inorganic.
  • materials for the hole injection layer and hole transport layer other than the condensed ring compound (1-IV) include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, Phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, conductive polymer oligomers (especially thiophene oligomers), porphyrins compounds, aromatic tertiary amine compounds, styrylamine compounds, and the like. Among these, porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds are preferred, and aromatic tertiary amine compounds are particularly preferred.
  • aromatic tertiary amine compounds and styrylamine compounds include N,N,N',N'-tetraphenyl-4,4'-diaminophenyl, N,N'-diphenyl-N,N'- Bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine (TPD), 2,2-bis(4-di-p-tolylaminophenyl)propane, 1,1-bis (4-di-p-tolylaminophenyl)cyclohexane, N,N,N',N'-tetra-p-tolyl-4,4'-diaminobiphenyl, 1,1-bis(4-di-p-tolyl aminophenyl)-4-phenylcyclohexane, bis(4-dimethylamino-2-methylphenyl)phenylmethane, bis(4-di-p-tolylaminophenyl,
  • Inorganic compounds such as p-type-Si and p-type-SiC can also be cited as examples of the material for the hole injection layer and the material for the hole transport layer.
  • the hole injection layer and the hole transport layer may have a single layer structure composed of one or more materials, or may have a laminated structure composed of multiple layers having the same composition or different compositions.
  • a charge generation layer 104-IV may be provided between the hole injection layer 103-IV and the hole transport layer 105-IV.
  • the material of the charge generation layer is not particularly limited, and examples thereof include HATCN described above.
  • the charge generation layer may have a single-layer structure composed of one or more materials, or may have a laminated structure composed of multiple layers having the same composition or different compositions.
  • Light emitting layer 106-IV A light-emitting layer 106-IV is provided between the hole-transporting layer 105-IV and an electron-transporting layer 107-IV described later.
  • Materials for the light-emitting layer include phosphorescent light-emitting materials, fluorescent light-emitting materials, and thermally activated delayed fluorescent light-emitting materials. In the light-emitting layer, electron-hole pairs recombine, resulting in light emission.
  • the light emitting layer may consist of a single small molecule material or a single polymer material, but more commonly consists of a host material doped with a guest compound. Emission comes primarily from dopants and can have any color.
  • host materials include compounds having biphenyl groups, fluorenyl groups, triphenylsilyl groups, carbazole groups, pyrenyl groups, and anthryl groups. More specifically, DPVBi (4,4'-bis(2,2-diphenylvinyl)-1,1'-biphenyl), BCzVBi (4,4'-bis(9-ethyl-3-carbazovinylene) 1, 1′-biphenyl), TBADN (2-tert-butyl-9,10-di(2-naphthyl)anthracene), ADN (9,10-di(2-naphthyl)anthracene), CBP (4,4′-bis (carbazol-9-yl)biphenyl), CDBP (4,4′-bis(carbazol-9-yl)-2,2′-dimethylbiphenyl), 2-(9-phenylcarbazol-3-yl)-9- [4-(4-phenyl)
  • fluorescent dopants examples include anthracene, pyrene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine, quinacridone, dicyanomethylenepyran compounds, thiopyran compounds, polymethine compounds, pyrylium, thiapyrylium compounds, fluorene derivatives, periflanthene derivatives, and indenoperylenes. derivatives, bis(azinyl)amine boron compounds, bis(azinyl)methane compounds, carbostyril compounds, and the like.
  • the fluorescent dopant may be a combination of two or more selected from these.
  • phosphorescent dopants include organometallic complexes of transition metals such as iridium, platinum, palladium, and osmium.
  • fluorescent dopants and phosphorescent dopants include Alq3 (tris(8-hydroxyquinoline)aluminum), DPAVBi (4,4′-bis[4-(di-p-tolylamino)styryl]biphenyl), perylene, bis[ 2-(4-n-hexylphenyl)quinoline](acetylacetonato)iridium(III), Ir(PPy)3(tris(2-phenylpyridine)iridium(III)), and FIrPic (bis(3,5- difluoro-2-(2-pyridyl)phenyl-(2-carboxypyridyl)iridium (III))) and the like.
  • the luminescent material is not limited to being contained only in the luminescent layer.
  • the light-emitting material may be contained in a layer adjacent to the light-emitting layer (hole-transporting layer 105-IV or electron-transporting layer 107-IV). This can further increase the current efficiency of the organic electroluminescence device.
  • the light-emitting layer may have a single-layer structure composed of one or more materials, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions.
  • Electrode transport layer 107-IV An electron transport layer 107-IV is provided between the light emitting layer 106-IV and a cathode 108-IV described later.
  • the electron transport layer has a function of transmitting electrons injected from the cathode to the light emitting layer. By interposing an electron-transporting layer between the cathode and the light-emitting layer, electrons are injected into the light-emitting layer at a lower electric field.
  • the electron-transporting layer may further contain a conventionally known electron-transporting material in addition to the condensed ring compound (1-IV).
  • Conventionally known electron transport materials include, for example, 8-hydroxyquinolinate lithium (Liq), bis(8-hydroxyquinolinate) zinc, bis(8-hydroxyquinolinate) copper, bis(8-hydroxyquinolinate), tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)(o-cresolato)gallium, bis(2 -methyl-8-quinolinato)-1-naphtholatoaluminum, or bis(2-methyl-8-quinolinato)-2-naph
  • the electron-transporting layer may have a single-layer structure composed of one or more materials, or may have a laminated structure composed of multiple layers having the same composition or different compositions.
  • the electron-transporting layer has a two-layer structure in which the first electron-transporting layer is on the light-emitting layer side and the second electron-transporting layer is on the cathode side, either or both of the first electron-transporting layer and the second electron-transporting layer are condensed. It preferably contains a ring compound (1).
  • a cathode 108-IV is provided on the electron transport layer 107-IV.
  • the cathode can be made of any conductive material.
  • Cathode materials include sodium, sodium-potassium alloys, magnesium, lithium, magnesium/copper mixtures, magnesium/silver mixtures, magnesium/aluminum mixtures, magnesium/indium mixtures, aluminum/aluminum oxide (Al2O3) mixtures, indium, lithium/ Examples include aluminum mixtures, rare earth metals, and the like.
  • a buffer layer (electrode interface layer) may be provided on the cathode (on the electron transport layer side).
