WO2022050146A1 - Élément de conversion photoélectrique, élément d'imagerie, capteur optique et composé - Google Patents

Élément de conversion photoélectrique, élément d'imagerie, capteur optique et composé Download PDF

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WO2022050146A1
WO2022050146A1 PCT/JP2021/031165 JP2021031165W WO2022050146A1 WO 2022050146 A1 WO2022050146 A1 WO 2022050146A1 JP 2021031165 W JP2021031165 W JP 2021031165W WO 2022050146 A1 WO2022050146 A1 WO 2022050146A1
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atom
group
formula
substituent
sulfur atom
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PCT/JP2021/031165
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Japanese (ja)
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寛記 杉浦
康智 米久田
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富士フイルム株式会社
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
    • 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 photoelectric conversion element, an image pickup element, an optical sensor, and a compound.
  • Patent Document 1 discloses an organic semiconductor material using the following compound.
  • the photoelectric conversion element is required to further improve the photoelectric conversion efficiency for visible light (specifically, light having a wavelength of 400 to 700 nm). Further, it is also required that the electric field strength dependence of the photoelectric conversion efficiency is low. Specifically, it is required that the fluctuation of the photoelectric conversion efficiency is small even when the electric field strength is different.
  • the low electric field strength dependence of the photoelectric conversion efficiency is excellent in the electric field strength dependence.
  • the present inventors have studied a photoelectric conversion element using a compound disclosed in Patent Document 1, and found that the photoelectric conversion efficiency and electric field strength dependence on visible light do not satisfy the required performance, and further improvement is required. I found that there is.
  • the present invention provides a photoelectric conversion element having excellent photoelectric conversion efficiency for visible light (specifically, light having a wavelength of 400 to 700 nm) and also having excellent electric field strength dependence. Make it an issue.
  • Another object of the present invention is to provide an image pickup device, an optical sensor, and a compound related to the photoelectric conversion element.
  • a photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, wherein the photoelectric conversion film is a compound represented by the formula (1), a dye, and an n-type.
  • the group represented by (Ar 11 ) n11 is a group represented by the formula (A3), a group represented by the formula (A4), and a group represented by the formula (A5).
  • the photoelectric conversion element according to [1] which is any of the groups represented by the formula (A33).
  • the group represented by (Ar 11 ) n11 is a group represented by the formula (A3), a group represented by the formula (A4), and a group represented by the formula (A5).
  • the photoelectric conversion element according to.
  • Ar 14 to Ar 15 are composed of a pyridine ring group, a pyrimidine ring group, a thiazole ring group, a benzothiazole ring group, a thiazorothiazole ring group, a quinoline ring group, and an isoquinoline ring group.
  • Aromatic heterocyclic group selected from the group or A benzene ring group substituted with an aromatic ring group selected from the group consisting of a pyridine ring group, a pyrimidine ring group, a thiazole ring group, a benzothiazole ring group, a thiazolothiazole ring group, a quinoline ring group, and an isoquinoline ring group.
  • the present invention it is possible to provide a photoelectric conversion element having excellent photoelectric conversion efficiency for visible light (specifically, light having a wavelength of 400 to 700 nm) and also having excellent electric field strength dependence. Further, according to the present invention, it is possible to provide an image pickup device, an optical sensor, and a compound related to the photoelectric conversion element.
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the numerical range represented by using “-” means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • the hydrogen atom may be a light hydrogen atom (ordinary hydrogen atom) or a heavy hydrogen atom (double hydrogen atom or the like).
  • the photoelectric conversion element of the present invention is a photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order, and the photoelectric conversion film is a compound represented by the formula (1) (hereinafter referred to as a compound). Also referred to as a "specific compound"), dyes, and n-type semiconductor materials.
  • the mechanism by which the photoelectric conversion element obtains the desired effect by adopting the above configuration is not always clear, but the present inventors speculate as follows.
  • the specific compound has, for example, a group represented by Ar 11 acting as a donor and a group acting as an acceptor at both ends of the donor in the molecule.
  • the specific compound has a structure in which the donor is sandwiched by the acceptors. Since such a specific compound has both donor and acceptor structures, the absorption wavelength can be lengthened. Further, it is presumed that the photoelectric conversion film further contains a dye and an n-type semiconductor material, so that the photoelectric conversion efficiency with respect to visible light is excellent. Further, it is considered that the etenyl group in the specific compound is rotated around a single bond, so that the donor unit can form a favorable assembly state for charge transport, and thus is excellent in electric field strength dependence.
  • At least one of the effects of the photoelectric conversion efficiency for visible light of the photoelectric conversion element (specifically, light having a wavelength of 400 to 700 nm) being more excellent and the electric field strength dependence of the photoelectric conversion element being more excellent. It is also said that the effect of the present invention is more excellent.
  • FIG. 1 shows a schematic cross-sectional view of an embodiment of the photoelectric conversion element of the present invention.
  • the photoelectric conversion element 10a shown in FIG. 1 includes a conductive film (hereinafter, also referred to as a lower electrode) 11 that functions as a lower electrode, an electron blocking film 16A, a photoelectric conversion film 12 containing a specific compound described later, and an upper electrode. It has a structure in which functional transparent conductive films (hereinafter, also referred to as “upper electrodes”) 15 are laminated in this order.
  • FIG. 2 shows a configuration example of another photoelectric conversion element.
  • FIGS. 1 and 2 has a configuration in which an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15 are laminated in this order on a lower electrode 11.
  • the stacking order of the electron blocking film 16A, the photoelectric conversion film 12, and the hole blocking film 16B in FIGS. 1 and 2 may be appropriately changed depending on the application and characteristics.
  • the photoelectric conversion element 10a it is preferable that light is incident on the photoelectric conversion film 12 via the upper electrode 15.
  • a voltage can be applied.
  • the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and the voltage applied between the pair of electrodes is 1.0 ⁇ 10-5 to 1.0 ⁇ 10 7 V / cm.
  • 1.0 ⁇ 10 -4 to 1.0 ⁇ 10 7 V / cm is more preferable, and 1.0 ⁇ 10 -3 to 5.0 ⁇ 10 6 V / cm is further preferable from the viewpoint of performance and power consumption. preferable.
  • the voltage application method it is preferable to apply the voltage so that the electron blocking film 16A side becomes the cathode and the photoelectric conversion film 12 side becomes the anode in FIGS. 1 and 2.
  • a voltage can be applied by the same method.
