WO2020261933A1 - Photoelectric conversion element, imaging element, optical sensor, and photoelectric conversion element material - Google Patents

Photoelectric conversion element, imaging element, optical sensor, and photoelectric conversion element material Download PDF

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Publication number
WO2020261933A1
WO2020261933A1 PCT/JP2020/022287 JP2020022287W WO2020261933A1 WO 2020261933 A1 WO2020261933 A1 WO 2020261933A1 JP 2020022287 W JP2020022287 W JP 2020022287W WO 2020261933 A1 WO2020261933 A1 WO 2020261933A1
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substituent
group
photoelectric conversion
conversion element
formula
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PCT/JP2020/022287
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French (fr)
Japanese (ja)
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花木　直幸
知昭 吉岡
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富士フイルム株式会社
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Priority to JP2021527593A priority Critical patent/JP7382404B2/en
Publication of WO2020261933A1 publication Critical patent/WO2020261933A1/en

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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
    • 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 sensor, an optical sensor, and a material for a photoelectric conversion element.
  • Patent Document 1 discloses a photoelectric conversion element containing a predetermined compound.
  • a photoelectric conversion element is required to have excellent responsiveness when receiving light.
  • the compound represented by the formula (1) described later is a compound represented by the formula (2) described later, a compound represented by the formula (3) described later, or a compound represented by the formula (4) described later.
  • the present invention it is possible to provide a photoelectric conversion element having excellent responsiveness. Further, according to the present invention, it is possible to provide a material for an image sensor, an optical sensor, and a photoelectric conversion element.
  • the "substituent” includes a group exemplified by the substituent W described later, unless otherwise specified.
  • the substituent W is, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkyl group, a bicycloalkyl group, and an alkenyl group).
  • a halogen atom fluorine atom, chlorine atom, bromine atom, iodine atom, etc.
  • an alkyl group including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group
  • an alkenyl group including a cycloalkyl group, a bicycloalkyl group, and an alkenyl group.
  • each of the above-mentioned groups may further have a substituent (for example, one or more groups of each of the above-mentioned groups) if possible.
  • a substituent for example, one or more groups of each of the above-mentioned groups
  • an alkyl group which may have a substituent is also included as a form of the substituent W.
  • the substituent W has a carbon atom
  • the number of carbon atoms of the substituent W is, for example, 1 to 20.
  • the number of atoms other than the hydrogen atom of the substituent W is, for example, 1 to 30.
  • the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6.
  • the alkyl group may be linear, branched, or cyclic. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, an n-hexyl group, a cyclopentyl group and the like.
  • the alkyl group may be, for example, a cycloalkyl group, a bicycloalkyl group, or a tricycloalkyl group, and may have a cyclic structure thereof as a partial structure.
  • the substituent that the alkyl group may have is not particularly limited, and examples thereof include a substituent W, and an aryl group (preferably 6 to 18 carbon atoms, more preferably). 6), a heteroaryl group (preferably 5 to 18, more preferably 5 to 6 carbon atoms), or a halogen atom (preferably a fluorine atom or a chlorine atom).
  • the above-mentioned alkyl group is preferable as the alkyl group portion of the alkoxy group.
  • the above-mentioned alkyl group is preferable as the alkyl group moiety in the alkylthio group.
  • the substituent that the alkoxy group may have includes the same examples as the substituent in the alkyl group that may have a substituent.
  • the substituent which the alkylthio group may have includes the same examples as the substituent in the alkyl group which may have a substituent.
  • the alkenyl group may be linear, branched chain, or cyclic.
  • the alkenyl group preferably has 2 to 20 carbon atoms.
  • the substituent which the alkenyl group may have includes the same examples as the substituent in the alkyl group which may have a substituent.
  • the alkynyl group may be linear, branched chain, or cyclic.
  • the alkynyl group preferably has 2 to 20 carbon atoms.
  • the substituent which the alkynyl group may have includes the same examples as the substituent in the alkyl group which may have a substituent.
  • the aryl group is preferably an aryl group having 6 to 18 ring members, unless otherwise specified.
  • the aryl group may be monocyclic or polycyclic.
  • the aryl group is preferably, for example, a phenyl group, a naphthyl group, an anthryl group, or a phenanthrenyl group.
  • the substituent which the aryl group may have is not particularly limited, and examples thereof include a substituent W, and an alkyl group which may have a substituent (preferably).
  • the number of carbon atoms is preferably 1 to 10), and a methyl group is more preferable.
  • the heteroaryl group includes a hetero atom such as a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and / or a boron atom.
  • a heteroaryl group having a monocyclic or polycyclic ring structure is preferable.
  • the number of carbon atoms in the ring member atom of the heteroaryl group is not particularly limited, and is preferably 3 to 18 and more preferably 3 to 5.
  • the number of heteroatoms in the ring member atom of the heteroaryl group is not particularly limited, and is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 to 2.
  • the number of ring members of the heteroaryl group is not particularly limited, and is preferably 5 to 8, more preferably 5 to 7, and even more preferably 5 to 6.
  • the heteroaryl group includes a fryl group, a pyridyl group, a quinolyl group, an isoquinolyl group, an acridinyl group, a phenanthridinyl group, a pteridinyl group, a pyrazinyl group, a quinoxalinyl group, a pyrimidinyl group, a quinazolyl group, a pyridadinyl group, a synnolinyl group and a phthalazinyl group.
  • the substituent the substituent
  • the silyl group which may have a substituent includes, for example, a group represented by —Si ( RS1 ) ( RS2 ) ( RS3 ).
  • R S1 , R S2 , and R S3 independently have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and a substituent.
  • 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 deuterium 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 "specific compound”), and n-type semiconductor materials.
  • a compound represented by the formula (1)
  • specific compound also referred to as "specific compound”
  • n-type semiconductor materials n-type semiconductor materials.
  • the specific compound Since the specific compound has such a characteristic structure, it is presumed that the responsiveness of the photoelectric conversion element is excellent when the specific compound is used for the photoelectric conversion element. Further, the photoelectric conversion element having a photoelectric conversion film manufactured by using a specific compound is also excellent in heat resistance. It is believed that this is due to the rigid structure of the particular compound.
  • the excellent responsiveness and / or heat resistance of the obtained photoelectric conversion element is also simply referred to as "the effect of the present invention is 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. Further, when the photoelectric conversion element 10a (or 10b) is used, a voltage can be applied. In this case, it is preferable that the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and a voltage of 1 ⁇ 10 -5 to 1 ⁇ 10 7 V / cm is applied between the pair of electrodes. From the viewpoint of performance and power consumption, the applied voltage is more preferably 1 ⁇ 10 -4 to 1 ⁇ 10 7 V / cm, further preferably 1 ⁇ 10 -3 to 5 ⁇ 10 6 V / cm.
  • the voltage application method it is preferable to apply the voltage so that the electron blocking film 16A side serves as the cathode and the photoelectric conversion film 12 side serves as 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 sensor application.
  • the photoelectric conversion film is a film containing a specific compound.
  • the specific compound will be described in detail.
  • R a1 and R a2 each independently represent a hydrogen atom or a substituent.
  • substituent W which includes a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent.
  • An alkylthio group which may have a substituent, a silyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent is preferable.
  • R a1 and R a2 are each independently preferably a hydrogen atom.
  • R a1 when a plurality of R a1 is present, R a1 may have respectively be the same or different where there exist a plurality. In the formula (1), when a plurality of R a2 are present, R a2 may have respectively be the same or different where there exist a plurality.
  • the 5-membered ring containing X 1 and Y 1 is an aromatic hetero ring
  • the 5-membered ring containing X 2 and Y 2 is an aromatic hetero ring.
  • it is preferable that one of X 1 and Y 1 represents -CR a1 and the other represents -O-, -S-, or -Se-.
  • Ra3 may have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and a substituent.
  • R a3 when a plurality of R a3 is present, R a3 may have respectively be the same or different where there exist a plurality.
  • Ar 1 to Ar 4 each independently represent an aromatic ring group which may have a substituent.
  • the aromatic ring group may be monocyclic or polycyclic.
  • the aromatic ring group has one or more (preferably 1 to 3) heteroatoms (nitrogen atom, sulfur atom, oxygen atom, selenium atom, tellurium atom, phosphorus atom, silicon atom, and / or boron atom, etc.) as ring member atoms. ) May or may not be included.
  • the number of ring members of the aromatic ring group is preferably 5 to 18.
  • the monocyclic aromatic ring group includes, for example, a benzene ring group, a frill ring group, a pyridine ring group, a pyrazine ring group, a pyrimidine ring group, and a pyridazine ring group.
  • a polycyclic aromatic ring group is a group formed by condensing single rings having aromaticity.
  • a polycyclic aromatic ring group two or more of the ring member atoms of each monocycle (monocycle having aromaticity) constituting the polycyclic aromatic ring are other singles constituting the polycyclic aromatic ring group. It is also a ring member atom of a ring (a single ring having aromaticity).
  • the aromatic ring group is a polycyclic aromatic ring group
  • the polycyclic aromatic ring group includes, for example, a naphthalene ring group, an anthracene ring group, a quinoline ring group, an isoquinolin ring group, an acrydin ring group, and phenanthridin.
  • Ring group pteridine ring group, quinoxaline ring group, quinazoline ring group, cinnoline ring group, phthalazine ring group, benzoxazole ring group, benzothiazole ring group, benzimidazole ring group, indazole ring group, benzoisooxazole ring group, benzoiso Thiazole ring group, benzofuran ring group, benzothiophene ring group, benzoselenophen ring group, dibenzofuran ring group, dibenzothiophene ring group, dibenzoselenophen ring group, thienothiophene ring group, thienopyrol ring group, dithienopyrrole ring group, indol ring group , Imidazopyridine ring group, and carbazole ring group.
  • the substituent that the aromatic ring group in Ar 1 and Ar 2 may have is not L 1 . Further, the substituent that the aromatic ring group in Ar 2 may have is not Ar 1 . Similarly, the substituent that the aromatic ring group in Ar 3 and Ar 3 may have is not L 2 . Further, the substituent that the aromatic ring group in Ar 3 may have is not Ar 4 . Further, Ar 1 and Ar 2 are directly bonded to each other by a single bond specified in the formula (1). Similarly, Ar 3 and Ar 4 are directly bonded to each other by a single bond specified in the formula (1).
  • Examples of the substituent which the aromatic ring group in Ar 1 to Ar 4 may have include the substituent W, and among them, a halogen atom, an alkyl group which may have a substituent, and a substituent are included.
  • a aryl group which may have a substituent or a heteroaryl group which may have a substituent is preferable.
  • the aromatic ring group further has an aromatic ring group as a substituent.
  • Examples of the above-mentioned "aromatic ring group as a substituent” include the above-mentioned monocyclic aromatic ring group and polycyclic aromatic ring group.
  • the aromatic ring group further has an aromatic ring group as a substituent
  • one or more of these aromatic ring groups may have further different substituents.
  • the different substituents of each of these aromatic ring groups may be bonded to each other. That is, these aromatic ring groups may be bonded to each other by forming a further different ring between them.
  • the further different ring formed between these aromatic ring groups is a non-aromatic ring.
  • the aromatic ring group A further has an aromatic ring group B as a substituent
  • the aromatic ring group A may further have a substituent A
  • the aromatic ring group B further contains a substituent B. You may have.
  • Substituent A and substituent B may be bonded to each other to form a further different ring (non-aromatic ring) between the aromatic ring group A and the aromatic ring group B.
  • aromatic ring groups are bonded to each other by forming a further different ring (non-aromatic ring) between them, for example, these aromatic ring groups jointly form a fluorene ring group.
  • Ar 1 to Ar 4 preferably Ar 1 and / or Ar 4
  • Ar 2 and Ar 3 are preferably a monocyclic aromatic ring group which may have a substituent, and more preferably a benzene ring group which may have a substituent. Further, from the viewpoint that the effect of the present invention is more excellent, it is preferable that at least one of Ar 1 and Ar 2 is a benzene ring group which may have a substituent, and at least one of Ar 3 and Ar 4 has a substituent. It is also preferable that it is a benzene ring group which may have. As will be described later, Ar 1 and Ar 2 may have a bond via L 1 in addition to the single bond specified in the equation (1).
  • Ar 1 and Ar 2 are benzene ring groups which may have a substituent
  • Ar 1 and Ar 2 have a bond via L 1
  • Ar 1 and Ar 2 are jointly used.
  • a fluorene ring group which may have a substituent may be formed.