  • the organic electroluminescence element according to one aspect of the present invention may be used as a kind of lamp such as an illumination light source or an exposure light source, a type of projection device that projects an image, or a still image or a moving image that can be directly viewed. You may use it as a display apparatus (display) of the type to carry out.
  • the driving method may be either a simple matrix (passive matrix) method or an active matrix method. Further, by using two or more kinds of organic electroluminescence elements of this embodiment having different emission colors, a full-color display device can be produced.
  • the condensed ring compound (1-IV) can be used as a charge-transporting material for a photoelectric conversion device for an imaging device. That is, the charge-transporting material for photoelectric conversion elements for imaging devices of the present embodiment contains the condensed ring compound represented by formula (1-IV) of the present embodiment.
  • the charge-transporting material for photoelectric conversion elements for imaging devices for example, hole-transporting materials for photoelectric conversion devices for imaging devices are preferable.
  • the photoelectric conversion element for an image pickup device of the present embodiment includes the charge transport material for a photoelectric conversion device for an image pickup device or the charge blocking material for a photoelectric conversion device for an image pickup device described above.
  • the configuration of the photoelectric conversion element for the imaging device is not particularly limited, but includes, for example, the following configurations (i) to (v).
  • the buffer layer may be replaced with a layer having another name or function as needed.
  • Layers having other names or functions include, for example, a hole injection layer and a work function adjusting layer.
  • the photoelectric conversion element for an imaging device includes at least one layer selected from the group consisting of an electron transport layer (hole blocking layer), a photoelectric conversion layer, a hole transport layer (electron blocking layer) and a buffer layer.
  • a charge transport material for devices or a charge blocking material for photoelectric conversion devices for imaging devices may be included.
  • the photoelectric conversion element for an image pickup device contains a charge transport material for a photoelectric conversion device for an image pickup device or a charge blocking material for a photoelectric conversion device for an image pickup device in the photoelectric conversion layer and/or the hole transport layer (electron blocking layer). is preferred, and it is more preferred that the hole transport layer (electron blocking layer) contains a charge transport material for a photoelectric conversion device for an imaging device or a charge blocking material for a photoelectric conversion device for an imaging device.
  • the charge-transporting material for a photoelectric conversion element for an image pickup device or the charge blocking material for a photoelectric conversion device for an image pickup device may be included in a plurality of layers provided in the photoelectric conversion device for an image pickup device.
  • FIG. 10 is a schematic cross-sectional view showing an example of a lamination structure of a photoelectric conversion element for an image pickup element containing the charge transport material for the photoelectric conversion element for the image pickup element or the charge blocking material for the photoelectric conversion element for the image pickup element according to the present embodiment. .
  • the photoelectric conversion element 300-IV for an imaging device in FIG. An electron blocking layer) 205-IV, a buffer layer 206-IV, and an upper electrode 207-IV are provided in this order.
  • some of these layers may be omitted, or other layers may be added.
  • the photoelectric conversion element 300-IV for the imaging element light enters from below the transparent lower electrode 202-IV. Further, in the photoelectric conversion element 300-IV for an imaging device, among the charges (holes and electrons) generated in the photoelectric conversion layer 204-IV, electrons move to the lower electrode 202-IV, and holes move to the upper electrode 207-IV. A voltage is applied to move to IV. That is, the photoelectric conversion element 300-IV for an imaging device uses the lower electrode 202-IV as an electron collection electrode and the upper electrode 207-IV as a hole collection electrode.
  • the photoelectric conversion element 300-IV for an imaging device includes an electron transport layer (hole blocking layer) 203-IV, a photoelectric conversion layer 204-IV, a hole transport layer (electron blocking layer) 205-IV, and a buffer layer 206-IV. At least one layer selected from the group consisting of a photoelectric conversion element material for an imaging element is included.
  • the photoelectric conversion element 300-IV for an imaging element includes a charge transport material for a photoelectric conversion element for an imaging element or a photoelectric conversion element for an imaging element in the photoelectric conversion layer 204-IV and/or the hole transport layer (electron blocking layer) 205-IV.
  • the hole-transporting layer (electron blocking layer) 205-IV contains a charge-transporting material for a photoelectric conversion device for an imaging device or a charge-blocking material for a photoelectric conversion device for an imaging device.
  • the charge transporting material for the photoelectric conversion element for the imaging element or the charge blocking material for the photoelectric conversion element for the imaging element may be included in a plurality of layers included in the photoelectric conversion element for the imaging element 300-IV.
  • the photoelectric conversion element 300-IV in which the hole transport layer (electron blocking layer) 205-IV contains the charge transport material for the photoelectric conversion element for the image pickup element or the charge blocking material for the photoelectric conversion element for the image pickup element will be described below. .
  • the substrate is not particularly limited, and examples thereof include a glass plate, a quartz plate, a plastic plate and the like.
  • the substrate 201-IV preferably has high transmittance (for example, transmittance of 80% or more, preferably transmittance of 90% or more) with respect to the wavelength of light. .
  • a lower electrode 202-IV is provided on the substrate 201-IV.
  • the lower electrode 202-IV has a high transmittance (for example, transmittance) with respect to the wavelength of the incident light. transmittance of 80% or higher, preferably 90% or higher).
  • the transparent material used for the lower electrode 202-IV is not particularly limited.
  • the material constituting the lower electrode 202-IV includes, for example, indium-tin oxide (ITO), indium-zinc oxide (IZO), and tin oxide. , aluminum-doped tin oxide, magnesium-indium oxide, nickel-tungsten oxide, other metal oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, metal sulfides such as zinc sulfide etc.
  • the transmission characteristics of the lower electrode 202-IV are not important. Accordingly, examples of materials used for the lower electrode 202-IV in this case may be gold, iridium, molybdenum, palladium, platinum, and the like.
  • Electrode (hole blocking layer) 203-IV An electron transport layer (hole blocking layer) 203-IV is provided between the lower electrode 202-IV and the photoelectric conversion layer 204-IV.
  • the electron transport layer (hole blocking layer) 203-IV has a role of transporting electrons generated in the photoelectric conversion layer 204-IV to the lower electrode 202-IV, and a role of transporting holes generated in the photoelectric conversion layer 204-IV to the lower electrode. 202-IV.
  • the electron-transporting layer (hole-blocking layer) 203-IV may have a single-layer structure composed of one or more materials, or may have a laminated structure composed of multiple layers having the same composition or different compositions.