  • the photoelectric conversion element 10a (or 10b) can be suitably applied to an image pickup device application.
  • the photoelectric conversion film contains a specific compound, a dye, and an n-type semiconductor material.
  • the maximum absorption wavelength of the photoelectric conversion film is not particularly limited, and is preferably in the range of 300 to 700 nm, more preferably in the range of 400 to 700 nm.
  • the photoelectric conversion film is substantially composed only of a specific compound described later, a dye, and an n-type semiconductor material.
  • the fact that the photoelectric conversion film is substantially composed of only the specific compound, the dye, and the n-type semiconductor material means that the total content of the specific compound, the dye, and the n-type semiconductor material is based on the total mass of the photoelectric conversion film. , 95-100% by mass.
  • the photoelectric conversion film is preferably a mixed layer formed by mixing a specific compound, a dye, and an n-type semiconductor material.
  • the mixed layer is a layer in which two or more kinds of materials are mixed in a single layer.
  • the photoelectric conversion film containing a specific compound is a non-luminescent film, and has characteristics different from those of an organic light emitting device (OLED: Organic Light Emitting Diode).
  • the non-luminescent film is intended to be a film having an emission quantum efficiency of 1% or less.
  • the emission quantum efficiency is preferably 0.5% or less, more preferably 0.1% or less.
  • the lower limit is not particularly limited, but 0 is preferable.
  • the thickness of the photoelectric conversion film is preferably 10 to 1000 nm, more preferably 50 to 800 nm, further preferably 50 to 600 nm, and particularly preferably 50 to 500 nm.
  • Ar 11 is formed by an aromatic ring selected from the group consisting of a thiophene ring, a benzene ring, a furan ring, and a selenophene ring, contains at least one thiophene ring, and has a substituent.
  • the fused polycyclic aromatic group represented by Ar 11 is formed by an aromatic ring selected from the group consisting of a thiophene ring and a benzene ring, and at least one thiophene is formed. It is preferable to include a ring.
  • the total number of rings (number of rings) of the condensed polycyclic aromatic group represented by Ar 11 is preferably 3 to 7, and more preferably 4 to 7.
  • substituent W include a group exemplified by the substituent W described later, which are an alkyl group having 1 to 7 carbon atoms, an aryl group, a heteroaryl group, a halogen atom, a cyano group, or a group thereof. Is preferable.
  • n11 represents an integer of 1 to 2.
  • n11 is preferably an integer of 1 to 2.
  • n11 is preferably 2.
  • n11 A preferred embodiment of n11 is that it represents any of the groups represented by the formulas (A1) to (A33) in that the effect of the present invention is more excellent, and (Ar 11 ) n11 .
  • (Ar 11 ) As a more preferable aspect of n11 , a group represented by the formula (A3), a group represented by the formula (A4), a group represented by the formula (A5), and a group represented by the formula (A6) are represented.
  • R 11A represents a hydrogen atom or a substituent.
  • R 12A represents a hydrogen atom or a substituent.
  • At least one of X 11 , X 11A , X 12 and X 12A represents a sulfur atom. * Represents the bond position.
  • R 11A and R 12A are not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • X 21 to X 23 independently represent a sulfur atom, an oxygen atom, or a selenium atom. At least one of X 21 to X 23 represents a sulfur atom. * Represents the bond position. It is preferable that X 21 to X 23 represent a sulfur atom.
  • X 31 to X 32 independently represent a sulfur atom, an oxygen atom, or a selenium atom. At least one of X 31 to X 32 represents a sulfur atom. * Represents the bond position. It is preferable that X 31 to X 32 represent a sulfur atom.
  • R 41 represents a hydrogen atom or a substituent.
  • R 42 represents a hydrogen atom or a substituent.
  • At least one of X 41 , X 41A , X 42 and X 42A represents a sulfur atom. * Represents the bond position.
  • R 41 and R 42 are not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • R 51 represents a hydrogen atom or a substituent.
  • R 52 represents a hydrogen atom or a substituent.
  • At least one of X 51 , X 51A , X 52 and X 52A represents a sulfur atom. * Represents the bond position.
  • R 51 and R 52 are not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • X 61 to X 64 independently represent a sulfur atom, an oxygen atom, or a selenium atom. At least one of X 61 to X 64 represents a sulfur atom. * Represents the bond position. It is preferable that X 61 to X 64 represent a sulfur atom.
  • X 71 to X 74 independently represent a sulfur atom, an oxygen atom, or a selenium atom. At least one of X 71 to X 74 represents a sulfur atom. * Represents the bond position. It is preferable that X 71 to X 74 represent a sulfur atom.
  • X 81 represents a sulfur atom. * Represents the bond position.
  • X 91 represents a sulfur atom. * Represents the bond position.
  • R 101 represents a hydrogen atom or a substituent.
  • R 102 represents a hydrogen atom or a substituent.
  • At least one of X 101 , X 101A , X 102 and X 102A represents a sulfur atom. * Represents the bond position.
  • the substituents represented by R 101 and R 102 are not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • X 111 to X 112 independently represent a sulfur atom, an oxygen atom, or a selenium atom. At least one of X 111 to X 112 represents a sulfur atom. * Represents the bond position. It is preferable that X 111 to X 112 represent a sulfur atom.
  • X 121 represents a sulfur atom, an oxygen atom, or a selenium atom.
  • R 122 represents a hydrogen atom or a substituent.
  • R 123 represents a hydrogen atom or a substituent.
  • At least one of X 121 , X 122 , X 122A , X 123 and X 123A represents a sulfur atom.
  • the substituents represented by R 121 and R 122 are not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • R 131 represents a hydrogen atom or a substituent.
  • R 132 represents a hydrogen atom or a substituent.
  • At least one of X 131 , X 131A , X 132 and X 132A represents a sulfur atom. * Represents the bond position.
  • the substituents represented by R 131 and R 132 are not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • R 141 represents a hydrogen atom or a substituent.
  • R 142 represents a hydrogen atom or a substituent.
  • At least one of X 141 , X 141A , X 142 and X 142A represents a sulfur atom. * Represents the bond position.
  • the substituents represented by R 141 and R 142 are not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • X 151 to X 153 independently represent a sulfur atom, an oxygen atom, or a selenium atom. At least one of X 151 to X 153 represents a sulfur atom. * Represents the bond position. It is preferable that X 151 to X 153 represent a sulfur atom.