  • Ar 3 and Ar 4 may have a bond via L 2 in addition to the single bond specified in the formula (1).
  • Ar 3 and Ar 4 are benzene ring groups which may have a substituent
  • Ar 3 and Ar 4 have a bond via L 2
  • Ar 3 and Ar 4 are jointly used.
  • a fluorene ring group which may have a substituent may be formed.
  • Ar 1 and Ar 4 are polycyclic aromatic ring groups which may have substituents or groups represented by the formula (R), respectively. It is preferable to have it.
  • the number of ring members of the polycyclic aromatic ring group is preferably 9 to 18.
  • Examples of the polycyclic aromatic ring group are as described above, and a naphthalene ring group or a benzothiophene ring group is preferable.
  • * 1 and * 2 independently represent the coupling positions. Specifically, in Ar 1 which is a group represented by the formula (R), * 1 represents the bonding position with Ar 2 and * 2 represents the bonding position with (L 1 ) m 1 . In Ar 4 which is a group represented by the formula (R), * 1 represents a bond position with Ar 3 and * 2 represents a bond position with (L 2 ) m 2 . However, as described later, m1 and m2 may be 0. In Ar 1 which is a group represented by the formula (R), when m1 is 0, * 2 does not exist. In Ar 4 which is a group represented by the formula (R), when m2 is 0, * 2 does not exist.
  • Ar X represents a monocyclic aromatic ring group which may have a substituent other than Ar Y.
  • Examples of the monocyclic aromatic ring group are as described above, and among them, a benzene ring group is preferable.
  • Ar Y represents an aromatic ring group which may have a substituent.
  • Examples of the aromatic ring group of Ar Y include the above-mentioned monocyclic aromatic ring group and the above-mentioned polycyclic aromatic ring group, and among them, the benzene ring group is preferable.
  • the monocyclic aromatic ring group in Ar X and the aromatic ring group in Ar Y have ring-membered atoms bonded to each other by a single bond.
  • Examples of the substituent that the monocyclic aromatic ring group in Ar X may have other than Ar Y and the substituent that the aromatic ring group in Ar Y may have include the substituent W. It is also preferable that the monocyclic aromatic ring group in Ar X has no substituent other than Ar Y. Further, the substituent which the aromatic ring group may have in Ar Y has a halogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Heteroaryl groups may be preferred. However, the substituent that the monocyclic aromatic ring group in Ar X may have other than Ar Y and the substituent that the aromatic ring group in Ar Y may have do not bond to each other. That is, Ar X and Ar Y are not combined except for the single bond specified in the formula (R). For example, the group represented by the formula (R) does not include a fluorene ring group.
  • m1 and m2 independently represent 0 or 1, respectively.
  • L 1 and L 2 independently form -S-, -O-, -Se- , -SiR a4 R a5- , -NR a6- , or -CR a7 R a8- , respectively.
  • R a4 to R a8 are independently hydrogen atom, halogen atom, alkyl group which may have a substituent, alkoxy group which may have a substituent, and an alkylthio group which may have a substituent.
  • L 1 and L 2 each independently, -CR a7 R a8 - preferably, R a7 and R a8 are -CR a7 R a8 is an alkyl group which may have a substituent - are more preferred, -C (CH 3 ) 2 -is more preferable.
  • L 1 is directly bonded to each aromatic ring group in Ar 1 and Ar 2 .
  • L 2 is directly attached to the respective aromatic ring groups in Ar 3 and Ar 4 .
  • the compound represented by the formula (1) is represented by the compound represented by the formula (2), the compound represented by the formula (3), or the compound represented by the formula (4). It is preferably a compound. Among them, the compound represented by the formula (1) is more preferably the compound represented by the formula (3).
  • Y 3 and Y 4 independently represent -O-, -S-, or -Se-, respectively.
  • R 1 to R 4 independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. It represents an alkylthio group which may have a substituent, a silyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.
  • Ar 1 to Ar 4 each independently represent an aromatic ring group which may have a substituent.
  • m1 and m2 independently represent 0 or 1, respectively.
  • L 1 and L 2 independently form -S-, -O-, -Se- , -SiR a4 R a5- , -NR a6- , or -CR a7 R a8- , respectively.
  • R a4 to R a8 independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent.
  • alkylthio group which may have a substituent a silyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, Alternatively, it represents a heteroaryl group which may have a substituent.
  • m1 represents 0, L 1 is absent, and Ar 1 and Ar 2 are connected only by a single bond, which is specified in the above formula (2).
  • m2 represents 0, L 2 does not exist, and Ar 3 and Ar 4 are connected only by the single bond specified in the above equation (2).
  • Ar 1 to Ar 4 , m1, m2, L 1 , L 2 and R a4 to R a8 in the formula (2) are Ar 1 to Ar 4 , m1, m2, L 1 , in the formula (1). It is the same as L 2 and R a4 to R a8 , respectively.
  • Y 3 and X 3 independently represent -O-, -S-, or -Se-, respectively.
  • R 1 to R 3 and R 5 are independently a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent, respectively.
  • Ar 1 to Ar 4 each independently represent an aromatic ring group which may have a substituent.
  • m1 and m2 independently represent 0 or 1, respectively.
  • L 1 and L 2 independently form -S-, -O-, -Se- , -SiR a4 R a5- , -NR a6- , or -CR a7 R a8- , respectively.
  • R a4 to R a8 independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent.
  • alkylthio group which may have a substituent a silyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, Alternatively, it represents a heteroaryl group which may have a substituent.
  • m1 represents 0, L 1 is absent, and Ar 1 and Ar 2, are connected only by a single bond, which is specified in the above formula (3).
  • m2 represents 0, L 2 does not exist, and Ar 3 and Ar 4 are connected only by the single bond specified in the above equation (3).
  • Ar 1 to Ar 4 , m1, m2, L 1 , L 2 and R a4 to R a8 in the formula (3) are Ar 1 to Ar 4 , m1, m2, L 1 , L 1 in the formula (1). It is the same as L 2 and R a4 to R a8 , respectively.
  • X 3 and X 4 independently represent -O-, -S-, or -Se-, respectively.
  • R 1 to R 2 and R 5 to R 6 independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and an alkoxy group which may have a substituent.
  • Ar 1 to Ar 4 each independently represent an aromatic ring group which may have a substituent.
  • m1 and m2 independently represent 0 or 1, respectively.
  • L 1 and L 2 independently form -S-, -O-, -Se- , -SiR a4 R a5- , -NR a6- , or -CR a7 R a8- , respectively.
  • R a4 to R a8 independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent.
  • alkylthio group which may have a substituent a silyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, Alternatively, it represents a heteroaryl group which may have a substituent.
  • m1 represents 0, L 1 is absent, and Ar 1 and Ar 2, are connected only by a single bond which is expressly in the formula (4).
  • m2 represents 0, L 2 does not exist, and Ar 3 and Ar 4 are connected only by the single bond specified in the above equation (4).
  • Ar 1 ⁇ Ar 4 in, m1, m2, L 1, L 2 and,, R a4 ⁇ R a8 are, Ar 1 ⁇ Ar 4 in the formula (1), m1, m2, L 1, It is the same as L 2 and R a4 to R a8 , respectively.
  • the molecular weight of the specific compound is not particularly limited, and is preferably 425 to 1200, more preferably 450 to 900. When the molecular weight is 1200 or less, the vapor deposition temperature does not rise and the decomposition of the compound is unlikely to occur. When the molecular weight is 425 or more, the glass transition point of the vapor-deposited film is not lowered, and the heat resistance of the photoelectric conversion element is improved.
  • the specific compound may be used alone or in combination of two or more.
  • the specific compound is particularly useful as a material for a photoelectric conversion film used in an image sensor or an optical sensor.
  • 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 specific compound is preferably a compound having 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, for example, 300 to 500 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.
  • the maximum absorption wavelength of the photoelectric conversion film is not particularly limited, and is preferably in the range of, for example, 300 to 700 nm.
  • the photoelectric conversion film contains an n-type semiconductor material as a component other than the above-mentioned specific compound.
  • 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. More specifically, the n-type semiconductor material refers to an organic compound having a higher electron affinity than the specific compound when used in contact with the above-mentioned specific compound.
  • the electron affinity of the n-type semiconductor material is preferably 3.0 to 5.0 eV.
  • the n-type semiconductor material includes, for example, fullerenes selected from the group consisting of fullerene and derivatives thereof, condensed aromatic carbocyclic compounds (for example, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and , Fluolanthene derivative); 5- to 7-membered heterocyclic compound having at least one nitrogen atom, oxygen atom, and sulfur atom (eg, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxalin, quinazoline, phthalazine) , Synnoline, Isoquinolin, Pteridine, Aclysine, Phenazine, Phenantroline, Tetrazole, Pyrazole, Imidazole, and Thiazole, etc.); Polyarylene compounds; Fluorene compounds; Cyclop
  • the n-type semiconductor material preferably contains fullerenes selected from the group consisting of fullerenes and derivatives thereof.
  • 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.
  • the fullerene derivative include compounds in which a substituent is added to the fullerene.
  • the substituent is preferably an alkyl group, an aryl group, or a heterocyclic group.
  • the fullerene derivative the compound described in JP-A-2007-123707 is preferable.
  • the thickness) ⁇ 100) in terms of a single layer is preferably 15 to 100% by volume, more preferably 35 to 100% by volume.
  • An organic dye may be used as the n-type semiconductor material in place of the n-type semiconductor material described in the upper row or together with the n-type semiconductor material described in the upper row.
  • an organic dye By using an organic dye as the n-type semiconductor material, it is easy to control the absorption wavelength (maximum absorption wavelength) of the photoelectric conversion element in an arbitrary wavelength range.
  • the organic pigments include, for example, cyanine pigments, styryl pigments, hemicyanine pigments, merocyanine pigments (including zero methine merocyanin (simple merocyanin)), rodacianin pigments, allopolar pigments, oxonols pigments, hemioxonor pigments, squalium pigments, croconium pigments, etc.
  • the n-type semiconductor material contains an organic dye
  • the film thickness) ⁇ 100) in terms of a single layer is preferably 15 to 100% by volume, more preferably 35 to 100% by volume.
  • the molecular weight of the n-type semiconductor material is preferably 200 to 1200, more preferably 200 to 1000.
  • the photoelectric conversion film preferably has a bulk heterostructure formed in a state where a specific compound and an n-type semiconductor material are mixed.
  • the bulk heterostructure is a layer in which a specific compound and an n-type semiconductor material are mixed and dispersed in a photoelectric conversion film.
  • the bulk heterostructure is described in detail in paragraphs [0013] to [0014] of JP-A-2005-303266.
  • the film thickness of the n-type semiconductor material (thickness in terms of a single layer) ⁇ 100) is preferably 15 to 75% by volume, more preferably 35 to 75% by volume.
  • the photoelectric conversion film is substantially composed of a specific compound and an n-type semiconductor material. Substantially means that the total content of the specific compound and the n-type semiconductor material is 95% by mass or more with respect to the total mass of the photoelectric conversion film.
  • the n-type semiconductor material contained in the photoelectric conversion film may be used alone or in combination of two or more.
  • the photoelectric conversion film containing a specific compound is a non-luminescent film, and has characteristics different from those of an organic electroluminescent device (OLED: Organic Light Emitting Diode).
  • the non-emission film is intended to be a film having an emission quantum efficiency of 1% or less, and an emission quantum efficiency of 0.5% or less is preferable, and 0.1% or less is more preferable.
  • the photoelectric conversion film can be formed mainly by a dry film forming method.
  • the dry film forming method includes, for example, a physical vapor deposition method such as a vapor deposition method (particularly a vacuum vapor deposition method), a sputtering method, an ion plating method, an MBE (Molecular Beam Epitaxy) method, and a CVD method such as plasma polymerization. (Chemical Vapor Deposition) method can be mentioned. Of these, the vacuum deposition method is preferable.
  • the manufacturing conditions such as the degree of vacuum and the vapor deposition temperature can be set according to a conventional method.
  • the thickness of the photoelectric conversion film is preferably 10 to 1000 nm, more preferably 50 to 800 nm, further preferably 50 to 500 nm, and particularly preferably 50 to 300 nm.
  • the electrodes 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 is, for example, antimony or fluorine-doped tin oxide (ATO: Antimony Tin Oxide, FTO: Fluorine topped Tin Oxide), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO: Conductive metal oxides such as Indium Tin Oxide) and indium zinc oxide (IZO); metal thin films such as gold, silver, chromium, and nickel; these metals and conductive metal oxides Mixtures or laminates; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and the like. Of these, conductive metal oxides are preferable from the viewpoints of high conductivity and transparency.