  • the electron transport layer (hole blocking layer) 203-IV includes, for example, a layer adjacent to the photoelectric conversion layer 204-IV made of a material specialized for hole blocking, and a lower layer made of a material specialized for electron transport. and a layer adjacent to electrode 202-IV.
  • the electron transport layer (hole blocking layer) 203-IV may be a layer containing a conventionally known electron transport material.
  • Conventionally known electron transport materials include, for example, bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, BCP ( 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis(2-methyl-8-quinolinolate)-4-( phenylphenolate)aluminum), 4,6-bis(3,5-di(pyridin-4-yl)phenyl)-2-methylpyrimidine, N,N'-diphenyl-1,4,5,8-naphthalenetetra carboxylic acid diimide, N,N'-di(4-pyridyl)-1,4,5,8-naphthalenetetrac
  • a photoelectric conversion layer 204-IV is provided between the electron transport layer (hole blocking layer) 203-IV and the hole transport layer (electron blocking layer) 205-IV described later.
  • the photoelectric conversion layer 204-IV contains a material having a photoelectric conversion function.
  • the photoelectric conversion layer 204-IV may have a single-layer structure composed of one or more materials, or may have a multilayer structure composed of multiple layers having the same composition or different compositions.
  • single-layer photoelectric conversion layers made of one type of material include photoelectric conversion layers made of materials such as coumarin and its derivatives, quinacridone and its derivatives, and phthalocyanine and its derivatives.
  • a photoelectric conversion layer having a single layer structure made of two materials for example, (i) a first material selected from the group consisting of coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, ( ii) a photoelectric conversion layer containing a second material selected from the group consisting of fullerenes and derivatives thereof;
  • the photoelectric conversion layer may further contain (iii) a hole transport material.
  • the photoelectric conversion layer 204-IV made of these materials may be formed, for example, by evaporation using a mixed powder in which powders of each material are mixed, or by co-evaporation of each material in an arbitrary ratio. good too.
  • coumarin derivatives include coumarin 6 and coumarin 30.
  • quinacridone derivatives include N,N-dimethylquinacridone and the like.
  • phthalocyanine derivative include boron-subphthalocyanine chloride, boron-subnaphthalocyanine chloride (SubNC), and the like.
  • fullerene and derivatives thereof include [60] fullerene, [70] fullerene, [6,6]-phenyl-C61-methylbutyrate ([60]PCBM), and the like.
  • the hole-transporting material may be any known hole-transporting material;
  • hole transport materials include aromatic tertiary amine compounds, naphthalene compounds, anthracene compounds, tetracene compounds, pentacene compounds, phenanthrene compounds, pyrene compounds, perylene compounds, fluorene compounds, carbazole compounds, indole compounds, pyrrole compounds, picene compounds, thiophene compounds, benzotrifuran compounds, benzotrithiophene compounds, naphthodithiophene compounds, naphthothienothiophene compounds, benzodifuran compounds, benzodithiophene compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, chrysenodithiophene compounds, benzothienobenzothiophene compounds, indolocarbazole compounds, and the like.
  • fluorene compounds preferred are fluorene compounds, naphthodithiophene compounds, naphthothienothiophene compounds, benzodifuran compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, chrysenodithiophene compounds, benzothienobenzothiophene compounds, indolocarbazole compounds, and the like.
  • Fluorene compounds, chrysenodithiophene compounds, benzothienobenzothiophene compounds, and indolocarbazole compounds are more preferred.
  • hole transport materials include 9,9′-(9,9′-spirobi[9H-fluorene]-2,7′-diyl)bis[9H-carbazole], 2,7-diphenyl[1] benzothieno[3,2-b][1]benzothiophene (DiPh-BTBT), benzo[1,2-b:3,4-b′:5,6-b′′]trifuran compounds, benzo[1,2 -b:3,4-b':5,6-b'']trithiophene compound, naphtho[1,2-b:5,6-b']dithiophene, naphtho[2,3-b]naphtho[2 ',3':4,5]thieno[2,3-d]thiophene, benzo[1,2-b:4,5-b']difuran, benzo[1,2-b:4,5-b' ] dithiophene, benzo[1,2-b:4,5-b′]bis[1]benz
  • the material having the photoelectric conversion function described above may be contained only in the photoelectric conversion layer 204-IV, or may be contained in layers other than the photoelectric conversion layer 204-IV.
  • layers adjacent to the photoelectric conversion layer 204-IV contain a material having a photoelectric conversion function. may be
  • a hole transport layer (electron blocking layer) 205-IV is provided between the photoelectric conversion layer 204-IV and a buffer layer 206-IV described later.
  • the hole-transporting layer (electron-blocking layer) 205-IV serves to transport holes generated in the photoelectric conversion layer 204-IV to the upper electrode 207-IV side, and to transport electrons generated in the photoelectric conversion layer 204-IV to the upper side. It also has a role of blocking movement to the electrode 207-IV side.
  • the hole-transporting layer (electron-blocking layer) 205-IV preferably contains the charge-transporting material for a photoelectric conversion element for an imaging device or the charge-blocking material for a photoelectric conversion device for an imaging device described above.
  • the hole-transporting layer (electron-blocking layer) 205-IV may have a single-layer structure composed of one or more materials, or may have a laminated structure composed of multiple layers having the same composition or different compositions.
  • the hole transport layer (electron blocking layer) 205-IV includes, for example, a layer adjacent to the photoelectric conversion layer 204-IV made of a material specialized for electron blocking and a buffer made of a material specialized for hole transport. and a layer adjacent to layer 206-IV.
  • the hole-transporting layer (electron-blocking layer) 205-IV may further contain a conventionally known hole-transporting material in addition to the above-described photoelectric conversion element materials for imaging elements.
  • a conventionally known hole-transporting material in addition to the above-described photoelectric conversion element materials for imaging elements.
  • Preferable compounds and specific examples of conventionally known hole-transporting materials include the same as the hole-transporting materials described in the item of photoelectric conversion layer 204-IV.
  • a buffer layer 206-IV is provided between the hole transport layer (electron blocking layer) 205-IV and an upper electrode 207-IV described later.
  • the buffer layer 206-IV serves to reduce damage to the organic layer (for example, the hole transport layer (electron blocking layer) 205-IV) during sputtering.
  • the work function of the buffer layer 206-IV it also plays a role of efficiently accepting holes from the hole transport layer (electron blocking layer) 205-IV, and is also called a hole injection layer or a work function adjustment layer. Called.