  • X 161 to X 162 independently represent a sulfur atom, an oxygen atom, or a selenium atom. At least one of X 161 to X 162 represents a sulfur atom. * Represents the bond position. It is preferable that X 161 to X 162 represent a sulfur atom.
  • X 171 to X 175 independently represent a sulfur atom, an oxygen atom, or a selenium atom. At least one of X 171 to X 175 represents a sulfur atom. * Represents the bond position. It is preferable that X 171 to X 175 represent a sulfur atom.
  • X 181 to X 182 independently represent a sulfur atom, an oxygen atom, or a selenium atom. At least one of X 181 to X 182 represents a sulfur atom. * Represents the bond position. It is preferable that X 181 to X 182 represent a sulfur atom.
  • R191 represents a hydrogen atom or a substituent.
  • X 192 to X 193 independently represent a sulfur atom, an oxygen atom, or a selenium atom.
  • R194 represents a hydrogen atom or a substituent.
  • the substituents represented by R 191 and R 194 are not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • R 201 represents a hydrogen atom or a substituent.
  • R202 represents a hydrogen atom or a substituent.
  • At least one of X 201 , X 201A , X 202 and X 202A represents a sulfur atom. * Represents the bond position.
  • the substituents represented by R 201 and R 202 are not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • R 211 represents a hydrogen atom or a substituent.
  • R 212 represents a hydrogen atom or a substituent.
  • At least one of X 211 , X 211A , X 212 and X 212A represents a sulfur atom. * Represents the bond position.
  • the substituents represented by R 211 and R 212 are not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • X 221 to X 222 independently represent a sulfur atom, an oxygen atom, or a selenium atom. At least one of X 221 to X 222 represents a sulfur atom. * Represents the bond position. It is preferable that X 221 to X 222 represent a sulfur atom.
  • X 231 to X 232 independently represent a sulfur atom, an oxygen atom, or a selenium atom.
  • R233 represents a hydrogen atom or a substituent.
  • R234 represents a hydrogen atom or a substituent.
  • the substituents represented by R 233 and R 234 are not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • X 241 to X 242 independently represent a sulfur atom, an oxygen atom, or a selenium atom.
  • R243 represents a hydrogen atom or a substituent.
  • R244 represents a hydrogen atom or a substituent.
  • the substituents represented by R 243 and R 244 are not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • X 251 to X 254 independently represent a sulfur atom, an oxygen atom, or a selenium atom. At least one of X 251 to X 254 represents a sulfur atom. * Represents the bond position. It is preferable that X 251 to X 254 represent a sulfur atom.
  • X 261 to X 262 independently represent a sulfur atom, an oxygen atom, or a selenium atom. At least one of X 261 to X 262 represents a sulfur atom. * Represents the bond position. It is preferable that X 261 to X 262 represent a sulfur atom.
  • X 271 to X 274 independently represent a sulfur atom, an oxygen atom, or a selenium atom. At least one of X 271 to X 274 represents a sulfur atom. * Represents the bond position. It is preferable that X 271 to X 274 represent a sulfur atom.
  • X 281 to X 282 independently represent a sulfur atom, an oxygen atom, or a selenium atom. At least one of X 281 to X 282 represents a sulfur atom. * Represents the bond position. It is preferable that X 281 to X 282 represent a sulfur atom.
  • X 291 to X 296 independently represent a sulfur atom, an oxygen atom, or a selenium atom. At least one of X 291 to X 296 represents a sulfur atom. * Represents the bond position. It is preferable that X 291 to X 296 represent a sulfur atom.
  • X 301 to X 304 independently represent a sulfur atom, an oxygen atom, or a selenium atom. At least one of X 301 to X 304 represents a sulfur atom. * Represents the bond position. It is preferable that X 301 to X 304 represent a sulfur atom.
  • X 311 to X 314 independently represent a sulfur atom, an oxygen atom, or a selenium atom. At least one of X 311 to X 314 represents a sulfur atom. * Represents the bond position. It is preferable that X 311 to X 314 represent a sulfur atom.
  • R321 represents a hydrogen atom or a substituent.
  • R 322 represents a hydrogen atom or a substituent.
  • R 323 represents a hydrogen atom or a substituent.
  • R324 represents a hydrogen atom or a substituent.
  • the substituents represented by R 321 to R 324 are not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • X 331 to X 336 independently represent a sulfur atom, an oxygen atom, or a selenium atom. At least one of X 331 to X 336 represents a sulfur atom. * Represents the bond position. It is preferable that X 331 to X 336 represent a sulfur atom.
  • Ar 12 to Ar 13 are independently composed of a monocyclic arylene group, a monocyclic heteroarylene group, a fused arylene group having a total number of rings of 2, and a fused heteroarylene group having a total number of rings of 2.
  • the first aromatic ring group may have a substituent. That is, Ar 12 to Ar 13 may independently have a monocyclic arylene group which may have a substituent, a monocyclic heteroarylene group which may have a substituent, and a substituent.
  • the total number of good rings represents a first aromatic ring group selected from the group consisting of two fused arylene groups and the total number of rings which may have substituents is two fused heteroarylene groups.
  • Ar 12 to Ar 13 preferably represent a monocyclic arylene group which may have a substituent or a monocyclic heteroarylene group which may have a substituent, and represent a monocyclic heteroarylene group. Is more preferable.
  • the type of the above-mentioned substituent is not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • an alkyl group having 1 to 7 carbon atoms, a halogen atom, or a group in combination thereof is preferable.
  • the number of ring members of the monocyclic ring constituting the monocyclic arylene group and the monocyclic heteroarylene group is preferably 3 to 10, more preferably 4 to 8, and even more preferably 5 to 6.
  • the number of ring members of the single ring constituting the fused arylene group having two rings and the fused heteroarylene group having two rings is preferably 3 to 10, more preferably 4 to 8, and 5 to 5. 6 is more preferable.
  • Examples of the groups represented by Ar 12 to Ar 13 include a monocyclic arylene group having a benzene ring and the like; a fused arylene group having a total of two rings having a naphthalene ring and an azulene ring and the like; a thiophene ring and a furan ring.
  • a condensed heteroarylene group having a total number of 2 is mentioned.
  • the aromatic ring constituting the first aromatic ring group is preferably selected from the group consisting of a thiophene ring, a benzene ring, and a thiazole ring, and the thiophene ring and the thiazole ring are preferably selected from the viewpoint that the effect of the present invention is more excellent. It is more preferable to be selected from the group consisting of rings.
  • Ar 12 to Ar 13 preferably represent groups having the same structure.