  • the sheet resistance is preferably 100 to 10000 ⁇ / ⁇ .
  • the degree of freedom in the range of film thickness that can be thinned is large.
  • Increasing the light transmittance is preferable because it increases the light absorption in the photoelectric conversion film and increases the photoelectric conversion ability.
  • the film thickness of the upper electrode 15 is preferably 5 to 100 nm, more preferably 5 to 20 nm.
  • the lower electrode 11 may be transparent or may reflect light without being transparent, depending on the intended use.
  • the materials constituting the lower electrode 11 are, for example, antimony or fluorine-doped tin oxide (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO).
  • Conductive metal oxides such as gold, silver, chromium, nickel, titanium, tungsten, and metals such as aluminum, oxides of these metals, or conductive compounds such as nitrides (as an example, titanium nitride (TiN)). ); Mixtures or laminates of these metals and conductive metal oxides; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole.
  • the method for forming the electrode is not particularly limited and can be appropriately selected depending on the electrode material. Specifically, a wet method such as a printing method and a coating method; a physical method such as a vacuum deposition method, a sputtering method, and an ion plating method; and a chemical method such as CVD and a plasma CVD method. , Etc. can be mentioned.
  • a wet method such as a printing method and a coating method
  • a physical method such as a vacuum deposition method, a sputtering method, and an ion plating method
  • a chemical method such as CVD and a plasma CVD method.
  • Etc. can be mentioned.
  • the electrode material is ITO
  • methods such as 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 can be mentioned.
  • the photoelectric conversion element of the present invention preferably 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.
  • the charge blocking film include an electron blocking film and a hole blocking film. Each film will be described in detail below.
  • the electron blocking film is a donor organic semiconductor material (compound), and for example, the following p-type organic semiconductors can be used.
  • One type of p-type organic semiconductor may be used alone, or two or more types may be used.
  • 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) a compound described in paragraphs [0128] to [0148] of JP2011-228614A, JP-A-2011-176259.
  • JP2011-228614A JP-A-2011-176259.
  • Pyrazole compounds polyarylene compounds, condensed aromatic carbocyclic compounds (eg, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pentacene derivatives, pyrene derivatives, perylene derivatives, and fluorantene derivatives. Body), porphyrin compounds, phthalocyanine compounds, triazole compounds, oxadiazole compounds, imidazole compounds, polyarylalkane compounds, pyrazolone compounds, amino-substituted calcon compounds, oxazole compounds, fluorenone compounds, silazane compounds, and nitrogen-containing heterocyclic compounds.
  • condensed aromatic carbocyclic compounds eg, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pentacene derivatives, pyrene derivatives, perylene derivatives, and fluorantene derivatives
  • Examples thereof include a metal complex having as a ligand.
  • Examples of the p-type organic semiconductor include compounds having a smaller ionization potential than the n-type semiconductor material, and if this condition is satisfied, the organic dye exemplified as the n-type semiconductor material 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, pyrrole, pyrrole, picolin, thiophene, acetylene, and diacetylene, and derivatives thereof.
  • the electron blocking film may be composed of a plurality of films.
  • the electron blocking film may be made of an inorganic material.
  • Inorganic materials that can serve as electron blocking films include, 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, and indium copper oxide. , Indium silver oxide, and iridium oxide.
  • the hole blocking film is an acceptor-type organic semiconductor material (compound), and the above-mentioned n-type semiconductor material can be used.
  • 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.
  • Examples of 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. From the viewpoint of precision patterning, the inkjet method is preferable.
  • 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 type of substrate used is not particularly limited, and examples thereof include a semiconductor substrate, a glass substrate, and a plastic substrate.
  • the position of the substrate is not particularly limited, and usually, a conductive film, a photoelectric conversion film, and a transparent conductive film are laminated on the substrate in this order.
  • the photoelectric conversion element may further have a sealing layer.
  • the performance of the photoelectric conversion material may be significantly deteriorated due to the presence of deterioration factors such as water molecules. Therefore, the entire photoelectric conversion film is coated with a ceramic such as a dense metal oxide, metal nitride, or metal nitride that does not allow water molecules to permeate, or a sealing layer such as diamond-like carbon (DLC: Diamond-like Carbon). The above deterioration can be prevented by coating and sealing.
  • the sealing layer may be selected and manufactured as a material in accordance with paragraphs [0210] to [0215] of JP2011-082508.
  • An image sensor is an element that converts optical information of an image into an electric signal.
  • a plurality of photoelectric conversion elements are arranged on a matrix in the same plane, and each photoelectric conversion element (pixel) has an optical signal. Is converted into an electric signal, and the electric signal can be sequentially output to the outside of the image sensor for each pixel. Therefore, each pixel is composed of one or more photoelectric conversion elements and one or more transistors.
  • FIG. 3 is a schematic cross-sectional view showing a schematic configuration of an image pickup device for explaining an embodiment of the present invention.
  • This image pickup element is mounted on an image pickup element such as a digital camera and a digital video camera, an electronic endoscope, and an image pickup module such as a mobile phone.
  • the imaging element 20a shown in FIG. 3 includes a photoelectric conversion element 10a (green photoelectric conversion element 10a) of the present invention, a blue photoelectric conversion element 22, and a red photoelectric conversion element 24, and these include a direction in which light is incident. Are laminated.
  • the photoelectric conversion element 10a is the photoelectric conversion element of the present invention, and is mainly used as a green photoelectric conversion element by controlling the absorption wavelength so that green light can be received. Examples of the method of controlling the absorption wavelength of the photoelectric conversion element of the present invention include a method of using an organic dye suitable as an n-type semiconductor material.
  • the image sensor 20a is a so-called laminated body type color-separated image sensor.
  • the wavelength spectra detected by the photoelectric conversion element 10a, the blue photoelectric conversion element 22, and the red photoelectric conversion element 24 are different from each other. That is, the blue photoelectric conversion element 22 and the red photoelectric conversion element 24 correspond to photoelectric conversion elements that receive light having a wavelength different from the light received (absorbed) by the photoelectric conversion element 10a.
  • the photoelectric conversion element 10a can mainly receive green light
  • the blue photoelectric conversion element 22 can mainly receive blue light
  • the red photoelectric conversion element can mainly receive red light.
  • the green light is intended to be light having a wavelength in the range of 500 to 600 nm
  • the blue light is intended to be light in the wavelength range of 400 to 500 nm
  • the red light is intended to be light in the wavelength range of 600 to 700 nm.
  • the photoelectric conversion element 10a mainly absorbs green light, but blue light and red light pass through the photoelectric conversion element 10a.
  • the blue light is mainly absorbed, but the red light is transmitted through the blue photoelectric conversion element 22.
  • the red photoelectric conversion element 24 is absorbed by the red photoelectric conversion element 24.
  • the image sensor 20a which is a laminated color-separated image sensor, one pixel can be composed of three light receiving units of green, blue, and red, and a large area of the light receiving unit can be obtained.
  • the configurations of the blue photoelectric conversion element 22 and the red photoelectric conversion element 24 are not particularly limited.
  • a photoelectric conversion element having a configuration in which silicon is used to separate colors according to the difference in light absorption length may be used.
  • the blue photoelectric conversion element 22 and the red photoelectric conversion element 24 may both be made of silicon.
  • the photoelectric conversion element 10a mainly receives the green light having the middle wavelength, and the remaining blue light. And red light can be easily separated.
  • blue light is easily absorbed near the surface of silicon, and red light reaches a relatively deep position in silicon. Can invade.
  • blue light is mainly received by the blue photoelectric conversion element 22 existing at a shallower position
  • red light is mainly received by the red photoelectric conversion element 24 existing at a deeper position.
  • the blue photoelectric conversion element 22 and the red photoelectric conversion element 24 have a conductive film, an organic photoelectric conversion film having a maximum absorption maximum for blue light or red light, and a transparent conductive film formation in this order.
  • a photoelectric conversion element (blue photoelectric conversion element 22 or red photoelectric conversion element 24) may be used.
  • the blue photoelectric conversion element 22 may be the photoelectric conversion element of the present invention in which the absorption wavelength is controlled so that the blue light has an absorption maximum.
  • the red photoelectric conversion element 24 may be the photoelectric conversion element of the present invention in which the absorption wavelength is controlled so that the red light has an absorption maximum.
  • the photoelectric conversion element, the blue photoelectric conversion element, and the red photoelectric conversion element of the present invention are arranged in this order from the incident side of the light, but the present invention is not limited to this, and the arrangement is not limited to this. You may.
  • the blue photoelectric conversion element, the photoelectric conversion element of the present invention, and the red photoelectric conversion element may be arranged in this order from the side where the light is incident.
  • the green photoelectric conversion element may be used as a photoelectric conversion element other than the photoelectric conversion element of the present invention, and the blue photoelectric conversion element and / or the red photoelectric conversion element may be used as the photoelectric conversion element of the present invention.
  • the configuration in which the photoelectric conversion elements of the three primary colors of blue, green, and red are stacked has been described, but the number of layers (2 colors) or 4 layers (4 colors) or more is large. It doesn't matter.
  • the photoelectric conversion element 10a of the present invention may be arranged on the arranged blue photoelectric conversion element 22 and the red photoelectric conversion element 24. If necessary, a color filter that further absorbs light having a predetermined wavelength may be arranged on the incident side of the light.
  • the form of the image sensor is not limited to that shown in FIG. 3 and the above-mentioned form, and may be another form.
  • the photoelectric conversion element, the blue photoelectric conversion element, and the red photoelectric conversion element of the present invention may be arranged at the same in-plane position.
  • the photoelectric conversion element may be used in a single layer.
  • a blue, red, and green color filters may be arranged on the photoelectric conversion element 10a of the present invention to separate colors.
  • the photoelectric conversion element of the present invention may be used by the photoelectric conversion element alone, or may be used as a line sensor in which the photoelectric conversion element is arranged in a straight line, or a two-dimensional sensor in which the photoelectric conversion element is arranged on a plane.
  • the present invention also includes the invention of a material for a photoelectric conversion element.
  • the material for a photoelectric conversion element of the present invention is a material used for manufacturing a photoelectric conversion element (preferably a photoelectric conversion element for an image sensor or an optical sensor) containing a compound (specific compound) represented by the formula (1).
  • a photoelectric conversion element preferably a photoelectric conversion element for an image sensor or an optical sensor
  • the compound represented by the formula (1) in the material for a photoelectric conversion element is the same as the compound represented by the above formula (1), and the preferable conditions are also the same. It is preferable that each of the specific compounds contained in the material for the photoelectric conversion element is used for producing the photoelectric conversion film of the photoelectric conversion film contained in the photoelectric conversion element.
  • the content of the specific compound contained in the material for the photoelectric conversion element is preferably 30 to 100% by mass, more preferably 70 to 100% by mass, and 99 to 100% by mass, respectively, of the total mass of the material for the photoelectric conversion element. More preferred.
  • the specific compound contained in the material for the photoelectric conversion element may be one kind alone or two or more kinds.
  • Titanium tetrachloride (12.4 g, 65.3 mmol) was dissolved in THF (tetrahydrofuran, 455 mL) in a 1000 mL three-necked flask under a nitrogen atmosphere. Further, after the liquid temperature in the flask was set to ⁇ 10 ° C., zinc powder (8.54 g, 131 mmol) was added to the flask. THF of intermediate 7a (2.42 g, 10.9 mmol; synthesized according to the synthetic method of S4j described in Supporting information of Chemistry A European Journal 2015, 21, 12871-12875) while heating and refluxing the obtained mixture. The (200 mL) solution was added over 5 hours.
  • THF tetrahydrofuran
  • reaction product was purified by silica gel column chromatography to obtain 1.73 g of Intermediate 7b. Yield 84%.
  • the measurement results of the intermediate 7b by ESI-MS were as follows.
  • a dehydrated THF (7 mL) solution of tributyltin chloride (2.6 g, 7.9 mmol) was added dropwise to the solution while maintaining the internal temperature of the solution at ⁇ 66 ° C. or lower, and then the solution was added to room temperature (7 mL). The temperature was returned to 23 ° C.) and reacted at room temperature for 1 hour to obtain a reaction solution.
  • Water (50 mL) was measured in a 300 mL Erlenmeyer flask, and the obtained reaction solution was added thereto to stop the reaction.
  • the reaction product contained in the obtained liquid was extracted with ethyl acetate.