  • Materials constituting the buffer layer 206-IV may be known materials such as naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA), 2,3,6,7,10, 11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN) and the like.
  • NTCDA naphthalene-1,4,5,8-tetracarboxylic dianhydride
  • HTCN 2,3,6,7,10, 11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene
  • An upper electrode 207-IV is provided on the buffer layer 206-IV.
  • the material of the upper electrode 207-IV is not particularly limited, and examples include sodium, sodium-potassium alloy, magnesium, lithium, magnesium/copper mixture, silver, magnesium/silver mixture, aluminum, magnesium/aluminum mixture, magnesium/indium mixture, It may be aluminum/aluminum oxide (Al 2 O 3 ) mixtures, indium, lithium/aluminum mixtures, rare earth metals, and the like.
  • each layer other than the lower electrode 202-IV and the upper electrode 207-IV the material of each layer (and, if necessary, a material such as a binder resin, a solvent, etc.) is applied, for example, by a vacuum evaporation method, a spin coating method, or a casting method. , LB (Langmuir-Blodgett method), or the like.
  • the thickness of each layer other than the lower electrode 202-IV and the upper electrode 207-IV is not particularly limited, and can be appropriately selected depending on the situation.
  • the thickness of each layer other than the lower electrode 202-IV and the upper electrode 207-IV is usually in the range of 5 nm or more and 5 ⁇ m or less.
  • the lower electrode 202-IV and the upper electrode 207-IV can be formed by thinning an electrode material by a method such as vapor deposition or sputtering. If the lower electrode 202-IV and the upper electrode 207-IV have a pattern, the pattern can be formed through a mask having a desired shape, for example. Alternatively, after forming a thin film by vapor deposition, sputtering, or the like, a pattern having a desired shape may be formed by photolithography.
  • the film thickness of the lower electrode 202-IV and the upper electrode 207-IV may be 1 ⁇ m or less, preferably 10 nm or more and 200 nm or less.
  • the materials constituting the lower electrode 202-IV and the upper electrode 207-IV may be exchanged as necessary (also called an inverted structure).
  • the photoelectric conversion element for an imaging device is configured such that light passes through the upper electrode 207-IV and is incident on the photoelectric conversion layer 204-IV.
  • An imaging device equipped with a photoelectric conversion device can be applied to, for example, imaging devices such as digital cameras and digital video cameras, and imaging devices built in mobile phones and the like.
  • imaging devices such as digital cameras and digital video cameras, and imaging devices built in mobile phones and the like.
  • the obtained solid was reprecipitated (ethyl acetate/methanol) to obtain 1.40 g (2.46 mmol) of pale yellow powder of compound (A1-1) (yield 76.9%, HPLC purity 95.0%). 0%).
  • the sublimation temperature of compound (A1-1) was 320° C., and it was confirmed that the sublimated compound (A1-1) was glassy. Identification of the compound was carried out by 1 H-NMR measurement.
  • the obtained solid was recrystallized (toluene) to obtain 1.83 g (2.83 mmol) of pale yellow powder of compound (A1-46) (yield 73.2%, HPLC purity 98.8%). .
  • the sublimation temperature of compound (A1-46) was 340° C., and it was confirmed that the sublimated compound (A1-46) was glassy. Identification of the compound was carried out by 1 H-NMR measurement.
  • the obtained solid was recrystallized (toluene) to obtain 1.20 g (2.11 mmol) of white powder of compound (A3-1) (yield 51.4%, HPLC purity 99.8).
  • the sublimation temperature of compound (A3-1) was 320° C., and it was confirmed that the sublimated compound (A3-1) was glassy. Identification of the compound was carried out by 1 H-NMR measurement.
  • the obtained solid was recrystallized (toluene) to obtain 1.12 g (1.97 mmol) of white powder of compound (A4-1) (yield 46.9%, HPLC purity 99.9%).
  • the sublimation temperature of compound (A4-1) was 320° C., and it was confirmed that the sublimated compound (A4-1) was glassy. Identification of the compound was carried out by 1 H-NMR measurement.
  • the organic layer obtained by liquid-separating a water layer and an organic layer was concentrated under reduced pressure after drying with anhydrous magnesium sulfate.
  • the concentrate was purified by silica gel column chromatography (toluene) to obtain 1.44 g (2.31 mmol) of compound (A4-57) as a colorless powder (yield 48.6%, HPLC purity 96.5%). ).
  • the sublimation temperature of compound (A4-57) was 340° C., and it was confirmed that the sublimated compound (A4-57) was glassy. Identification of the compound was carried out by 1 H-NMR measurement.
  • the organic layer obtained by liquid-separating a water layer and an organic layer was concentrated under reduced pressure after drying with anhydrous magnesium sulfate.
  • the concentrate was recrystallized (toluene/hexane) to obtain 2.26 g (3.21 mmol) of compound (B1-55) as a colorless powder (yield 80.3%, HPLC purity 98.3%).
  • the sublimation temperature of compound (B1-55) was 350° C., and it was confirmed that the sublimated compound (B1-55) was glassy. Identification of the compound was carried out by 1 H-NMR measurement.
  • the organic layer obtained by liquid-separating a water layer and an organic layer was concentrated under reduced pressure after drying with anhydrous magnesium sulfate.
  • 2.50 g (3.55 mmol) of pale yellow powder of compound (B2-55) was obtained (yield 88.8%, HPLC purity 97.6%).
  • the sublimation temperature of compound (B2-55) was 350° C., and it was confirmed that the sublimated compound (B2-55) was glassy. Identification of the compound was carried out by 1 H-NMR measurement.
  • Comparative Examples -1 to 4 As Comparative Examples-1 to 4, compounds (X1) to (X4) represented by the following formulas were used. Compounds (X2) and (X3) were synthesized according to the method disclosed in JP-A-2011-006397. Compound (X4) was synthesized according to the method disclosed in JP-A-2019-034939.
  • bandgap It was calculated from the HOMO value of a deposited film of the compound (100 nm formed on a quartz substrate at a rate of 0.10 nm/sec) and the wavelength edge of the absorption spectrum.
  • the HOMO value of the deposited film was measured using an atmospheric photoelectron spectrometer (AC-3) manufactured by Riken Keiki Co., Ltd., and the absorption spectrum was measured using a UV-visible near-infrared spectrophotometer (V-750) manufactured by JASCO Corporation. was measured using Table 1 shows the results.