  • n12 to n13 independently represents an integer of 0 to 1. Among them, n12 to n13 preferably represent 0. It is preferable that n12 to n13 represent the same integer.
  • Ar 14 to Ar 15 are independently composed of a monocyclic aryl group, a monocyclic heteroaryl group, a fused aryl group having a total number of rings of 2, and a fused heteroaryl group having a total number of rings of 2.
  • the second aromatic ring group includes a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkyl halide group, an alkoxy halide group, an alkoxycarbonyl group, an acyloxy group, a cyano group, an aryl group, an aryl halide group, and a hetero.
  • Ar 14 to Ar 15 independently have a monocyclic aryl group which may have a specific substituent, a monocyclic heteroaryl group which may have a specific substituent, and a specific substituent.
  • Ar 14 to Ar 15 examples include a monocyclic aryl group having a benzene ring and the like; a fused aryl group having a total of two rings having a naphthalene ring and an azulene ring and the like; a thiophene ring, a furan ring, a selenophene ring and a pyrrole.
  • Triazine ring monocyclic heteroaryl group having tetradine ring and the like; benzofuran ring, isobenzofuran ring, benzothiophene ring, benzoisothiophene ring, indazole ring, indole ring, isoindole ring, indridin ring, quinoline ring,
  • the total number of rings having an isoquinoline ring, a benzoxazole ring, a benzoisoxazole ring, a benzothiazole ring, a benzoisothiazole ring, a benzoimidazole ring, a benzotriazole ring, a thienopyridine ring, a thienothiophene ring, and a thiazolothiazole ring is two. Condensed heteroaryl group of.
  • a pyridine ring group and a pyrimidine ring group can be mentioned.
  • Ar 14 to Ar 15 are aromatics selected from the group consisting of a pyridine ring group, a pyrimidine ring group, a thiazole ring group, a benzothiazole ring group, a thiazolothiazole ring group, a quinoline ring group, and an isoquinoline ring group.
  • the number of ring members of the monocyclic ring constituting the monocyclic aryl group and the monocyclic heteroaryl group is preferably 3 to 10, more preferably 4 to 8, and even more preferably 5 to 6.
  • the number of ring members of a single ring constituting a fused aryl group having two rings and a fused heteroaryl group having two rings is preferably 3 to 10, more preferably 4 to 8, and 5 to 6. Is more preferable.
  • Ar 14 to Ar 15 preferably represent groups of the same structure.
  • R 11 to R 14 independently represent a hydrogen atom or a substituent.
  • the type of the above-mentioned substituent is not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • the substituent an alkyl group having 1 to 7 carbon atoms, an aryl group, a heteroaryl group, a halogen atom, a cyano group, or a group obtained by a combination thereof is preferable, and an alkyl group having 1 to 7 carbon atoms, an aryl group, and the like.
  • a heteroaryl group is more preferable.
  • R 11 to R 14 preferably represent a hydrogen atom.
  • substituent W examples include a halogen atom, an alkyl group having 1 to 7 carbon atoms, an alkenyl group having 1 to 7 carbon atoms (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group having 1 to 7 carbon atoms, and an aryl.
  • heterocyclic group cyano group, hydroxy group, nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (Including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group , Heterocyclic thio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group,
  • the substituent W may be further substituted with the substituent W.
  • an alkyl group having 1 to 7 carbon atoms may be further substituted with a halogen atom.
  • the specific compound does not have any of a carboxy group, a carboxy group salt, a phosphoric acid group, a phosphoric acid group salt, a sulfonic acid group, and a sulfonic acid group salt. Is preferable.
  • the compounds represented by the formulas (1-1) to (1-6) are also preferable.
  • X 11 to X 12 independently represent a sulfur atom, an oxygen atom, or a selenium atom. At least one of X 11 to X 12 represents a sulfur atom. It is preferable that X 11 to X 12 represent a sulfur atom.
  • the definitions of Ar 12 to Ar 13 , Ar 14 to Ar 15 and R 11 to R 14 are defined as Ar 12 to Ar 13 , Ar 14 to Ar 15 and R in the above formula (1). It is synonymous with the definition of 11 to R14 .
  • Each of m12 to m13 independently represents an integer of 1 to 2. It is preferable that m12 to m13 represent 1. It is preferable that m12 to m13 represent the same integer.
  • X 21 to X 23 independently represent a sulfur atom, an oxygen atom, or a selenium atom. At least one of X 21 to X 23 represents a sulfur atom. It is preferable that X 21 to X 23 represent a sulfur atom.
  • the definitions of Ar 12 to Ar 13 , Ar 14 to Ar 15 and R 11 to R 14 are defined as Ar 12 to Ar 13 , Ar 14 to Ar 15 and R in the above formula (1). It is synonymous with the definition of 11 to R14 .
  • Each of m12 to m13 independently represents an integer of 1 to 2. It is preferable that m12 to m13 represent 1. It is preferable that m12 to m13 represent the same integer.
  • X 31 to X 32 independently represent a sulfur atom, an oxygen atom, or a selenium atom. At least one of X 31 to X 32 represents a sulfur atom. It is preferable that X 31 to X 32 represent a sulfur atom.
  • the definitions of Ar 12 to Ar 13 , Ar 14 to Ar 15 and R 11 to R 14 are defined as Ar 12 to Ar 13 , Ar 14 to Ar 15 and R in the above formula (1). It is synonymous with the definition of 11 to R14 .
  • Each of m12 to m13 independently represents an integer of 1 to 2. It is preferable that m12 to m13 represent 1. It is preferable that m12 to m13 represent the same integer.
  • X 71 to X 74 independently represent a sulfur atom, an oxygen atom, or a selenium atom. At least one of X 71 to X 74 represents a sulfur atom. It is preferable that X 71 to X 74 represent a sulfur atom.
  • the definitions of Ar 12 to Ar 13 , Ar 14 to Ar 15 and R 11 to R 14 are defined as Ar 12 to Ar 13 , Ar 14 to Ar 15 and R in the above formula (1). It is synonymous with the definition of 11 to R14 .
  • Each of m12 to m13 independently represents an integer of 1 to 2. It is preferable that m12 to m13 represent 1. It is preferable that m12 to m13 represent the same integer.
  • X 31 to X 32 independently represent a sulfur atom, an oxygen atom, or a selenium atom. At least one of X 31 to X 32 represents a sulfur atom. It is preferable that X 31 to X 32 represent a sulfur atom.