  • the organic phase containing the reaction product obtained by the extraction treatment was dried over sodium sulfate and concentrated under reduced pressure.
  • 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.
  • an 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 (B-1) is further vacuumed on the lower electrode 11.
  • An electron blocking film 16A was formed by forming a film by a heat vapor deposition method.
  • a photoelectric conversion film 12 having a bulk heterostructure of 200 nm was formed by co-depositing and forming a film by a vacuum vapor deposition method so as to have a temperature of 100 nm and 100 nm (photoelectric conversion film forming step). Further, the following compound (B-2) was formed on the photoelectric conversion film 12 to form a hole blocking film 16B (thickness: 10 nm).
  • an 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).
  • a SiO film is formed on the upper electrode 15 as a sealing layer by a vacuum vapor deposition method, and then an aluminum oxide (Al 2 O 3 ) layer is formed on the SiO film by an ALCVD (Atomic Layer Chemical Vapor Deposition) method to form a photoelectric conversion element.
  • ALCVD Atomic Layer Chemical Vapor Deposition
  • the responsiveness of each of the obtained elements (A) was evaluated. A voltage is applied so that the electric field intensity of 1.0 ⁇ 10 5 V / cm in each element (A), was irradiated with light of 400nm from the upper electrode (transparent conductive film) side. Assuming that the value of the photocurrent 10 milliseconds after the start of irradiation was 100%, the time required for the photocurrent to reach 97% or more was calculated. The responsiveness of each element (A) was evaluated by a relative value when the value of the element (A) of Example 1 (the time required for the photocurrent to reach 97% or more) was set to 1.
  • Evaluation was performed with a relative value of 0.5 or less as A, a value larger than 0.5 and 1 or less as B, a value larger than 1 and 2 or less as C, and a value larger than 2 as D. Practically, A or B is preferable, and A is more preferable. The results are shown in Table 1.
  • Table 1 below shows the results of tests conducted using photoelectric conversion elements manufactured using each compound.
  • Table 1 below shows the results of tests conducted using photoelectric conversion elements manufactured using each compound.
  • the column "Formula (3)” indicates whether or not the specific compound used corresponds to the compound represented by the formula (3). If this requirement is met, it is designated as A, and if it is not met, it is designated as B.
  • the photoelectric conversion element of the present invention using a specific compound for the photoelectric conversion film has excellent responsiveness. It was also confirmed that the photoelectric conversion element of the present invention is also excellent in heat resistance.
  • the photoelectric conversion element using the compound R-1 in which the aromatic ring group corresponding to Ar 1 and Ar 4 in the formula (1) does not exist has insufficient responsiveness.
  • the heat resistance was also inferior to that of the photoelectric conversion element of the present invention.
  • the photoelectric conversion element using the compound R-2 having a mother nucleus having a structure different from that of the specific compound had insufficient responsiveness.
  • the heat resistance was also inferior to that of the photoelectric conversion element of the present invention.
  • the group corresponding to the group represented by Ar 1 or Ar 4 in the formula (1) in the specific compound is represented by a polycyclic aromatic ring group which may have a substituent or a formula (R). It was confirmed that the obtained photoelectric conversion element has more excellent heat resistance in the case of a group (see the results of Examples 2, 3, 6, 7, 8 and the like).

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Abstract

The present invention provides a photoelectric conversion element having excellent responsivity, and also provides an imaging element, an optical sensor, and a photoelectric conversion element material. This photoelectric conversion element includes, in the order given, a conductive film (11), a photoelectric conversion film (12), and a transparent conductive film (15). The photoelectric conversion film contains a compound represented by a formula (1) and an n-type semiconductor material.

Description

光電変換素子、撮像素子、光センサ、光電変換素子用材料Materials for photoelectric conversion elements, image sensors, optical sensors, photoelectric conversion elements
　本発明は、光電変換素子、撮像素子、光センサ、及び、光電変換素子用材料に関する。 The present invention relates to a photoelectric conversion element, an image sensor, an optical sensor, and a material for a photoelectric conversion element.
　近年、光電変換膜を有する素子（例えば、撮像素子）の開発が進んでいる。
　例えば、特許文献１において、所定の化合物を含む光電変換素子が開示されている。 In recent years, the development of an element having a photoelectric conversion film (for example, an image sensor) has been progressing.
For example, Patent Document 1 discloses a photoelectric conversion element containing a predetermined compound.
特開２０１７－３９６６２号公報Japanese Unexamined Patent Publication No. 2017-39662
　近年、撮像素子及び光センサ等の性能向上の要求に伴い、これらに使用される光電変換素子に求められる諸特性に関してもさらなる向上が求められている。
　例えば、光電変換素子は、受光した際の応答性に優れることが求められている。 In recent years, with the demand for performance improvement of image sensors, optical sensors, and the like, further improvement is required for various characteristics required for photoelectric conversion elements used therein.
For example, a photoelectric conversion element is required to have excellent responsiveness when receiving light.
　本発明は、上記実情に鑑みて、応答性に優れる光電変換素子を提供することを課題とする。
　また、本発明は、撮像素子、光センサ、及び、光電変換素子用材料を提供することも課題とする。 An object of the present invention is to provide a photoelectric conversion element having excellent responsiveness in view of the above circumstances.
Another object of the present invention is to provide a material for an image sensor, an optical sensor, and a photoelectric conversion element.
　本発明者らは、上記課題について鋭意検討した結果、下記構成により上記課題を解決できることを見出し、本発明を完成するに至った。 As a result of diligent studies on the above problems, the present inventors have found that the above problems can be solved by the following configuration, and have completed the present invention.
　〔１〕
　導電性膜、光電変換膜、及び、透明導電性膜をこの順で有する光電変換素子であって、
　上記光電変換膜が、後述する式（１）で表される化合物、及び、ｎ型半導体材料を含む、光電変換素子。
　〔２〕
　後述する式（１）で表される化合物が、後述する式（２）で表される化合物、後述する式（３）で表される化合物、又は、後述する式（４）で表される化合物である、〔１〕に記載の光電変換素子。
　〔３〕
　式中、Ａｒ２及びＡｒ３が、置換基を有してもよい単環の芳香環基を表す、〔１〕又は〔２〕に記載の光電変換素子。
　〔４〕
　後述する式（１）で表される化合物の分子量が４５０～９００である、〔１〕～〔３〕のいずれかに記載の光電変換素子。
　〔５〕
　上記光電変換膜が、後述する式（１）で表される化合物と上記ｎ型半導体材料とが混合された状態で形成されるバルクへテロ構造を有する、〔１〕～〔４〕のいずれかに記載の光電変換素子。
　〔６〕
　上記導電性膜と上記透明導電性膜との間に、上記光電変換膜の他に１種以上の中間層を有する、〔１〕～〔５〕のいずれかに記載の光電変換素子。
　〔７〕
　上記ｎ型半導体材料が、フラーレン及びその誘導体からなる群より選択されるフラーレン類を含む、〔１〕～〔６〕のいずれかに記載の光電変換素子。
　〔８〕
　〔１〕～〔７〕のいずれかに記載の光電変換素子を有する、撮像素子。
　〔９〕
　〔１〕～〔７〕のいずれかに記載の光電変換素子を有する、光センサ。
　〔１０〕
　後述する式（１）で表される化合物を含む、光電変換素子用材料。 [1]
A photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order.
A photoelectric conversion element in which the photoelectric conversion film contains a compound represented by the formula (1) described later and an n-type semiconductor material.
[2]
The compound represented by the formula (1) described later is a compound represented by the formula (2) described later, a compound represented by the formula (3) described later, or a compound represented by the formula (4) described later. The photoelectric conversion element according to [1].
[3]
The photoelectric conversion element according to [1] or [2], wherein Ar 2 and Ar 3 represent a monocyclic aromatic ring group which may have a substituent.
[4]
The photoelectric conversion element according to any one of [1] to [3], wherein the compound represented by the formula (1) described later has a molecular weight of 450 to 900.
[5]
Any of [1] to [4], wherein the photoelectric conversion film has a bulk heterostructure formed in a state where the compound represented by the formula (1) described later and the n-type semiconductor material are mixed. The photoelectric conversion element according to.
[6]
The photoelectric conversion element according to any one of [1] to [5], which has one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film.
[7]
The photoelectric conversion element according to any one of [1] to [6], wherein the n-type semiconductor material contains fullerenes selected from the group consisting of fullerenes and derivatives thereof.
[8]
An image pickup device having the photoelectric conversion element according to any one of [1] to [7].
[9]
An optical sensor having the photoelectric conversion element according to any one of [1] to [7].
[10]
A material for a photoelectric conversion element containing a compound represented by the formula (1) described later.
　本発明によれば、応答性に優れる光電変換素子を提供できる。
　また、本発明によれば、撮像素子、光センサ、及び、光電変換素子用材料を提供できる。 According to the present invention, it is possible to provide a photoelectric conversion element having excellent responsiveness.
Further, according to the present invention, it is possible to provide a material for an image sensor, an optical sensor, and a photoelectric conversion element.
光電変換素子の一構成例を示す断面模式図である。It is sectional drawing which shows one structural example of a photoelectric conversion element. 光電変換素子の一構成例を示す断面模式図である。It is sectional drawing which shows one structural example of a photoelectric conversion element. 撮像素子の一実施形態の断面模式図である。It is sectional drawing of one Embodiment of an image sensor.
　以下に、本発明の光電変換素子の好適実施形態について説明する。
　また、本明細書において、「置換基」は、特段の断りがない限り、後述する置換基Ｗで例示される基が挙げられる。 Hereinafter, preferred embodiments of the photoelectric conversion element of the present invention will be described.
Further, in the present specification, the "substituent" includes a group exemplified by the substituent W described later, unless otherwise specified.
（置換基Ｗ）
　本明細書における置換基Ｗについて記載する。
　置換基Ｗは、例えば、ハロゲン原子（フッ素原子、塩素原子、臭素原子、及び、ヨウ素原子等）、アルキル基（シクロアルキル基、ビシクロアルキル基、及び、トリシクロアルキル基を含む）、アルケニル基（シクロアルケニル基、及び、ビシクロアルケニル基を含む）、アルキニル基、アリール基、ヘテロアリール基（ヘテロ環基といってもよい。）、シアノ基、ヒドロキシ基、カルボキシ基、ニトロ基、アルコキシ基、アリールオキシ基、シリルオキシ基、ヘテロ環オキシ基、アシルオキシ基、カルバモイルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アミノ基（アニリノ基を含む。）、アンモニオ基、アシルアミノ基、アミノカルボニルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルファモイルアミノ基、アルキル又はアリールスルホニルアミノ基、メルカプト基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基、スルファモイル基、アルキル又はアリールスルフィニル基、アルキル又はアリールスルホニル基、アシル基、アリールオキシカルボニル基、アルコキシカルボニル基、カルバモイル基、アリール又はヘテロ環アゾ基、イミド基、ホスフィノ基、ホスフィニル基、ホスフィニルオキシ基、ホスフィニルアミノ基、ホスホノ基、シリル基、ヒドラジノ基、ウレイド基、及び、ボロン酸基（－Ｂ（ＯＨ）２）が挙げられる。また、上述の各基は、可能な場合、更に置換基（例えば、上述の各基のうちの１以上の基）を有してもよい。例えば、置換基を有してもよいアルキル基も、置換基Ｗの一形態として含まれる。
　また、置換基Ｗが炭素原子を有する場合、置換基Ｗが有する炭素数は、例えば、１～２０である。
　置換基Ｗが有する水素原子以外の原子の数は、例えば、１～３０である。 (Substituent W)
Substituent W in the present specification will be described.
The substituent W is, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), an alkyl group (including a cycloalkyl group, a bicycloalkyl group, and a tricycloalkyl group), an alkenyl group (including a cycloalkyl group, a bicycloalkyl group, and an alkenyl group). Cycloalkenyl group and bicycloalkenyl group), alkynyl group, aryl group, heteroaryl group (may be called heterocyclic group), cyano group, hydroxy group, carboxy group, nitro group, alkoxy group, aryl Oxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anirino 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 aryl Sulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl Examples include a group, a hydrazino group, a ureido group, and a boronate group (-B (OH) 2 ). Further, each of the above-mentioned groups may further have a substituent (for example, one or more groups of each of the above-mentioned groups) if possible. For example, an alkyl group which may have a substituent is also included as a form of the substituent W.
When the substituent W has a carbon atom, the number of carbon atoms of the substituent W is, for example, 1 to 20.
The number of atoms other than the hydrogen atom of the substituent W is, for example, 1 to 30.