  • FIG. 2 a laminated structure consisting of substrate 101-I/lower electrode 102-I/hole injection layer 103-I/hole transport layer 104-I/buffer layer 105-I/upper electrode 106-I is employed.
  • a hole-only device 1000-I was fabricated, and the hole transport properties of the device were evaluated.
  • a substrate having a lower electrode on its surface As a substrate having a lower electrode on its surface, a glass substrate with an ITO transparent electrode, in which an indium-tin oxide (ITO) film (thickness: 110 nm) with a width of 2 mm was patterned in stripes, was prepared. Then, after washing the substrate with isopropyl alcohol, the surface was treated by ozone ultraviolet washing.
  • ITO indium-tin oxide
  • each layer was vacuum-deposited on the surface-treated substrate after cleaning by a vacuum deposition method to laminate each layer.
  • the glass substrate was introduced into a vacuum deposition tank, and the pressure was reduced to 7.0 ⁇ 10 ⁇ 5 Pa. Then, each layer was produced in the following order according to the film forming conditions of each layer.
  • a hole injection layer 103-I was prepared by depositing a sublimation-purified compound (HATCN) shown below to a thickness of 10 nm at a rate of 0.10 nm/sec.
  • HTCN sublimation-purified compound
  • buffer layer 105-I A sublimation-purified compound (HATCN) shown below was deposited at a rate of 0.10 nm/second to a thickness of 10 nm to form a buffer layer 105-I.
  • HOD hole-only device 1000-I having an area of 4 mm 2 as shown in FIG. 2 was produced.
  • Each film thickness was measured with a stylus film thickness meter (DEKTAK, manufactured by Bruker).
  • this device was sealed in a nitrogen atmosphere glove box with an oxygen and moisture concentration of 1 ppm or less. Sealing was performed by using a bisphenol F-type epoxy resin (manufactured by Nagase ChemteX Corporation) between the glass sealing cap and the film formation substrate (element).
  • a bisphenol F-type epoxy resin manufactured by Nagase ChemteX Corporation
  • the compound of the present application has a high amorphous property and exhibits stable hole mobility, whereas the compound (X1) has a high crystallinity and is difficult to form a stable amorphous film. It is presumed that this indicates the degree of In fact, in the differential scanning calorimetry (DSC measurement) of each sublimation powder, no peak indicating crystallization was observed in the compounds of Element Examples A-1 to A-11, whereas the compound (X1) A crystallization peak was observed around 150°C.
  • substrate 1-I and lower electrode 2-I As a substrate having a lower electrode on its surface, a glass substrate with an ITO transparent electrode, in which an indium-tin oxide (ITO) film (thickness: 110 nm) with a width of 2 mm was patterned in stripes, was prepared. Then, after washing the substrate with isopropyl alcohol, the surface was treated by ozone ultraviolet washing.
  • ITO indium-tin oxide
  • Each layer was laminated by a vacuum vapor deposition method on the surface-treated substrate after cleaning. Specifically, a glass substrate with an ITO transparent electrode was introduced into a vacuum deposition tank, and the pressure was reduced to 7.0 ⁇ 10 ⁇ 5 Pa. And each layer was produced in the following order.
  • Sublimation purified 4,6-bis(3,5-di(pyridin-4-yl)phenyl)-2-methylpyrimidine was deposited at a rate of 0.10 nm/sec to form a 10 nm film, forming an electron transport layer (hole blocking layer ) 3-I was prepared.
  • buffer layer 6-I Sublimation-purified 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN) was added at 0.10 nm/ A film of 10 nm was formed at a speed of 1 second to prepare a buffer layer 6-I.
  • HTCN 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene
  • a metal mask was arranged so as to be perpendicular to the ITO stripes on the substrate, and an upper electrode 7-I was formed.
  • the upper electrode was formed by depositing silver to a thickness of 80 nm. The deposition rate of silver was 0.1 nm/sec.
  • An imaging photoelectric conversion element having an area of 4 mm 2 was produced by the above method.
  • the thickness of each layer was measured with a stylus film thickness meter (DEKTAK, manufactured by Bruker).
  • the fabricated device was sealed in a nitrogen atmosphere glove box with an oxygen and water concentration of 1 ppm or less. Sealing was performed using a glass sealing cap and a bisphenol F type epoxy resin (manufactured by Nagase ChemteX Corporation).
  • the obtained solid was recrystallized (toluene) to obtain 1.38 g (2.19 mmol) of compound (AT-2) as a colorless powder (yield 60.5%, HPLC purity 99.9%).
  • the sublimation temperature of compound (AT-2) was 370° C., and it was confirmed that the sublimated compound (AT-2) was glassy. Identification of the compound was carried out by 1 H-NMR measurement.
  • Comparative examples -1 to 4 As Comparative Examples-1 to 4, compounds (X1) to (X4) represented by the following formulas were used. Compounds (X2) and (X3) were synthesized according to the method disclosed in JP-A-2011-006397. Compound (X4) was synthesized according to the method disclosed in JP-A-2019-034939.
  • bandgap It was calculated from the HOMO value of a deposited film of the compound (100 nm formed on a quartz substrate at a rate of 0.10 nm/sec) and the wavelength edge of the absorption spectrum.
  • the HOMO value of the deposited film was measured using an atmospheric photoelectron spectrometer (AC-3) manufactured by Riken Keiki Co., Ltd., and the absorption spectrum was measured using a UV-visible near-infrared spectrophotometer (V-750) manufactured by JASCO Corporation. was measured using Table 4 shows the results.
  • FIG. 4 (Device Example A-1: Fabrication of hole-only device using compound (AA-3)) As shown in FIG. 4, a laminated structure consisting of substrate 101-II/lower electrode 102-II/hole injection layer 103-II/hole transport layer 104-II/buffer layer 105-II/upper electrode 106-II is employed. A hole-only device 1000-II was fabricated and the hole transport properties of the device were evaluated.
  • substrate 101-II and lower electrode 102-II As a substrate having a lower electrode on its surface, a glass substrate with an ITO transparent electrode, in which an indium-tin oxide (ITO) film (thickness: 110 nm) with a width of 2 mm was patterned in stripes, was prepared. Then, after washing the substrate with isopropyl alcohol, the surface was treated by ozone ultraviolet washing.
  • ITO indium-tin oxide
  • each layer was vacuum-deposited on the surface-treated substrate after cleaning by a vacuum deposition method to laminate each layer.