  • R 11 to R 14 independently represent a hydrogen atom or a substituent.
  • Ar 16 to Ar 17 each independently represent any of the groups represented by the formulas (Ar-x1) to (Ar-x7).
  • X 71 to X 74 independently represent a sulfur atom, an oxygen atom, or a selenium atom. At least one of X 71 to X 74 represents a sulfur atom. It is preferable that X 71 to X 74 represent a sulfur atom.
  • R 11 to R 14 independently represent a hydrogen atom or a substituent.
  • Ar 16 to Ar 17 each independently represent any of the groups represented by the formulas (Ar-x1) to (Ar-x7).
  • R 11 to R 14 have the same meaning as R 11 to R 14 in the formula (1), and the preferable range is also the same.
  • Ar 14 to Ar 15 are preferably any of the groups represented by the formulas (Ar-x1) to (Ar-x7) described later.
  • Xa1 represents a sulfur atom, an oxygen atom, or a selenium atom.
  • X a1 preferably represents a sulfur atom.
  • R a1 represents a hydrogen atom or a substituent.
  • At least one of Y a1 to Y a5 preferably represents a nitrogen atom, and more preferably Y a1 represents a nitrogen atom.
  • the type of the above-mentioned substituent is not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • an alkyl group having 1 to 7 carbon atoms, a halogen atom, or a group in combination thereof is preferable, a halogen atom is more preferable, and a fluorine atom is particularly preferable.
  • R b1 represents a hydrogen atom or a substituent. * Represents the bond position.
  • the type of the above-mentioned substituent is not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • an alkyl group having 1 to 7 carbon atoms, a halogen atom, or a group in combination thereof is preferable, a halogen atom is more preferable, and a fluorine atom is particularly preferable.
  • R c1 represents a hydrogen atom or a substituent. * Represents the bond position.
  • the type of the above-mentioned substituent is not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • an alkyl group having 1 to 7 carbon atoms, a halogen atom, or a group in combination thereof is preferable, a halogen atom is more preferable, and a fluorine atom is particularly preferable.
  • X d1 to X d2 independently represent a sulfur atom, an oxygen atom, or a selenium atom. It is preferable that X d1 to X d2 represent a sulfur atom.
  • R d1 represents a hydrogen atom or a substituent. * Represents the bond position.
  • the type of the above-mentioned substituent is not particularly limited, and examples thereof include the groups exemplified by the substituent W described later. As the substituent, an alkyl group having 1 to 7 carbon atoms, a halogen atom, or a group in combination thereof is preferable, a halogen atom is more preferable, and a fluorine atom is further preferable.
  • R e1 represents a hydrogen atom or a substituent. * Represents the bond position.
  • the type of the above-mentioned substituent is not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • an alkyl group having 1 to 7 carbon atoms, a halogen atom, or a group in combination thereof is preferable, a halogen atom is more preferable, and a fluorine atom is further preferable.
  • X f1 represents a sulfur atom, an oxygen atom, or a selenium atom.
  • X f1 preferably represents a sulfur atom.
  • R f1 represents a hydrogen atom or a substituent. * Represents the bond position.
  • the type of the above-mentioned substituent is not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • an alkyl group having 1 to 7 carbon atoms, a halogen atom, or a group in combination thereof is preferable, a halogen atom is more preferable, and a fluorine atom is further preferable.
  • X g1 represents a sulfur atom, an oxygen atom, or a selenium atom.
  • X g1 preferably represents a sulfur atom.
  • R g1 represents a hydrogen atom or a substituent. * Represents the bond position.
  • the type of the above-mentioned substituent is not particularly limited, and examples thereof include the groups exemplified by the substituent W described later.
  • an alkyl group having 1 to 7 carbon atoms, a halogen atom, or a group in combination thereof is preferable, a halogen atom is more preferable, and a fluorine atom is further preferable.
  • the specific compound does not have an aliphatic hydrocarbon group having 8 or more carbon atoms as a substituent.
  • the specific compound preferably does not have an aliphatic hydrocarbon group having 6 or more carbon atoms as a substituent, more preferably does not have an aliphatic hydrocarbon group having 3 or more carbon atoms, and has a carbon number of carbon atoms. It is more preferable that it does not have two or more aliphatic hydrocarbon groups, and it is particularly preferable that it does not have an aliphatic hydrocarbon group.
  • the fact that the specific compound does not have an aliphatic hydrocarbon group having 8 or more carbon atoms means that the specific compound does not have the aliphatic hydrocarbon group itself having 8 or more carbon atoms, and the specific compound is a part of the substituent. It means both having no substituent containing an aliphatic hydrocarbon group having 8 or more carbon atoms.
  • Tables 1 to 4 Examples of combinations of possible forms of Ar 12 to Ar 15 , R 11 to R 15 , and n 12 to n 13 in the specific compound shown in the upper row are shown in Tables 1 to 4 below.
  • H represents a hydrogen atom
  • Me represents a methyl group
  • Ph represents a phenyl group
  • * represents a bond position.
  • Ar 12 or Ar 13 can take two or more kinds of first aromatic ring groups
  • the bonding order of each first aromatic ring group is not limited to the order shown in the table.
  • Ar 12 is composed of a thiazole ring and a thiophene ring
  • the binding order may be-thiazole ring-thiophene ring-or-thiophene ring-thiazole ring.
  • the molecular weight of the specific compound is preferably 400 to 1200, more preferably 400 to 900.
  • the molecular weight is 1200 or less, the vapor deposition temperature does not rise and the decomposition of the compound is unlikely to occur.
  • the molecular weight is 400 or more, the glass transition point of the vapor-film deposition film is not lowered, and the heat resistance of the photoelectric conversion element is improved.
  • the specific compound preferably has an ionization potential of -5.0 to -6.0 eV in a single membrane in terms of matching the energy level with the n-type semiconductor material described later.
  • the maximum absorption wavelength of the specific compound is not particularly limited, and is preferably in the range of 400 to 700 nm, more preferably in the range of 350 to 550 nm, and further preferably in the range of 400 to 550 nm.
  • the maximum absorption wavelength is a value measured in a solution state (solvent: chloroform) by adjusting the absorption spectrum of the specific compound to a concentration such that the absorbance becomes 0.5 to 1.
  • solvent chloroform
  • the specific compound may be used alone or in combination of two or more.