　また、本明細書において、特段の断りがない限り、アルキル基の炭素数は、１～２０が好ましく、１～１０がより好ましく、１～６が更に好ましい。
　アルキル基は、直鎖状、分岐鎖状、及び、環状のいずれであってもよい。
　アルキル基は、例えば、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｔ－ブチル基、ｎ－ヘキシル基、及び、シクロペンチル基等が挙げられる。
　また、アルキル基は、例えば、シクロアルキル基、ビシクロアルキル基、及び、トリシクロアルキル基であってもよく、これらの環状構造を部分構造として有してもよい。
　置換基を有してもよいアルキル基において、アルキル基が有してもよい置換基は特に制限されず、例えば、置換基Ｗが挙げられ、アリール基（好ましくは炭素数６～１８、より好ましくは炭素数６）、ヘテロアリール基（好ましくは炭素数５～１８、より好ましくは炭素数５～６）、又は、ハロゲン原子（好ましくはフッ素原子又は塩素原子）が好ましい。 Further, in the present specification, unless otherwise specified, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6.
The alkyl group may be linear, branched, or cyclic.
Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, an n-hexyl group, a cyclopentyl group and the like.
Further, the alkyl group may be, for example, a cycloalkyl group, a bicycloalkyl group, or a tricycloalkyl group, and may have a cyclic structure thereof as a partial structure.
Among the alkyl groups that may have a substituent, the substituent that the alkyl group may have is not particularly limited, and examples thereof include a substituent W, and an aryl group (preferably 6 to 18 carbon atoms, more preferably). 6), a heteroaryl group (preferably 5 to 18, more preferably 5 to 6 carbon atoms), or a halogen atom (preferably a fluorine atom or a chlorine atom).
　本明細書において、特段の断りがない限り、アルコキシ基におけるアルキル基部分は上記アルキル基が好ましい。アルキルチオ基におけるアルキル基部分は上記アルキル基が好ましい。
　置換基を有してもよいアルコキシ基において、アルコキシ基が有してもよい置換基は、置換基を有してもよいアルキル基における置換基と同様の例が挙げられる。置換基を有してもよいアルキルチオ基において、アルキルチオ基が有してもよい置換基は、置換基を有してもよいアルキル基における置換基と同様の例が挙げられる。 In the present specification, unless otherwise specified, the above-mentioned alkyl group is preferable as the alkyl group portion of the alkoxy group. The above-mentioned alkyl group is preferable as the alkyl group moiety in the alkylthio group.
Among the alkoxy groups that may have a substituent, the substituent that the alkoxy group may have includes the same examples as the substituent in the alkyl group that may have a substituent. Among the alkylthio groups which may have a substituent, the substituent which the alkylthio group may have includes the same examples as the substituent in the alkyl group which may have a substituent.
　本明細書において、特段の断りがない限り、アルケニル基は、直鎖状、分岐鎖状、及び、環状のいずれであってもよい。上記アルケニル基の炭素数は、２～２０が好ましい。置換基を有してもよいアルケニル基において、アルケニル基が有してもよい置換基は、置換基を有してもよいアルキル基における置換基と同様の例が挙げられる。
　本明細書において、特段の断りがない限り、アルキニル基は、直鎖状、分岐鎖状、及び、環状のいずれであってもよい。上記アルキニル基の炭素数は、２～２０が好ましい。置換基を有してもよいアルキニル基において、アルキニル基が有してもよい置換基は、置換基を有してもよいアルキル基における置換基と同様の例が挙げられる。 In the present specification, unless otherwise specified, the alkenyl group may be linear, branched chain, or cyclic. The alkenyl group preferably has 2 to 20 carbon atoms. Among the alkenyl groups which may have a substituent, the substituent which the alkenyl group may have includes the same examples as the substituent in the alkyl group which may have a substituent.
In the present specification, unless otherwise specified, the alkynyl group may be linear, branched chain, or cyclic. The alkynyl group preferably has 2 to 20 carbon atoms. Among the alkynyl groups which may have a substituent, the substituent which the alkynyl group may have includes the same examples as the substituent in the alkyl group which may have a substituent.
　本明細書において、特段の断りがない限り、アリール基は、環員数が６～１８のアリール基が好ましい。
　アリール基は、単環でも多環でもよい。
　アリール基は、例えば、フェニル基、ナフチル基、アントリル基、又は、フェナントレニル基が好ましい。
　置換基を有してもよいアリール基において、アリール基が有してもよい置換基は特に制限されず、例えば、置換基Ｗが挙げられ、置換基を有してもよいアルキル基（好ましくは炭素数１～１０）が好ましく、メチル基がより好ましい。 In the present specification, the aryl group is preferably an aryl group having 6 to 18 ring members, unless otherwise specified.
The aryl group may be monocyclic or polycyclic.
The aryl group is preferably, for example, a phenyl group, a naphthyl group, an anthryl group, or a phenanthrenyl group.
Among the aryl groups which may have a substituent, the substituent which the aryl group may have is not particularly limited, and examples thereof include a substituent W, and an alkyl group which may have a substituent (preferably). The number of carbon atoms is preferably 1 to 10), and a methyl group is more preferable.
　本明細書において、特段の断りがない限り、ヘテロアリール基は、窒素原子、硫黄原子、酸素原子、セレン原子、テルル原子、リン原子、ケイ素原子、及び／又は、ホウ素原子等のヘテロ原子を含む、単環又は多環の環構造を有するヘテロアリール基が好ましい。
　上記ヘテロアリール基の環員原子中の炭素数は特に制限されず、３～１８が好ましく、３～５がより好ましい。
　ヘテロアリール基の環員原子中のヘテロ原子の数は特に制限されず、１～１０が好ましく、１～４がより好ましく、１～２が更に好ましい。
　ヘテロアリール基の環員数は特に制限されず、５～８が好ましく、５～７がより好ましく、５～６が更に好ましい。
　上記ヘテロアリール基は、フリル基、ピリジル基、キノリル基、イソキノリル基、アクリジニル基、フェナントリジニル基、プテリジニル基、ピラジニル基、キノキサリニル基、ピリミジニル基、キナゾリル基、ピリダジニル基、シンノリニル基、フタラジニル基、トリアジニル基、オキサゾリル基、ベンゾオキサゾリル基、チアゾリル基、ベンゾチアゾリル基、イミダゾリル基、ベンゾイミダゾリル基、ピラゾリル基、インダゾリル基、イソオキサゾリル基、ベンゾイソオキサゾリル基、イソチアゾリル基、ベンゾイソチアゾリル基、オキサジアゾリル基、チアジアゾリル基、トリアゾリル基、テトラゾリル基、ベンゾフリル基、チエニル基、ベンゾチエニル基、ジベンゾフリル基、ジベンゾチエニル基、ピロリル基、インドリル基、イミダゾピリジニル基、及び、カルバゾリル基等が挙げられる。
　置換基を有してもよいヘテロアリール基において、ヘテロアリール基が有してもよい置換基は特に制限されず、例えば、置換基Ｗが挙げられる。 In the present specification, unless otherwise specified, the heteroaryl group includes a hetero atom such as a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and / or a boron atom. , A heteroaryl group having a monocyclic or polycyclic ring structure is preferable.
The number of carbon atoms in the ring member atom of the heteroaryl group is not particularly limited, and is preferably 3 to 18 and more preferably 3 to 5.
The number of heteroatoms in the ring member atom of the heteroaryl group is not particularly limited, and is preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 to 2.
The number of ring members of the heteroaryl group is not particularly limited, and is preferably 5 to 8, more preferably 5 to 7, and even more preferably 5 to 6.
The heteroaryl group includes a fryl group, a pyridyl group, a quinolyl group, an isoquinolyl group, an acridinyl group, a phenanthridinyl group, a pteridinyl group, a pyrazinyl group, a quinoxalinyl group, a pyrimidinyl group, a quinazolyl group, a pyridadinyl group, a synnolinyl group and a phthalazinyl group. , Triazinyl group, oxazolyl group, benzoxazolyl group, thiazolyl group, benzothiazolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, indazolyl group, isooxazolyl group, benzoisoxazolyl group, isothiazolyl group, benzoisothiazolyl group, Examples thereof include an oxadiazolyl group, a thiadiazolyl group, a triazolyl group, a tetrazolyl group, a benzofuryl group, a thienyl group, a benzothienyl group, a dibenzofuryl group, a dibenzothienyl group, a pyrrolyl group, an indolyl group, an imidazoly pyridinyl group and a carbazolyl group. ..
Among the heteroaryl groups which may have a substituent, the substituent which the heteroaryl group may have is not particularly limited, and examples thereof include a substituent W.
　本明細書において、特段の断りがない限り、置換基を有してもよいシリル基は、例えば、－Ｓｉ（ＲＳ１）（ＲＳ２）（ＲＳ３）で表される基が挙げられる。ＲＳ１、ＲＳ２、及び、ＲＳ３は、それぞれ独立に、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいアリール基、又は、置換基を有してもよいヘテロアリール基を表す。 In the present specification, unless otherwise specified, the silyl group which may have a substituent includes, for example, a group represented by —Si ( RS1 ) ( RS2 ) ( RS3 ). R S1 , R S2 , and R S3 independently have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and a substituent. Represents an aryl group which may have a group or a heteroaryl group which may have a substituent.
　また、本明細書において、「～」を用いて表される数値範囲は、「～」前後に記載される数値を下限値及び上限値として含む範囲を意味する。 Further, in the present specification, 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.
　本明細書において、水素原子は、軽水素原子（通常の水素原子）であってもよいし、重水素原子（二重水素原子等）であってもよい。 In the present specification, the hydrogen atom may be a light hydrogen atom (ordinary hydrogen atom) or a deuterium atom (double hydrogen atom or the like).
　本発明の光電変換素子は、導電性膜、光電変換膜、及び、透明導電性膜をこの順で有する光電変換素子であって、光電変換膜が、式（１）で表される化合物（以下、「特定化合物」とも言う）、及び、ｎ型半導体材料を含む。
　本発明の光電変換素子がこのような構成をとることで上記課題を解決できるメカニズムは必ずしも明らかではないが、本発明者らは以下のように推測している。
　すなわち、特定化合物は、母核として中心部に特定の環が３個縮環した構造を有しており、更に上記母核の両端に芳香環基が連続して結合している。特定化合物がこのような特徴的な構造を有するため、特定化合物を光電変換素子に使用した場合に、光電変換素子の応答性が優れる、と推測している。
　また、特定化合物を使用して製造した光電変換膜を有する光電変換素子は耐熱性にも優れている。これは、特定化合物が有する剛直な構造に由来すると考えられている。
　以下、得られる光電変換素子の、応答性、及び／又は、耐熱性が優れることを、単に「本発明の効果が優れる」とも言う。 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 "specific compound"), and n-type semiconductor materials.
The mechanism by which the photoelectric conversion element of the present invention can solve the above problems by adopting such a configuration is not always clear, but the present inventors speculate as follows.
That is, the specific compound has a structure in which three specific rings are fused in the central portion as a mother nucleus, and aromatic ring groups are continuously bonded to both ends of the mother nucleus. Since the specific compound has such a characteristic structure, it is presumed that the responsiveness of the photoelectric conversion element is excellent when the specific compound is used for the photoelectric conversion element.
Further, the photoelectric conversion element having a photoelectric conversion film manufactured by using a specific compound is also excellent in heat resistance. It is believed that this is due to the rigid structure of the particular compound.
Hereinafter, the excellent responsiveness and / or heat resistance of the obtained photoelectric conversion element is also simply referred to as "the effect of the present invention is excellent".
　図１に、本発明の光電変換素子の一実施形態の断面模式図を示す。
　図１に示す光電変換素子１０ａは、下部電極として機能する導電性膜（以下、下部電極とも記す）１１と、電子ブロッキング膜１６Ａと、後述する特定化合物を含む光電変換膜１２と、上部電極として機能する透明導電性膜（以下、上部電極とも記す）１５とがこの順に積層された構成を有する。
　図２に別の光電変換素子の構成例を示す。図２に示す光電変換素子１０ｂは、下部電極１１上に、電子ブロッキング膜１６Ａと、光電変換膜１２と、正孔ブロッキング膜１６Ｂと、上部電極１５とがこの順に積層された構成を有する。なお、図１及び図２中の電子ブロッキング膜１６Ａ、光電変換膜１２、及び、正孔ブロッキング膜１６Ｂの積層順は、用途及び特性に応じて、適宜変更してもよい。 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. The photoelectric conversion element 10b shown in FIG. 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.