  • the glass substrate was introduced into a vacuum deposition tank, and the pressure was reduced to 7.0 ⁇ 10 ⁇ 5 Pa. Then, each layer was produced in the following order according to the film forming conditions of each layer.
  • a hole injection layer 103-II was prepared by depositing a sublimation-purified compound (HATCN) shown below to a thickness of 10 nm at a rate of 0.10 nm/sec.
  • HTCN sublimation-purified compound
  • buffer layer 105-II (Preparation of buffer layer 105-II) Sublimation-purified compound (HATCN) shown below was deposited at a rate of 0.10 nm/second to a thickness of 10 nm to prepare a buffer layer 105-II.
  • HOD hole-only device
  • HODII hole-only device 1000-II with an area of 4 mm 2 as shown in FIG. 4 was produced.
  • Each film thickness was measured with a stylus film thickness meter (DEKTAK, manufactured by Bruker).
  • this device was sealed in a nitrogen atmosphere glove box with an oxygen and moisture concentration of 1 ppm or less. Sealing was performed by using a bisphenol F-type epoxy resin (manufactured by Nagase ChemteX Corporation) between the glass sealing cap and the film formation substrate (element).
  • a bisphenol F-type epoxy resin manufactured by Nagase ChemteX Corporation
  • the compound of the present application has a high amorphous property and exhibits stable hole mobility, whereas the compound (X1) has a high crystallinity and is difficult to form a stable amorphous film. It is presumed that this indicates the degree of In fact, in differential scanning calorimetry (DSC measurement) of each sublimation powder, no peak indicating crystallization was observed for the compounds of Element Examples A-1 to A-7, whereas compound (X1) A crystallization peak was observed around 150°C.
  • Substrate 1-II and lower electrode 2-II were prepared in the same manner as in Device Example A-1.
  • a film of 120 nm was formed from N,N-dimethylquinacridone and C60 at a ratio of 4:1 (mass ratio) to prepare a photoelectric conversion layer 4-II.
  • the deposition rate was 0.15 nm/sec.
  • buffer layer 6-II (Preparation of buffer layer 6-II) Sublimation purified compound 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN) was deposited at a rate of 0.10 nm/sec to form a 10 nm film, A buffer layer 6-II was produced.
  • a photoelectric conversion element 100-II for an imaging element having an area of 4 mm 2 as shown in FIG. 3 was produced.
  • Each film thickness was measured with a stylus film thickness meter (DEKTAK, manufactured by Bruker).
  • this device was sealed in a nitrogen atmosphere glove box with an oxygen and moisture concentration of 1 ppm or less. Sealing was performed by using a bisphenol F-type epoxy resin (manufactured by Nagase ChemteX Corporation) between the glass sealing cap and the film formation substrate (element).
  • a bisphenol F-type epoxy resin manufactured by Nagase ChemteX Corporation
  • a current (dark current) in a dark place and an external quantum efficiency were evaluated when a voltage of 2.5 V was applied to the photoelectric conversion element for an imaging device manufactured as described above. Dark current measurements were evaluated using a Keithley Source Measure Unit 2636B. A solar cell spectral sensitivity measuring device (manufactured by Soma Kogaku Co., Ltd.) was used to measure the external quantum efficiency. The wavelength of the irradiation light was 560 nm, and the measurement was performed at an intensity of 50 ⁇ W/cm 2 . Table 6 shows the results.
  • the photoelectric conversion device materials for imaging devices containing the example compounds of the present invention according to one aspect of the present invention exhibited a higher external quantum efficiency than the photoelectric conversion device materials containing the comparative example compounds.
  • Comparative examples -1 to 4 As Comparative Examples-1 to 4, compounds (X1) to (X4) represented by the following formulas were used. Compounds (X2) and (X3) were synthesized according to the method disclosed in JP-A-2011-006397. Compound (X4) was synthesized according to the method disclosed in JP-A-2019-034939.
  • bandgap It was calculated from the HOMO value of a deposited film of the compound (100 nm formed on a quartz substrate at a rate of 0.10 nm/sec) and the wavelength edge of the absorption spectrum.
  • the HOMO value of the deposited film was measured using an atmospheric photoelectron spectrometer (AC-3) manufactured by Riken Keiki Co., Ltd., and the absorption spectrum was measured using a UV-visible near-infrared spectrophotometer (V-750) manufactured by JASCO Corporation. was measured using Table 7 shows the results.
  • FIG. 6 (Device Example A-1: Fabrication of hole-only device using compound (2A-13)) As shown in FIG. 6, a laminated structure consisting of substrate 101-III/lower electrode 102-III/hole injection layer 103-III/hole transport layer 104-III/buffer layer 105-III/upper electrode 106-III. A hole-only device 1000-III was fabricated and the hole transport properties of the device were evaluated.
  • substrate 101-III and lower electrode 102-III As a substrate having a lower electrode on its surface, a glass substrate with an ITO transparent electrode, in which an indium-tin oxide (ITO) film (thickness: 110 nm) with a width of 2 mm was patterned in stripes, was prepared. Then, after washing the substrate with isopropyl alcohol, the surface was treated by ozone ultraviolet washing.
  • ITO indium-tin oxide
  • each layer was vacuum-deposited on the surface-treated substrate after cleaning by a vacuum deposition method to laminate each layer.
  • the glass substrate was introduced into a vacuum deposition tank, and the pressure was reduced to 7.0 ⁇ 10 ⁇ 5 Pa. Then, each layer was produced in the following order according to the film forming conditions of each layer.
  • a hole injection layer 3-III was prepared by depositing a sublimation-purified compound (HATCN) shown below to a thickness of 10 nm at a rate of 0.10 nm/sec.
  • HTCN sublimation-purified compound
  • buffer layer 105-III (Preparation of buffer layer 105-III) Sublimation-purified compound (HATCN) shown below was deposited at a rate of 0.10 nm/sec to a thickness of 10 nm to prepare a buffer layer 5-III.
  • HOD hole-only device
  • DEKTAK stylus film thickness meter
  • this device was sealed in a nitrogen atmosphere glove box with an oxygen and moisture concentration of 1 ppm or less. Sealing was performed by using a bisphenol F-type epoxy resin (manufactured by Nagase ChemteX Corporation) between the glass sealing cap and the film formation substrate (element).