  • the content of the specific compound in the photoelectric conversion film [[(film thickness of the specific compound in terms of single layer) / (film thickness of specific compound in terms of single layer + single dye)
  • the film thickness in terms of layers + the film thickness in terms of a single layer of an n-type semiconductor material)] ⁇ 100] is preferably 15 to 75% by volume, more preferably 20 to 60% by volume, still more preferably 25 to 40% by volume. ..
  • the photoelectric conversion film contains a dye.
  • the dye an organic dye is preferable.
  • the pigments include cyanine pigments, styryl pigments, hemicyanine pigments, merocyanine pigments (including zero methine merocyanin (simple merocyanin)), rodacyanine pigments, allopolar pigments, oxonols pigments, hemioxonor pigments, squalium pigments, croconium pigments, and azamethines.
  • the molecular weight of the dye is preferably 400 to 1200, more preferably 400 to 900.
  • the maximum absorption wavelength of the dye is not particularly limited, and is preferably in the range of 400 to 700 nm, more preferably in the range of 500 to 700 nm.
  • the method for measuring the maximum absorption wavelength of the specific compound described above can be used.
  • the dye may be used alone or in combination of two or more.
  • Dye content in photoelectric conversion film [[(Dye single layer equivalent film thickness) / (Dye single layer equivalent film thickness + Dye single layer equivalent film thickness + n-type semiconductor material single) The film thickness)] ⁇ 100] is preferably 15 to 75% by volume, more preferably 20 to 60% by volume, and even more preferably 25 to 40% by volume.
  • the photoelectric conversion film includes an n-type semiconductor material.
  • the n-type semiconductor material is an acceptor-type organic semiconductor material (compound), and refers to an organic compound having a property of easily accepting electrons.
  • the n-type semiconductor material is preferably an organic compound having a higher electron affinity than the specific compound when used in contact with the above-mentioned specific compound. Further, the n-type semiconductor material is preferably an organic compound having a higher electron affinity than the dye when used in contact with the above-mentioned dye.
  • the electron affinity of the n-type semiconductor material is preferably 3.0 to 5.0 eV.
  • For the electron affinity value use the reciprocal value (value multiplied by -1) of the LUMO value obtained by the calculation of B3LYP / 6-31G (d) using Gaussian '09 (software manufactured by Gaussian). Can be done.
  • n-type semiconductor material examples include fullerene compounds selected from the group consisting of fullerene and derivatives thereof; fused aromatic carbocyclic compounds such as naphthalene, anthracene, phenanthrene, tetracene, pyrene, perylene, fluorantene, and derivatives thereof.
  • Nitrogen atoms such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acrydin, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, and thiazole, oxygen atoms, and A 5- to 7-membered heterocyclic compound having at least one sulfur atom; a polyarylene compound; a fluorene compound; a cyclopentadiene compound; a silyl compound; 1,4,5,8-naphthalenetetracarboxylic acid anhydride; 1,4 , 5,8-Naphthalenetetracarboxylic acid anhydride imide derivative and oxadiazole derivative; anthracinodimethane derivative; diphenylquinone derivative; vasocproin,
  • fullerenes selected from the group consisting of fullerenes and derivatives thereof are preferable.
  • fullerenes include fullerenes C60, fullerenes C70, fullerenes C76, fullerenes C78, fullerenes C80, fullerenes C82, fullerenes C84, fullerenes C90, fullerenes C96, fullerenes C240, fullerenes C540, and mixed fullerenes.
  • fullerene C60 is preferable.
  • the fullerene derivative include compounds in which a substituent is added to fullerene.
  • the substituent an alkyl group, an aryl group, or a heterocyclic group is preferable.
  • the fullerene derivative the compound described in JP-A-2007-123707 is preferable.
  • Fullerenes may be used alone or in combination of two or more.
  • the content of the fullerene with respect to the total content of each n-type semiconductor material [[(thickness of fullerene in terms of single layer) / (each n in terms of single layer) The total film thickness of the type semiconductor material)] ⁇ 100] is preferably 50 to 100% by volume, more preferably 80 to 100% by volume.
  • the molecular weight of the n-type semiconductor material is preferably 200 to 1200, more preferably 200 to 1000.
  • the n-type semiconductor material may be used alone or in combination of two or more.
  • Content of n-type semiconductor material in the photoelectric conversion film [[(Film thickness of n-type semiconductor material in single-layer conversion) / (Film thickness of specific compound in single-layer conversion + film thickness of dye in single-layer conversion)
  • the film thickness of the + n-type semiconductor material in terms of a single layer)] ⁇ 100] is preferably 15 to 75% by volume, more preferably 20 to 60% by volume, still more preferably 20 to 40% by volume.
  • Examples of the film forming method of the photoelectric conversion film include a dry film forming method.
  • Examples of the dry film forming method include a vapor deposition method (particularly, a vacuum vapor deposition method), a sputtering method, an ion plating method, a physical vapor deposition method such as an MBE (Molecular Beam Epitaxy) method, and plasma polymerization.
  • a CVD (Chemical Vapor Deposition) method can be mentioned.
  • the vacuum vapor deposition method is preferable as the film forming method.
  • the manufacturing conditions such as the degree of vacuum and the vapor deposition temperature can be set according to a conventional method.
  • the electrodes (upper electrode (transparent conductive film) 15 and lower electrode (conductive film) 11) are made of a conductive material.
  • the conductive material include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Since light is incident from the upper electrode 15, it is preferable that the upper electrode 15 is transparent to the light to be detected.
  • the material constituting the upper electrode 15 include antimony, fluorine-doped tin oxide (ATO: Antimony Tin Oxide, FTO: Fluorine topped Tin Oxide), tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO).
  • Indium Tin Oxide and conductive metal oxides such as indium oxide (IZO); metal thin films such as gold, silver, chromium, aluminum, and nickel; these metals and conductive metal oxidation.
  • conductive metal oxides such as indium oxide (IZO)
  • metal thin films such as gold, silver, chromium, aluminum, and nickel
  • these metals and conductive metal oxidation Mixtures or laminates with materials; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; carbon materials such as carbon nanotubes, graphene, and acetylene black.
  • a conductive metal oxide is preferable from the viewpoint of high conductivity and transparency.
  • the sheet resistance in the solid-state image pickup device incorporating the photoelectric conversion element according to the present embodiment is preferably 100 to 10000 ⁇ / ⁇ , and the degree of freedom in the range of the film thickness that can be thinned is large.
  • Increasing the light transmittance is preferable from the viewpoint of increasing the light absorption in the photoelectric conversion film and increasing the photoelectric conversion ability.