　光電変換素子１０ａ（又は１０ｂ）では、上部電極１５を介して光電変換膜１２に光が入射されることが好ましい。
　また、光電変換素子１０ａ（又は１０ｂ）を使用する場合には、電圧を印加できる。この場合、下部電極１１と上部電極１５とが一対の電極をなし、この一対の電極間に、１×１０－５～１×１０７Ｖ／ｃｍの電圧を印加することが好ましい。性能及び消費電力の点から、印加される電圧は、１×１０－４～１×１０７Ｖ／ｃｍがより好ましく、１×１０－３～５×１０６Ｖ／ｃｍが更に好ましい。
　なお、電圧印加方法については、図１及び図２において、電子ブロッキング膜１６Ａ側が陰極となり、光電変換膜１２側が陽極となるように印加することが好ましい。光電変換素子１０ａ（又は１０ｂ）を光センサとして使用した場合、また、撮像素子に組み込んだ場合も、同様の方法により電圧を印加できる。
　後段で、詳述するように、光電変換素子１０ａ（又は１０ｂ）は撮像素子用途に好適に適用できる。 In the photoelectric conversion element 10a (or 10b), it is preferable that light is incident on the photoelectric conversion film 12 via the upper electrode 15.
Further, when the photoelectric conversion element 10a (or 10b) is used, a voltage can be applied. In this case, it is preferable that the lower electrode 11 and the upper electrode 15 form a pair of electrodes, and a voltage of 1 × 10 -5 to 1 × 10 7 V / cm is applied between the pair of electrodes. From the viewpoint of performance and power consumption, the applied voltage is more preferably 1 × 10 -4 to 1 × 10 7 V / cm, further preferably 1 × 10 -3 to 5 × 10 6 V / cm.
Regarding the voltage application method, it is preferable to apply the voltage so that the electron blocking film 16A side serves as the cathode and the photoelectric conversion film 12 side serves as the anode in FIGS. 1 and 2. When the photoelectric conversion element 10a (or 10b) is used as an optical sensor or incorporated into an image sensor, a voltage can be applied by the same method.
As will be described in detail later, the photoelectric conversion element 10a (or 10b) can be suitably applied to an image sensor application.
　以下に、本発明の光電変換素子を構成する各層の形態について詳述する。 The form of each layer constituting the photoelectric conversion element of the present invention will be described in detail below.
＜光電変換膜＞
　光電変換膜は、特定化合物を含む膜である
　以下、特定化合物について詳述する。 <Photoelectric conversion film>
The photoelectric conversion film is a film containing a specific compound. Hereinafter, the specific compound will be described in detail.
（式（１）で表される化合物（特定化合物））
　特定化合物は、下記式（１）で表される化合物である。 (Compound represented by formula (1) (specific compound))
The specific compound is a compound represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　式（１）中、Ｘ１及びＹ１の一方が、－ＣＲａ１＝又は－Ｎ＝を表し、他方が、－Ｏ－、－Ｓ－、－Ｓｅ－、－Ｔｅ－、又は、－ＮＲａ２－を表す。
　Ｘ２及びＹ２の一方が、－ＣＲａ１＝又は－Ｎ＝を表し、他方が、－Ｏ－、－Ｓ－、－Ｓｅ－、－Ｔｅ－、又は、－ＮＲａ２－を表す。
　つまり、例えば、Ｘ１が－ＣＲａ１＝又は－Ｎ＝を表す場合、Ｙ１は－Ｏ－、－Ｓ－、－Ｓｅ－、－Ｔｅ－、又は、－ＮＲａ２－を表す。
　－ＣＲａ１＝及び－ＮＲａ２－における、Ｒａ１及びＲａ２は、それぞれ独立に、水素原子又は置換基を表す。
　Ｒａ１及びＲａ２で表される置換基としては、例えば、置換基Ｗが挙げられ、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいシリル基、置換基を有してもよいアリール基、又は、置換基を有してもよいヘテロアリール基が好ましい。
　Ｒａ１及びＲａ２は、それぞれ独立に、水素原子が好ましい。
　式（１）中に、複数のＲａ１が存在する場合、複数存在するＲａ１はそれぞれ同一でも異なっていてもよい。
　式（１）中に、複数のＲａ２が存在する場合、複数存在するＲａ２はそれぞれ同一でも異なっていてもよい。
　式（１）中における、Ｘ１及びＹ１を含む５員環は芳香族ヘテロ環であり、Ｘ２及びＹ２を含む５員環は芳香族ヘテロ環である。
　中でも、Ｘ１及びＹ１の一方が、－ＣＲａ１＝を表し、他方が、－Ｏ－、－Ｓ－、又は、－Ｓｅ－を表すのが好ましい。
　Ｘ２及びＹ２の一方が、－ＣＲａ１＝を表し、他方が、－Ｏ－、－Ｓ－、又は、－Ｓｅ－を表すのが好ましい。 In formula (1), one of X 1 and Y 1 represents -CR a1 = or -N =, and the other represents -O-, -S-, -Se-, -Te-, or -NR a2. -Represents.
One of X 2 and Y 2 represents -CR a1 = or -N =, and the other represents -O-, -S-, -Se-, -Te-, or -NR a2- .
That is, for example, when X 1 represents -CR a1 = or -N =, Y 1 represents -O-, -S-, -Se-, -Te-, or -NR a2- .
In -CR a1 = and -NR a2- , R a1 and R a2 each independently represent a hydrogen atom or a substituent.
Examples of the substituent represented by R a1 and R a2 include a substituent W, which includes a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. An alkylthio group which may have a substituent, a silyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent is preferable.
R a1 and R a2 are each independently preferably a hydrogen atom.
In the formula (1), when a plurality of R a1 is present, R a1 may have respectively be the same or different where there exist a plurality.
In the formula (1), when a plurality of R a2 are present, R a2 may have respectively be the same or different where there exist a plurality.
In the formula (1), the 5-membered ring containing X 1 and Y 1 is an aromatic hetero ring, and the 5-membered ring containing X 2 and Y 2 is an aromatic hetero ring.
Among them, it is preferable that one of X 1 and Y 1 represents -CR a1 = and the other represents -O-, -S-, or -Se-.
It is preferable that one of X 2 and Y 2 represents -CR a1 = and the other represents -O-, -S-, or -Se-.
　式（１）中、Ｚ１及びＺ２は、それぞれ独立に、－ＣＲａ３＝又は－Ｎ＝を表す。
　Ｒａ３は、水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいシリル基、置換基を有してもよいアリール基、又は、置換基を有してもよいヘテロアリール基を表す。
　なお、Ｚ１及びＺ２が共に－ＣＲａ３＝である場合においても、Ｒａ３同士が互いに結合して環を形成することはない。
　式（１）中に、複数のＲａ３が存在する場合、複数存在するＲａ３はそれぞれ同一でも異なっていてもよい。
　Ｚ１及びＺ２は、それぞれ独立に、－ＣＲａ３＝が好ましく、－ＣＨ＝がより好ましい。 In formula (1), Z 1 and Z 2 independently represent -CR a3 = or -N =, respectively.
Ra3 may have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and a substituent. Represents a good silyl group, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.
Even when Z 1 and Z 2 are both −CR a3 =, R a3s do not bond with each other to form a ring.
In the formula (1), when a plurality of R a3 is present, R a3 may have respectively be the same or different where there exist a plurality.
For Z 1 and Z 2 , -CR a3 = is preferable, and -CH = is more preferable, respectively.
　式（１）中、Ａｒ１～Ａｒ４は、それぞれ独立に、置換基を有してもよい芳香環基を表す。
　上記芳香環基は、単環でも多環でもよい。
　上記芳香環基は環員原子として１以上（好ましくは１～３）のヘテロ原子（窒素原子、硫黄原子、酸素原子、セレン原子、テルル原子、リン原子、ケイ素原子、及び／又は、ホウ素原子等）を含んでいてもよく、含んでいなくてもよい。上記芳香環基の環員数は５～１８が好ましい。
　上記芳香環基が単環の芳香環基である場合、上記単環の芳香環基としては、例えば、ベンゼン環基、フリル環基、ピリジン環基、ピラジン環基、ピリミジン環基、ピリダジン環基、トリアジン環基、オキサゾール環基、チアゾール環基、イミダゾール環基、ピラゾール環基、イソオキサゾール環基、イソチアゾール環基、オキサジアゾール環基、チアジアゾール環基、トリアゾール環基、テトラゾール環基、チオフェン環基、セレノフェン環基、及び、ピロール環基が挙げられる。
　多環の芳香環基は、芳香族性を有する単環同士が縮環してなる基である。多環の芳香環基において、多環の芳香環を構成するそれぞれの単環（芳香族性を有する単環）の環員原子の２以上は、多環の芳香環基を構成する他の単環（芳香族性を有する単環）の環員原子にもなっている。
　上記芳香環基が多環の芳香環基である場合、上記多環の芳香環基としては、例えば、ナフタレン環基、アントラセン環基、キノリン環基、イソキノリン環基、アクリジン環基、フェナントリジン環基、プテリジン環基、キノキサリン環基、キナゾリン環基、シンノリン環基、フタラジン環基、ベンゾオキサゾール環基、ベンゾチアゾール環基、ベンゾイミダゾール環基、インダゾール環基、ベンゾイソオキサゾール環基、ベンゾイソチアゾール環基、ベンゾフラン環基、ベンゾチオフェン環基、ベンゾセレノフェン環基、ジベンゾフラン環基、ジベンゾチオフェン環基、ジベンゾセレノフェン環基、チエノチオフェン環基、チエノピロール環基、ジチエノピロール環基、インドール環基、イミダゾピリジン環基、及び、カルバゾール環基が挙げられる。 In the formula (1), Ar 1 to Ar 4 each independently represent an aromatic ring group which may have a substituent.
The aromatic ring group may be monocyclic or polycyclic.
The aromatic ring group has one or more (preferably 1 to 3) heteroatoms (nitrogen atom, sulfur atom, oxygen atom, selenium atom, tellurium atom, phosphorus atom, silicon atom, and / or boron atom, etc.) as ring member atoms. ) May or may not be included. The number of ring members of the aromatic ring group is preferably 5 to 18.
When the aromatic ring group is a monocyclic aromatic ring group, the monocyclic aromatic ring group includes, for example, a benzene ring group, a frill ring group, a pyridine ring group, a pyrazine ring group, a pyrimidine ring group, and a pyridazine ring group. , Triazine ring group, oxazole ring group, thiazole ring group, imidazole ring group, pyrazole ring group, isooxazole ring group, isothiazole ring group, oxazole ring group, thiazazole ring group, triazole ring group, tetrazole ring group, thiophene Examples include a ring group, a selenophene ring group, and a pyrrole ring group.
A polycyclic aromatic ring group is a group formed by condensing single rings having aromaticity. In a polycyclic aromatic ring group, two or more of the ring member atoms of each monocycle (monocycle having aromaticity) constituting the polycyclic aromatic ring are other singles constituting the polycyclic aromatic ring group. It is also a ring member atom of a ring (a single ring having aromaticity).
When the aromatic ring group is a polycyclic aromatic ring group, the polycyclic aromatic ring group includes, for example, a naphthalene ring group, an anthracene ring group, a quinoline ring group, an isoquinolin ring group, an acrydin ring group, and phenanthridin. Ring group, pteridine ring group, quinoxaline ring group, quinazoline ring group, cinnoline ring group, phthalazine ring group, benzoxazole ring group, benzothiazole ring group, benzimidazole ring group, indazole ring group, benzoisooxazole ring group, benzoiso Thiazole ring group, benzofuran ring group, benzothiophene ring group, benzoselenophen ring group, dibenzofuran ring group, dibenzothiophene ring group, dibenzoselenophen ring group, thienothiophene ring group, thienopyrol ring group, dithienopyrrole ring group, indol ring group , Imidazopyridine ring group, and carbazole ring group.
　なお、Ａｒ１及びＡｒ２における芳香環基が有してもよい置換基とは、Ｌ１のことではない。また、Ａｒ２における芳香環基が有してもよい置換基とは、Ａｒ１のことでもない。
　同様に、Ａｒ３及びＡｒ３における芳香環基が有してもよい置換基とは、Ｌ２のことではない。また、Ａｒ３における芳香環基が有してもよい置換基とは、Ａｒ４のことでもない。
　また、Ａｒ１とＡｒ２とは、それぞれの芳香環基同士が式（１）中に明示される単結合で直接結合している。
　同様に、Ａｒ３とＡｒ４とは、それぞれの芳香環基同士が式（１）中に明示される単結合で直接結合している。 The substituent that the aromatic ring group in Ar 1 and Ar 2 may have is not L 1 . Further, the substituent that the aromatic ring group in Ar 2 may have is not Ar 1 .