  • a bisphenol F-type epoxy resin manufactured by Nagase ChemteX Corporation
  • Element Examples A-2 to A-4 and Element Comparative Examples A-1 to A-4) In the preparation of the hole transport layer 104-III of Device Example A-1, instead of the compound (2A-13), the compound (2B-13), the compound (2C-7), the compound (2C-17), Element Examples A-2 to A-4 were prepared in the same manner as in Element Example A-1, except that Compound (X1), Compound (X2), Compound (X3), or Compound (X4) was used. and element comparative examples A-1 to A-4 were fabricated, and the mobility in the SCLC region was measured by the same method as in element example A-1. Table 8 shows the results.
  • the compound of the present application has a high amorphous property and exhibits stable hole mobility, whereas the compound (X1) has a high crystallinity and is difficult to form a stable amorphous film. It is presumed that this indicates the degree of Actually, in the differential scanning calorimetry (DSC measurement) of each sublimation powder, no peak indicating crystallization was observed in the compounds of Element Examples A-1 to A-4, whereas the compound (X1) A crystallization peak was observed around 150°C.
  • Substrate 1-III and lower electrode 2-III were prepared in the same manner as in Device Example A-1.
  • a film of 120 nm was formed from N,N-dimethylquinacridone and C60 at a ratio of 4:1 (mass ratio) to prepare a photoelectric conversion layer 4-III.
  • the deposition rate was 0.15 nm/sec.
  • buffer layer 6-III Sublimation purified compound 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN) was deposited at a rate of 0.10 nm/sec to form a 10 nm film, A buffer layer 6-III was produced.
  • a photoelectric conversion element 100-III for an imaging element having an area of 4 mm 2 as shown in FIG. 5 was produced.
  • Each film thickness was measured with a stylus film thickness meter (DEKTAK, manufactured by Bruker).
  • this device was sealed in a nitrogen atmosphere glove box with an oxygen and moisture concentration of 1 ppm or less. Sealing was performed by using a bisphenol F-type epoxy resin (manufactured by Nagase ChemteX Corporation) between the glass sealing cap and the film formation substrate (element).
  • a bisphenol F-type epoxy resin manufactured by Nagase ChemteX Corporation
  • a current (dark current) in a dark place and an external quantum efficiency were evaluated when a voltage of 2.5 V was applied to the photoelectric conversion element for an imaging device manufactured as described above. Dark current measurements were evaluated using a Keithley Source Measure Unit 2636B. A solar cell spectral sensitivity measuring device (manufactured by Soma Kogaku Co., Ltd.) was used to measure the external quantum efficiency. The wavelength of the irradiation light was 560 nm, and the measurement was performed at an intensity of 50 ⁇ W/cm 2 . Table 9 shows the results.
  • the photoelectric conversion device materials for imaging devices containing the example compounds of the present invention according to one aspect of the present invention exhibited a higher external quantum efficiency than the photoelectric conversion device materials containing the comparative example compounds.
  • 1,3-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene (0.98 g, 2.7 mmol) was placed in a 200 mL two-necked flask under a nitrogen stream.
  • 2-chloro-dibenzo[g,p]chrysene (1.88 g, 5.7 mmol)
  • bis(dibenzylideneacetone) palladium(0) (24.8 mg, 0.03 mmol)
  • Xphos (51.7 mg, 0.7 mmol).
  • 11 mmol tetrahydrofuran (30 mL), and 2 M potassium phosphate aqueous solution (8.1 mL) were added, and the mixture was stirred at 70° C.
  • the washed solid was recrystallized (O-dichlorobenzene/ethanol) to obtain 2.25 g (3.44 mmol) of yellow powder of compound (3A-1) (yield 98.2%, HPLC purity 99.0%). 3%).
  • the sublimation temperature of compound (3A-1) was 380° C., and it was confirmed that the sublimated compound (3A-1) was glassy. Identification of the compound was carried out by 1H-NMR measurement.
  • Comparative examples -1 to 4 As Comparative Examples-1 to 4, compounds (X1) to (X4) represented by the following formulas were used. Compounds (X2) and (X3) were synthesized according to the method disclosed in JP-A-2011-006397. Compound (X4) was synthesized according to the method disclosed in JP-A-2019-034939.
  • bandgap It was calculated from the HOMO value of a deposited film of the compound (100 nm formed on a quartz substrate at a rate of 0.10 nm/sec) and the wavelength edge of the absorption spectrum.
  • the HOMO value of the deposited film was measured using an atmospheric photoelectron spectrometer (AC-3) manufactured by Riken Keiki Co., Ltd., and the absorption spectrum was measured using a UV-visible near-infrared spectrophotometer (V-750) manufactured by JASCO Corporation. was measured using Table 10 shows the results.
  • substrate 1-IV and lower electrode 2-IV As a substrate having a lower electrode on its surface, a glass substrate with an ITO transparent electrode, in which an indium-tin oxide (ITO) film (thickness: 110 nm) with a width of 2 mm was patterned in stripes, was prepared. Then, after washing the substrate with isopropyl alcohol, the surface was treated by ozone ultraviolet washing.
  • ITO indium-tin oxide
  • each layer was vacuum-deposited on the surface-treated substrate after cleaning by a vacuum deposition method to laminate each layer.
  • the glass substrate was introduced into a vacuum deposition tank, and the pressure was reduced to 7.0 ⁇ 10 ⁇ 5 Pa. Then, each layer was produced in the following order according to the film forming conditions of each layer.
  • a hole injection layer 3-IV was prepared by depositing a sublimation-purified compound (HATCN) shown below to a thickness of 10 nm at a rate of 0.10 nm/sec.
  • HTCN sublimation-purified compound
  • buffer layer 5-IV A sublimation-purified compound (HATCN) shown below was deposited at a rate of 0.10 nm/sec to a thickness of 10 nm to prepare a buffer layer 5-IV.
  • a hole-only device (HOD) 100-IV with an area of 4 mm 2 as shown in FIG. 7 was produced.
  • Each film thickness was measured with a stylus film thickness meter (DEKTAK, manufactured by Bruker). Further, this device was sealed in a nitrogen atmosphere glove box with an oxygen and water concentration of 1 ppm or less. Sealing was performed by using a bisphenol F-type epoxy resin (manufactured by Nagase ChemteX Corporation) between the glass sealing cap and the film formation substrate (element).
  • a direct current was applied to the organic electroluminescence device produced as described above, and a current density of 10 mA/cm 2 was measured. The mobility in the SCLC region was measured from the obtained JV curve. Table 11 shows the results.