  • the film thickness of the upper electrode 15 is preferably 5 to 100 nm, more preferably 5 to 20 nm, from the viewpoint of suppressing the leakage current, increasing the resistance value of the thin film, and increasing the transmittance.
  • the lower electrode 11 may be transparent or may reflect light without being transparent, depending on the intended use.
  • the material constituting the lower electrode 11 include tin oxide (ATO, FTO) doped with antimony or fluorine, tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO).
  • tin oxide ATO, FTO
  • ITO indium oxide
  • IZO indium zinc oxide
  • metal oxides metals such as gold, silver, chromium, nickel, titanium, tungsten, aluminum, and conductive compounds such as oxides or nitrides of these metals (as an example, titanium nitride (TiN)).
  • the method for forming the electrode is not particularly limited and can be appropriately selected depending on the electrode material. Specific examples include a printing method and a wet method such as a coating method; a physical method such as a vacuum vapor deposition method, a sputtering method, and an ion plating method; a chemical method such as CVD and a plasma CVD method. Be done.
  • the methods for forming the electrode include, for example, an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (sol-gel method, etc.), and a dispersion of indium tin oxide. Examples include methods such as coating.
  • the photoelectric conversion element has one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film.
  • the intermediate layer include a charge blocking film such as an electron blocking film and a hole blocking film.
  • the photoelectric conversion element preferably has a charge blocking film in that the characteristics of the photoelectric conversion element (photoelectric conversion efficiency, responsiveness, etc.) are more excellent.
  • the electron blocking film is a donor organic semiconductor material (compound).
  • Examples of the electron blocking film include p-type organic semiconductors.
  • the p-type organic semiconductor is, for example, a triarylamine compound (for example, N, N'-bis (3-methylphenyl)-(1,1'-biphenyl) -4,4'-diamine (TPD), 4,4.
  • TPD triarylamine
  • '-Bis [N- (naphthyl) -N-phenyl-amino] biphenyl ( ⁇ -NPD) the compound described in paragraphs [0128] to [0148] of JP2011-228614A, JP-A-2011-176259.
  • cyanine compounds oxonol compounds, polyamine compounds, indol compounds, pyrrol compounds, pyrazole compounds, polyarylene compounds, condensed aromatic carbocyclic compounds ( For example, naphthalene derivative, anthracene derivative, phenanthrene derivative, tetracene derivative, pentacene derivative, pyrene derivative, perylene derivative, and fluorantene derivative), porphyrin compound, phthalocyanine compound, triazole compound, oxadiazole compound, imidazole compound, polyarylalkane compound.
  • p-type organic semiconductor examples include compounds having a smaller ionization potential than the n-type semiconductor material, and if this condition is satisfied, the above-mentioned dye can also be used.
  • a polymer material can also be used as the electron blocking film.
  • the polymer material include polymers such as phenylene vinylene, fluorene, carbazole, indole, pyrene, pyrrole, picolin, thiophene, acetylene and diacetylene, and derivatives thereof.
  • the electron blocking film may be composed of a plurality of films or may be composed of an inorganic material.
  • the inorganic material has a higher dielectric constant than the organic material, when the inorganic material is used for the electron blocking film, a large voltage is applied to the photoelectric conversion film, and the photoelectric conversion efficiency becomes high.
  • the inorganic material as the electron blocking film is, for example, calcium oxide, chromium oxide, copper oxide, manganese oxide, cobalt oxide, nickel oxide, copper oxide, gallium copper oxide, strontium oxide copper, niobium oxide, molybdenum oxide, indium copper oxide. , Indium silver oxide, and iridium oxide.
  • the electron blocking film may be used alone or in combination of two or more.
  • the hole blocking film is an acceptor organic semiconductor material (compound).
  • Examples of the hole blocking film include the above-mentioned n-type semiconductor material and the like.
  • the hole blocking film may be used alone or in combination of two or more.
  • the method for producing the charge blocking film is not particularly limited, and examples thereof include a dry film forming method and a wet film forming method.
  • the dry film forming method include a vapor deposition method and a sputtering method.
  • the vapor deposition method may be any of a physical vapor deposition (PVD) method and a chemical vapor deposition (CVD) method, and a physical vapor deposition method such as a vacuum vapor deposition method is preferable.
  • the wet film forming method include an inkjet method, a spray method, a nozzle printing method, a spin coating method, a dip coating method, a casting method, a die coating method, a roll coating method, a bar coating method, and a gravure coating method.
  • the wet film forming method the inkjet method is preferable from the viewpoint of high-precision patterning.
  • the thickness of the charge blocking film is preferably 3 to 200 nm, more preferably 5 to 100 nm, and even more preferably 5 to 30 nm, respectively.
  • the photoelectric conversion element may further have a substrate.
  • the substrate included in the photoelectric conversion element include a semiconductor substrate, a glass substrate, and a plastic substrate.
  • the position of the substrate in the photoelectric conversion element is not particularly limited, and a conductive film, a photoelectric conversion film, and a transparent conductive film are usually laminated on the substrate in this order.
  • the photoelectric conversion element may further have a sealing layer.
  • the performance of the photoelectric conversion element may be deteriorated due to deterioration factors such as water molecules. Therefore, a photoelectric conversion film is provided by using a dense metal oxide, metal nitride, ceramics such as metal nitride oxide, or a sealing layer such as diamond-like carbon (DLC: Diamond-like Carbon) that does not allow water molecules to permeate. By covering and sealing the whole, it is possible to prevent performance deterioration due to water molecules and the like.
  • the sealing layer may be selected and manufactured from a material according to, for example, paragraphs [0210] to [0215] of JP-A-2011-082508.
  • the photoelectric conversion element includes, for example, an image pickup element and an optical sensor.
  • the image pickup device is an element that converts the optical information of an image into an electric signal.
  • each photoelectric conversion element pixel
  • each photoelectric conversion element can convert an optical signal into an electric signal, and the electric signal can be sequentially output to the outside of the image pickup element for each pixel.
  • each pixel is composed of one or more photoelectric conversion elements and one or more transistors.
  • the image pickup element is mounted on, for example, a digital camera, an image pickup element such as a digital video camera, an electronic endoscope, and an image pickup module such as a mobile phone.
  • the optical sensor may use the photoelectric conversion element alone, or may be used as a line sensor in which the photoelectric conversion elements are arranged in a straight line, or a two-dimensional sensor in which the photoelectric conversion elements are arranged in a plane.