Similarly, the substituent that the aromatic ring group in Ar 3 and Ar 3 may have is not L 2 . Further, the substituent that the aromatic ring group in Ar 3 may have is not Ar 4 .
Further, Ar 1 and Ar 2 are directly bonded to each other by a single bond specified in the formula (1).
Similarly, Ar 3 and Ar 4 are directly bonded to each other by a single bond specified in the formula (1).
　Ａｒ１～Ａｒ４における芳香環基が有してもよい置換基としては、例えば、置換基Ｗが挙げられ、中でも、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、又は、置換基を有してもよいヘテロアリール基が好ましい。
　また、上記芳香環基が、更に、置換基としての芳香環基を有するのも好ましい。上記「置換基としての芳香環基」としては、例えば、上述の、単環の芳香環基及び多環の芳香環基が挙げられる。
　また、芳香環基が、更に、置換基としての芳香環基を有する場合、これらの芳香環基の１以上がそれぞれ更に異なる置換基を有してもよい。また、これらの芳香環基がそれぞれ有する、上記更に異なる置換基同士が互いに結合していてもよい。つまり、これらの芳香環基同士が、その間に、更に異なる環を形成して結合していてもよい。ただし、これらの芳香環基同士の間に形成される、上記更に異なる環は、非芳香環である。
　例えば、芳香環基Ａが、更に、置換基としての芳香環基Ｂを有する場合において、芳香環基Ａは更に置換基Ａを有していてもよく、芳香環基Ｂは更に置換基Ｂを有していてもよい。置換基Ａと置換基Ｂとは互いに結合して、芳香環基Ａと芳香環基Ｂとの間に、更に異なる環（非芳香環）を形成していてもよい。
　芳香環基同士が、その間に、更に異なる環（非芳香環）を形成して結合している形態の具体例としては、例えば、これらの芳香環基同士が共同してフルオレン環基を形成している形態が挙げられる。つまり、例えば、Ａｒ１～Ａｒ４（好ましくは、Ａｒ１及び／又はＡｒ４）は、フルオレン環基（９，９－ジメチルフルオレン環基のような、置換基を有するフルオレン環基であってもよい）であってもよい。 Examples of the substituent which the aromatic ring group in Ar 1 to Ar 4 may have include the substituent W, and among them, a halogen atom, an alkyl group which may have a substituent, and a substituent are included. A aryl group which may have a substituent or a heteroaryl group which may have a substituent is preferable.
It is also preferable that the aromatic ring group further has an aromatic ring group as a substituent. Examples of the above-mentioned "aromatic ring group as a substituent" include the above-mentioned monocyclic aromatic ring group and polycyclic aromatic ring group.
Further, when the aromatic ring group further has an aromatic ring group as a substituent, one or more of these aromatic ring groups may have further different substituents. Further, the different substituents of each of these aromatic ring groups may be bonded to each other. That is, these aromatic ring groups may be bonded to each other by forming a further different ring between them. However, the further different ring formed between these aromatic ring groups is a non-aromatic ring.
For example, when the aromatic ring group A further has an aromatic ring group B as a substituent, the aromatic ring group A may further have a substituent A, and the aromatic ring group B further contains a substituent B. You may have. Substituent A and substituent B may be bonded to each other to form a further different ring (non-aromatic ring) between the aromatic ring group A and the aromatic ring group B.
As a specific example of a form in which aromatic ring groups are bonded to each other by forming a further different ring (non-aromatic ring) between them, for example, these aromatic ring groups jointly form a fluorene ring group. The form is mentioned. That is, for example, Ar 1 to Ar 4 (preferably Ar 1 and / or Ar 4 ) may be a fluorene ring group having a substituent, such as a fluorene ring group (9,9-dimethylfluorene ring group). It may be).
　中でも、Ａｒ２及びＡｒ３は、置換基を有してもよい単環の芳香環基が好ましく、置換基を有してもよいベンゼン環基がより好ましい。
　また、本発明の効果がより優れる点から、Ａｒ１及びＡｒ２の少なくとも一方が置換基を有してもよいベンゼン環基であるのも好ましく、Ａｒ３及びＡｒ４の少なくとも一方が置換基を有してもよいベンゼン環基であるのも好ましい。
　なお、後述する通り、Ａｒ１とＡｒ２とは、式（１）中に明示される単結合の他にも、Ｌ１を介する結合を有していてもよい。例えば、Ａｒ１及びＡｒ２の両方が置換基を有してもよいベンゼン環基である場合において、Ａｒ１とＡｒ２とがＬ１を介する結合を有し、Ａｒ１とＡｒ２とが共同して、置換基を有してもよいフルオレン環基を形成してもよい。
　同様に、Ａｒ３とＡｒ４とは、式（１）中に明示される単結合の他にも、Ｌ２を介する結合を有していてもよい。例えば、Ａｒ３及びＡｒ４の両方が置換基を有してもよいベンゼン環基である場合において、Ａｒ３とＡｒ４とがＬ２を介する結合を有し、Ａｒ３とＡｒ４とが共同して、置換基を有してもよいフルオレン環基を形成してもよい。 Among them, Ar 2 and Ar 3 are preferably a monocyclic aromatic ring group which may have a substituent, and more preferably a benzene ring group which may have a substituent.
Further, from the viewpoint that the effect of the present invention is more excellent, it is preferable that at least one of Ar 1 and Ar 2 is a benzene ring group which may have a substituent, and at least one of Ar 3 and Ar 4 has a substituent. It is also preferable that it is a benzene ring group which may have.
As will be described later, Ar 1 and Ar 2 may have a bond via L 1 in addition to the single bond specified in the equation (1). For example, when both Ar 1 and Ar 2 are benzene ring groups which may have a substituent, Ar 1 and Ar 2 have a bond via L 1 , and Ar 1 and Ar 2 are jointly used. Then, a fluorene ring group which may have a substituent may be formed.
Similarly, Ar 3 and Ar 4 may have a bond via L 2 in addition to the single bond specified in the formula (1). For example, when both Ar 3 and Ar 4 are benzene ring groups which may have a substituent, Ar 3 and Ar 4 have a bond via L 2 , and Ar 3 and Ar 4 are jointly used. Then, a fluorene ring group which may have a substituent may be formed.
　中でも、本発明の効果がより優れる点から、Ａｒ１及びＡｒ４は、それぞれ独立に、置換基を有してもよい多環の芳香環基、又は、式（Ｒ）で表される基であるのが好ましい。 Above all, from the viewpoint that the effect of the present invention is more excellent, Ar 1 and Ar 4 are polycyclic aromatic ring groups which may have substituents or groups represented by the formula (R), respectively. It is preferable to have it.
　上記多環の芳香環基の環員数は９～１８が好ましい。
　上記多環の芳香環基の例は上述の通りであり、ナフタレン環基又はベンゾチオフェン環基が好ましい。 The number of ring members of the polycyclic aromatic ring group is preferably 9 to 18.
Examples of the polycyclic aromatic ring group are as described above, and a naphthalene ring group or a benzothiophene ring group is preferable.
　式（Ｒ）で表される基を次に示す。 The group represented by the formula (R) is shown below.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　式（Ｒ）中、＊１及び＊２は、それぞれ独立に結合位置を表す。具体的には、式（Ｒ）で表される基であるＡｒ１において、＊１はＡｒ２との結合位置を表し、＊２は（Ｌ１）ｍ１との結合位置を表す。式（Ｒ）で表される基であるＡｒ４において、＊１はＡｒ３との結合位置を表し、＊２は（Ｌ２）ｍ２との結合位置を表す。
　ただし、後述のとおり、ｍ１及びｍ２は０でもよい。式（Ｒ）で表される基であるＡｒ１において、ｍ１が０である場合、＊２は存在しない。式（Ｒ）で表される基であるＡｒ４において、ｍ２が０である場合、＊２は存在しない。
　式（Ｒ）中、ＡｒＸは、ＡｒＹ以外にも置換基を有してもよい単環の芳香環基を表す。
　上記単環の芳香環基の例は上述の通りであり、中でも、ベンゼン環基が好ましい。
　式（Ｒ）中、ＡｒＹは、置換基を有してもよい芳香環基を表す。ＡｒＹの芳香環基の例としては、上述の単環の芳香環基、及び、上述の多環の芳香環基が挙げられ、中でも、ベンゼン環基が好ましい。
　ＡｒＸにおける単環の芳香環基と、ＡｒＹにおける芳香環基とは、互いに環員原子同士が単結合で結合している。
　ＡｒＸにおける単環の芳香環基がＡｒＹ以外にも有してもよい置換基、及び、ＡｒＹにおける芳香環基が有してもよい置換基としては、置換基Ｗが挙げられる。
　ＡｒＸにおける単環の芳香環基は、ＡｒＹ以外には置換基を有さないのも好ましい。
　また、ＡｒＹにおける芳香環基が有してもよい置換基は、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、又は、置換基を有してもよいヘテロアリール基が好ましい。
　ただし、ＡｒＸにおける単環の芳香環基がＡｒＹ以外にも有してもよい置換基と、ＡｒＹにおける芳香環基が有してもよい置換基とは、互いに結合することはない。つまり、ＡｒＸとＡｒＹとは、式（Ｒ）中に明示される単結合以外では結合しない。例えば、式（Ｒ）で表される基に、フルオレン環基は含まれない。 In the formula (R), * 1 and * 2 independently represent the coupling positions. Specifically, in Ar 1 which is a group represented by the formula (R), * 1 represents the bonding position with Ar 2 and * 2 represents the bonding position with (L 1 ) m 1 . In Ar 4 which is a group represented by the formula (R), * 1 represents a bond position with Ar 3 and * 2 represents a bond position with (L 2 ) m 2 .
However, as described later, m1 and m2 may be 0. In Ar 1 which is a group represented by the formula (R), when m1 is 0, * 2 does not exist. In Ar 4 which is a group represented by the formula (R), when m2 is 0, * 2 does not exist.
In the formula (R), Ar X represents a monocyclic aromatic ring group which may have a substituent other than Ar Y.
Examples of the monocyclic aromatic ring group are as described above, and among them, a benzene ring group is preferable.
In formula (R), Ar Y represents an aromatic ring group which may have a substituent. Examples of the aromatic ring group of Ar Y include the above-mentioned monocyclic aromatic ring group and the above-mentioned polycyclic aromatic ring group, and among them, the benzene ring group is preferable.
The monocyclic aromatic ring group in Ar X and the aromatic ring group in Ar Y have ring-membered atoms bonded to each other by a single bond.
Examples of the substituent that the monocyclic aromatic ring group in Ar X may have other than Ar Y and the substituent that the aromatic ring group in Ar Y may have include the substituent W.
It is also preferable that the monocyclic aromatic ring group in Ar X has no substituent other than Ar Y.
Further, the substituent which the aromatic ring group may have in Ar Y has a halogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Heteroaryl groups may be preferred.
However, the substituent that the monocyclic aromatic ring group in Ar X may have other than Ar Y and the substituent that the aromatic ring group in Ar Y may have do not bond to each other. That is, Ar X and Ar Y are not combined except for the single bond specified in the formula (R). For example, the group represented by the formula (R) does not include a fluorene ring group.
　式（１）中、ｍ１及びｍ２は、それぞれ独立に、０又は１を表す。
　式（１）中、Ｌ１及びＬ２は、それぞれ独立に、－Ｓ－、－Ｏ－、－Ｓｅ－、－ＳｉＲａ４Ｒａ５－、－ＮＲａ６－、又は、－ＣＲａ７Ｒａ８－を表す。
　Ｒａ４～Ｒａ８は、それぞれ独立に、水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいシリル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアリール基、又は、置換基を有してもよいヘテロアリール基を表す。
　中でも、Ｌ１及びＬ２は、それぞれ独立に、－ＣＲａ７Ｒａ８－が好ましく、Ｒａ７及びＲａ８が置換基を有してもよいアルキル基である－ＣＲａ７Ｒａ８－がより好ましく、－Ｃ（ＣＨ３）２－が更に好ましい。
　なお、Ｌ１は、Ａｒ１及びＡｒ２におけるそれぞれの芳香環基に対して直接結合している。
　同様に、Ｌ２は、Ａｒ３及びＡｒ４におけるそれぞれの芳香環基に対して直接結合している。 In formula (1), m1 and m2 independently represent 0 or 1, respectively.