  • Element Examples A-2 to A-4 and Element Comparative Examples A-1 to A-4) In the preparation of the hole transport layer 4-IV of Device Example A-1, instead of the compound (2A-1), the compound (2A-3), the compound (2A-6), the compound (3A-1), Element Examples A-2 to A-4 were prepared in the same manner as in Element Example A-1, except that Compound (X1), Compound (X2), Compound (X3), or Compound (X4) was used. and element comparative examples A-1 to A-4 were fabricated, and the mobility in the SCLC region was measured by the same method as in element example A-1. Table 11 shows the results.
  • substrate 201-IV, lower electrode 202-IV, electron transport layer (hole blocking layer) 203-IV, photoelectric conversion layer 204-IV, hole transport layer (electron blocking layer) 205-IV. , a buffer layer 206-IV, and an upper electrode 207-IV were fabricated, and the dark current and external quantum efficiency of the photoelectric conversion element were evaluated.
  • substrate 201-IV and lower electrode 202-IV Preparation of substrate 201-IV and lower electrode 202-IV.
  • the substrate 201-IV and the lower electrode 202-IV were prepared in the same procedure as in Device Example A-1.
  • a film of 120 nm was formed from N,N-dimethylquinacridone and C60 at a ratio of 4:1 (mass ratio) to prepare a photoelectric conversion layer 204-IV.
  • the deposition rate was 0.15 nm/sec.
  • buffer layer 206-IV (Preparation of buffer layer 206-IV) Sublimation purified compound 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN) was deposited at a rate of 0.10 nm/sec to form a 10 nm film, A buffer layer 206-IV was produced.
  • HTCN 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene
  • a photoelectric conversion element 300-IV for an imaging element having an area of 4 mm 2 as shown in FIG. 10 was manufactured.
  • Each film thickness was measured with a stylus film thickness meter (DEKTAK, manufactured by Bruker).
  • this device was sealed in a nitrogen atmosphere glove box with an oxygen and moisture concentration of 1 ppm or less. Sealing was performed by using a bisphenol F-type epoxy resin (manufactured by Nagase ChemteX Corporation) between the glass sealing cap and the film formation substrate (element).
  • a bisphenol F-type epoxy resin manufactured by Nagase ChemteX Corporation
  • a current (dark current) in a dark place and an external quantum efficiency were evaluated when a voltage of 2.5 V was applied to the photoelectric conversion element for an imaging device manufactured as described above. Dark current measurements were evaluated using a Keithley Source Measure Unit 2636B. A solar cell spectral sensitivity measuring device (manufactured by Soma Kogaku Co., Ltd.) was used to measure the external quantum efficiency. The wavelength of the irradiation light was 560 nm, and the measurement was performed at an intensity of 50 ⁇ W/cm 2 . Table 12 shows the results.
  • the dark current and external quantum efficiency of Device Example B-1 and Device Comparative Example B-2 are the reference values (1.0) for the dark current and external quantum efficiency of Device Comparative Example B-1, respectively. and (100).
  • the photoelectric conversion device material for an imaging device containing the example compound according to one aspect of the present invention exhibited a higher external quantum efficiency than the photoelectric conversion device material containing the comparative example compound.
  • substrate 101-IV and anode 102-IV Preparation of substrate 101-IV and anode 102-IV
  • a substrate having an anode on its surface a glass substrate with an ITO transparent electrode, in which an indium-tin oxide (ITO) film (thickness: 110 nm) with a width of 2 mm was patterned in stripes, was prepared. Then, after washing the substrate with isopropyl alcohol, the surface was treated by ozone ultraviolet washing.
  • ITO indium-tin oxide
  • each layer was produced in the following order according to the film forming conditions of each layer.
  • first hole transport layer 1051 (Preparation of first hole transport layer 1051) Sublimation purified N-[1,1′-biphenyl]-4-yl-9,9-dimethyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9H-fluorene-2 -Amine was deposited at a rate of 0.15 nm/sec to a thickness of 85 nm to prepare a first hole transport layer 1051 .
  • Second hole transport layer 1052 A film of 5 nm in thickness was formed from the sublimation-purified compound (2A-3) at a rate of 0.15 nm/sec to prepare a second hole transport layer 1052 .
  • Second electron transport layer 1072 (Preparation of second electron transport layer 1072) Sublimation purified 2-[4- ⁇ 4-(4′-cyano-1,1′-biphenyl-4-yl)-1-naphthyl ⁇ phenyl]-4,6-diphenyl-1,3,5-triazine and Liq was deposited at a ratio of 50:50 (mass ratio) to a thickness of 25 nm to form the second electron transport layer 1072 . The deposition rate was 0.15 nm/sec.
  • a metal mask was placed so as to be perpendicular to the ITO stripes on the substrate, and a cathode 108-IV was formed.
  • the cathode was formed by depositing silver/magnesium (mass ratio 1/10) and silver in this order to 80 nm and 20 nm, respectively, to form a two-layer structure.
  • the deposition rate of silver/magnesium was 0.5 nm/second, and the deposition rate of silver was 0.2 nm/second.
  • an organic electroluminescence device 200-IV having a light emitting area of 4 mm 2 as shown in FIG. 9 was produced.
  • Each film thickness was measured with a stylus film thickness meter (DEKTAK, manufactured by Bruker).
  • this device was sealed in a nitrogen atmosphere glove box with an oxygen and moisture concentration of 1 ppm or less. Sealing was performed by using a bisphenol F-type epoxy resin (manufactured by Nagase ChemteX Corporation) between the glass sealing cap and the film formation substrate (element).
  • a bisphenol F-type epoxy resin manufactured by Nagase ChemteX Corporation
  • a direct current was applied to the organic electroluminescence device produced as described above, and the luminescence characteristics were evaluated using a luminance meter (product name: BM-9, manufactured by Topcon Technohouse).
  • a luminance meter product name: BM-9, manufactured by Topcon Technohouse.
  • current efficiency cd/A
  • element life h
  • the device life was measured by measuring the luminance decay time during continuous lighting when the manufactured device was driven at an initial luminance of 1000 cd/m 2 , and was required until the luminance (cd/m 2 ) decreased by 5%. time was measured.
  • the voltage, current efficiency, and device life are relative values with the result of device comparative example B-1 as a reference value (100). Table 13 shows the measurement results obtained.

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