  • the present invention also relates to compounds.
  • the compound of the present invention is the above-mentioned specific compound.
  • the specific compound is particularly useful as a material for a photoelectric conversion film used in an image sensor, an optical sensor, or a photovoltaic cell.
  • the specific compound can also be used as a coloring material, a liquid crystal material, an organic semiconductor material, a charge transport material, a pharmaceutical material, and a fluorescence diagnostic agent material.
  • the dyes (B-1) to (B-20) shown below were used in the examples.
  • the dye mainly exhibits absorption in green light to red light (light having a wavelength of 500 to 700 nm).
  • the photoelectric conversion element includes a lower electrode 11, an electron blocking film 16A, a photoelectric conversion film 12, a hole blocking film 16B, and an upper electrode 15.
  • amorphous ITO is formed on a glass substrate by a sputtering method to form a lower electrode 11 (thickness: 30 nm), and the following compound (C-1) is further vacuumed on the lower electrode 11.
  • a film was formed by a heat vapor deposition method to form an electron blocking film 16A (thickness: 30 nm).
  • a specific compound, an n-type semiconductor material, and a dye shown in the table described later were vapor-deposited on the electron blocking film 16A to form a photoelectric conversion film 12. Further, the following compound (C-2) was deposited on the photoelectric conversion film 12 to form a hole blocking film 16B (thickness: 10 nm). Amorphous ITO was formed on the hole blocking film 16B by a sputtering method to form an upper electrode 15 (transparent conductive film) (thickness: 10 nm).
  • Example 1 After forming a SiO film as a sealing layer on the upper electrode 15 by a vacuum deposition method, an aluminum oxide (Al 2 O 3 ) layer is formed on the SiO film by an ALCVD (Atomic Layer Chemical Vapor Deposition) method, and Example 1 The photoelectric conversion element of the above was manufactured. Further, the photoelectric conversion elements of Examples 2 to 51 and Comparative Examples 1 to 4 were produced by the same procedure as in Example 1 except that each component was used according to Tables 5 to 6.
  • Equation (S) (integral value of photoelectric conversion efficiency in visible light (light having a wavelength of 400 to 700 nm) of each example or comparative example) / (photoelectric in visible light (light having a wavelength of 400 to 700 nm) of Example 1) (Integral value of conversion efficiency) (Evaluation criteria)
  • C Relative ratio of integrated value of photoelectric conversion efficiency is 1 .1 or more and less than 1.2
  • E Relative ratio of integrated values of photoelectric conversion efficiency is less than 0.8
  • the photoelectric conversion efficiency ratio was calculated from the following formula using the integrated value of the photoelectric conversion efficiency in visible light (light having a wavelength of 400 to 700 nm), and evaluated according to the following evaluation criteria.
  • Electric field strength dependence of photoelectric conversion efficiency (Integrated value of photoelectric conversion efficiency in visible light (light with wavelength of 400 to 700 nm) at electric field strength 1.5 x 105 V / cm) / (Electric field strength 2.5 x 10) Integrated value of photoelectric conversion efficiency in visible light (light with wavelength of 400 to 700 nm) at 5 V / cm) (Evaluation criteria)
  • Electric field strength dependence of photoelectric conversion efficiency is 0.65 or more
  • D Electric field strength dependence of photoelectric conversion efficiency is less than 0.65
  • the features of each photoelectric conversion element of the example or the comparative example, and the results of the tests conducted using each photoelectric conversion element of the example or the comparative example are shown in the following table. Each description in the table below indicates the following.
  • the "Ar 11 " column indicates a ring constituting a condensed polycyclic aromatic group represented by Ar 11 .
  • Ar 14 and Ar 15 " column a monocyclic aryl group, a monocyclic heteroaryl group, a condensed aryl group having two rings, and a total number of rings, represented by Ar 14 to Ar 15 , are two.
  • the ring constituting the condensed heteroaryl group of is shown.
  • the "Substituents of Ar 14 and Ar 15 " column represents the substituents of the second aromatic ring groups represented by Ar 14 to Ar 15 .
  • the column "-(Ar 11 ) n11-” indicates whether- (Ar 11 ) n11 -in each specific compound has any of the groups represented by the formulas (A1) to (A33).
  • the "ratio of each component” column shows the ratio of the film thickness (content) of each component in the photoelectric conversion film in terms of a single layer.
  • the group represented by (Ar 11 ) n11 in the formula (1) is a group represented by the formula (A3) and a group represented by the formula (A4).
  • the group represented by n11 is a group represented by the formula (A3), a group represented by the formula (A4), a group represented by the formula (A5), and a group represented by the formula (A6).
  • the group represented by the formula (A28), the group represented by the formula (A29), and the group represented by the formula (A30) it was confirmed that the efficiency is further excellent.
  • the pyridine ring and the thiazole ring were used in "Ar 14 and Ar 15 ", but the effect was inferior to that of the other examples. Examples 12, 14, 16-19, 22-25, 27-29, 31-35, 37-42 and 44-49, and Examples 11, 13, 15, 20-21, 26, 30, 36 and 43.
  • Ar 14 to Ar 15 consisted of a group consisting of a pyridine ring group, a pyrimidine ring group, a thiazole ring group, a benzothiazole ring group, a thiazorothiazole ring group, a quinoline ring group, and an isoquinoline ring group.
  • an aromatic ring group selected from the group consisting of a pyridine ring group, a pyrimidine ring group, a thiazole ring group, a benzothiazole ring group, a thiazolothiazole ring group, a quinoline ring group, and an isoquinoline ring group.
  • Thiophen ring group or thiazole ring group it was confirmed that the effect is more excellent.

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Abstract

La présente invention concerne : un élément de conversion photoélectrique qui présente un excellent rendement de conversion photoélectrique par rapport à la lumière visible (en particulier, la lumière ayant une longueur d'onde de 400 à 700 nm), et qui présente également une excellente dépendance à l'intensité du champ électrique ; un élément d'imagerie ; un capteur optique ; et un composé. Cet élément de conversion photoélectrique comprend un film conducteur, un film de conversion photoélectrique et un film conducteur transparent, dans l'ordre indiqué. Le film de conversion photoélectrique contient un composé représenté par la formule (1), un colorant et un matériau semi-conducteur de type n.
PCT/JP2021/031165 2020-09-01 2021-08-25 Élément de conversion photoélectrique, élément d'imagerie, capteur optique et composé WO2022050146A1 (fr)

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