In formula (1), L 1 and L 2 independently form -S-, -O-, -Se- , -SiR a4 R a5- , -NR a6- , or -CR a7 R a8- , respectively. Represent.
R a4 to R a8 are independently hydrogen atom, halogen atom, alkyl group which may have a substituent, alkoxy group which may have a substituent, and an alkylthio group which may have a substituent. It has a silyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents a optionally heteroaryl group.
Among them, L 1 and L 2 each independently, -CR a7 R a8 - preferably, R a7 and R a8 are -CR a7 R a8 is an alkyl group which may have a substituent - are more preferred, -C (CH 3 ) 2 -is more preferable.
In addition, L 1 is directly bonded to each aromatic ring group in Ar 1 and Ar 2 .
Similarly, L 2 is directly attached to the respective aromatic ring groups in Ar 3 and Ar 4 .
　ただし、ｍ１が０を表す場合、Ｌ１は存在せず、Ａｒ１とＡｒ２とは、式（１）中に明示された単結合のみで連結する。
　ｍ２が０を表す場合、Ｌ２は存在せず、Ａｒ３とＡｒ４とは、式（１）中に明示された単結合のみで連結する。
　例えば、ｍ１及びｍ２が０を表す場合、特定化合物は、下記式（１ａ）で表される化合物となる。同様に、ｍ１及びｍ２が１を表す場合、特定化合物は、下記式（１ｂ）で表される化合物となる。
　なお、下記式（１ａ）及び式（１ｂ）の各記号で表される基は、式（１）中の相当する基とそれぞれ同様である。 However, when m1 represents 0, L 1 does not exist, and Ar 1 and Ar 2 are connected only by the single bond specified in the equation (1).
When m2 represents 0, L 2 does not exist, and Ar 3 and Ar 4 are connected only by the single bond specified in the equation (1).
For example, when m1 and m2 represent 0, the specific compound is a compound represented by the following formula (1a). Similarly, when m1 and m2 represent 1, the specific compound is a compound represented by the following formula (1b).
The groups represented by the symbols of the following formulas (1a) and (1b) are the same as the corresponding groups in the formula (1).
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
（式（２）で表される化合物、式（３）で表される化合物、式（４）で表される化合物）
　本発明の効果がより優れる点から、式（１）で表される化合物は、式（２）で表される化合物、式（３）で表される化合物、又は、式（４）で表される化合物であるのが好ましい。中でも、式（１）で表される化合物は、式（３）で表される化合物であるのがより好ましい。 (Compound represented by formula (2), compound represented by formula (3), compound represented by formula (4))
From the viewpoint that the effect of the present invention is more excellent, the compound represented by the formula (1) is represented by the compound represented by the formula (2), the compound represented by the formula (3), or the compound represented by the formula (4). It is preferably a compound. Among them, the compound represented by the formula (1) is more preferably the compound represented by the formula (3).
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　式（２）中、Ｙ３及びＹ４は、それぞれ独立に、－Ｏ－、－Ｓ－、又は、－Ｓｅ－を表す。
　式（２）中、Ｒ１～Ｒ４は、それぞれ独立に、水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいシリル基、置換基を有してもよいアリール基、又は、置換基を有してもよいヘテロアリール基を表す。
　式（２）中、Ａｒ１～Ａｒ４は、それぞれ独立に、置換基を有してもよい芳香環基を表す。
　式（２）中、ｍ１及びｍ２は、それぞれ独立に、０又は１を表す。
　式（２）中、Ｌ１及びＬ２は、それぞれ独立に、－Ｓ－、－Ｏ－、－Ｓｅ－、－ＳｉＲａ４Ｒａ５－、－ＮＲａ６－、又は、－ＣＲａ７Ｒａ８－を表す。
　式（２）中、Ｒａ４～Ｒａ８は、それぞれ独立に、水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいシリル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアリール基、又は、置換基を有してもよいヘテロアリール基を表す。
　ただし、ｍ１が０を表す場合、Ｌ１は存在せず、Ａｒ１とＡｒ２とは、上記式（２）中に明示された単結合のみで連結する。ｍ２が０を表す場合、Ｌ２は存在せず、Ａｒ３とＡｒ４とは、上記式（２）中に明示された単結合のみで連結する。
　式（２）中のＡｒ１～Ａｒ４、ｍ１、ｍ２、Ｌ１、Ｌ２、及び、Ｒａ４～Ｒａ８は、式（１）中のＡｒ１～Ａｒ４、ｍ１、ｍ２、Ｌ１、Ｌ２、及び、Ｒａ４～Ｒａ８とそれぞれ同様である。 In formula (2), Y 3 and Y 4 independently represent -O-, -S-, or -Se-, respectively.
In the formula (2), R 1 to R 4 independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. It represents an alkylthio group which may have a substituent, a silyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.
In the formula (2), Ar 1 to Ar 4 each independently represent an aromatic ring group which may have a substituent.
In formula (2), m1 and m2 independently represent 0 or 1, respectively.
In formula (2), L 1 and L 2 independently form -S-, -O-, -Se- , -SiR a4 R a5- , -NR a6- , or -CR a7 R a8- , respectively. Represent.
In the formula (2), R a4 to R a8 independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. An alkylthio group which may have a substituent, a silyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, Alternatively, it represents a heteroaryl group which may have a substituent.
However, if m1 represents 0, L 1 is absent, and Ar 1 and Ar 2, are connected only by a single bond, which is specified in the above formula (2). When m2 represents 0, L 2 does not exist, and Ar 3 and Ar 4 are connected only by the single bond specified in the above equation (2).
Ar 1 to Ar 4 , m1, m2, L 1 , L 2 and R a4 to R a8 in the formula (2) are Ar 1 to Ar 4 , m1, m2, L 1 , in the formula (1). It is the same as L 2 and R a4 to R a8 , respectively.
Figure JPOXMLDOC01-appb-C000010
　式（３）中、Ｙ３及びＸ３は、それぞれ独立に、－Ｏ－、－Ｓ－、又は、－Ｓｅ－を表す。
　式（３）中、Ｒ１～Ｒ３及びＲ５は、それぞれ独立に、水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいシリル基、置換基を有してもよいアリール基、又は、置換基を有してもよいヘテロアリール基を表す。
　式（３）中、Ａｒ１～Ａｒ４は、それぞれ独立に、置換基を有してもよい芳香環基を表す。
　式（３）中、ｍ１及びｍ２は、それぞれ独立に、０又は１を表す。
　式（３）中、Ｌ１及びＬ２は、それぞれ独立に、－Ｓ－、－Ｏ－、－Ｓｅ－、－ＳｉＲａ４Ｒａ５－、－ＮＲａ６－、又は、－ＣＲａ７Ｒａ８－を表す。
　式（３）中、Ｒａ４～Ｒａ８は、それぞれ独立に、水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいシリル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアリール基、又は、置換基を有してもよいヘテロアリール基を表す。
　ただし、ｍ１が０を表す場合、Ｌ１は存在せず、Ａｒ１とＡｒ２とは、上記式（３）中に明示された単結合のみで連結する。ｍ２が０を表す場合、Ｌ２は存在せず、Ａｒ３とＡｒ４とは、上記式（３）中に明示された単結合のみで連結する。
　式（３）中のＡｒ１～Ａｒ４、ｍ１、ｍ２、Ｌ１、Ｌ２、及び、Ｒａ４～Ｒａ８は、式（１）中のＡｒ１～Ａｒ４、ｍ１、ｍ２、Ｌ１、Ｌ２、及び、Ｒａ４～Ｒａ８とそれぞれ同様である。
Figure JPOXMLDOC01-appb-C000010
In formula (3), Y 3 and X 3 independently represent -O-, -S-, or -Se-, respectively.
In the formula (3), R 1 to R 3 and R 5 are independently a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent, respectively. Represents an alkylthio group which may have a substituent, a silyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.
In the formula (3), Ar 1 to Ar 4 each independently represent an aromatic ring group which may have a substituent.
In formula (3), m1 and m2 independently represent 0 or 1, respectively.
In formula (3), L 1 and L 2 independently form -S-, -O-, -Se- , -SiR a4 R a5- , -NR a6- , or -CR a7 R a8- , respectively. Represent.
In the formula (3), R a4 to R a8 independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. An alkylthio group which may have a substituent, a silyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, Alternatively, it represents a heteroaryl group which may have a substituent.
However, if m1 represents 0, L 1 is absent, and Ar 1 and Ar 2, are connected only by a single bond, which is specified in the above formula (3). When m2 represents 0, L 2 does not exist, and Ar 3 and Ar 4 are connected only by the single bond specified in the above equation (3).
Ar 1 to Ar 4 , m1, m2, L 1 , L 2 and R a4 to R a8 in the formula (3) are Ar 1 to Ar 4 , m1, m2, L 1 , L 1 in the formula (1). It is the same as L 2 and R a4 to R a8 , respectively.
Figure JPOXMLDOC01-appb-C000011
　式（４）中、Ｘ３及びＸ４は、それぞれ独立に、－Ｏ－、－Ｓ－、又は、－Ｓｅ－を表す。
　式（４）中、Ｒ１～Ｒ２及びＲ５～Ｒ６は、それぞれ独立に、水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいシリル基、置換基を有してもよいアリール基、又は、置換基を有してもよいヘテロアリール基を表す。
　式（４）中、Ａｒ１～Ａｒ４は、それぞれ独立に、置換基を有してもよい芳香環基を表す。
　式（４）中、ｍ１及びｍ２は、それぞれ独立に、０又は１を表す。
　式（４）中、Ｌ１及びＬ２は、それぞれ独立に、－Ｓ－、－Ｏ－、－Ｓｅ－、－ＳｉＲａ４Ｒａ５－、－ＮＲａ６－、又は、－ＣＲａ７Ｒａ８－を表す。
　式（４）中、Ｒａ４～Ｒａ８は、それぞれ独立に、水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいシリル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアリール基、又は、置換基を有してもよいヘテロアリール基を表す。
　ただし、ｍ１が０を表す場合、Ｌ１は存在せず、Ａｒ１とＡｒ２とは、前記式（４）中に明示された単結合のみで連結する。ｍ２が０を表す場合、Ｌ２は存在せず、Ａｒ３とＡｒ４とは、前記式（４）中に明示された単結合のみで連結する。
　式（４）中のＡｒ１～Ａｒ４、ｍ１、ｍ２、Ｌ１、Ｌ２、及び、Ｒａ４～Ｒａ８は、式（１）中のＡｒ１～Ａｒ４、ｍ１、ｍ２、Ｌ１、Ｌ２、及び、Ｒａ４～Ｒａ８とそれぞれ同様である。
Figure JPOXMLDOC01-appb-C000011
In formula (4), X 3 and X 4 independently represent -O-, -S-, or -Se-, respectively.
In formula (4), R 1 to R 2 and R 5 to R 6 independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and an alkoxy group which may have a substituent. , An alkylthio group which may have a substituent, a silyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.
In the formula (4), Ar 1 to Ar 4 each independently represent an aromatic ring group which may have a substituent.
In formula (4), m1 and m2 independently represent 0 or 1, respectively.
In formula (4), L 1 and L 2 independently form -S-, -O-, -Se- , -SiR a4 R a5- , -NR a6- , or -CR a7 R a8- , respectively. Represent.
In the formula (4), R a4 to R a8 independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. An alkylthio group which may have a substituent, a silyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, Alternatively, it represents a heteroaryl group which may have a substituent.
However, if m1 represents 0, L 1 is absent, and Ar 1 and Ar 2, are connected only by a single bond which is expressly in the formula (4). When m2 represents 0, L 2 does not exist, and Ar 3 and Ar 4 are connected only by the single bond specified in the above equation (4).
Equation (4) Ar 1 ~ Ar 4 in, m1, m2, L 1, L 2 and,, R a4 ~ R a8 are, Ar 1 ~ Ar 4 in the formula (1), m1, m2, L 1, It is the same as L 2 and R a4 to R a8 , respectively.
　特定化合物の分子量は特に制限されず、４２５～１２００が好ましく、４５０～９００がより好ましい。分子量が１２００以下であれば、蒸着温度が高くならず、化合物の分解が起こりにくい。分子量が４２５以上であれば、蒸着膜のガラス転移点が低くならず、光電変換素子の耐熱性が向上する。
　特定化合物は１種単独で使用してもよく、２種以上使用してもよい。 The molecular weight of the specific compound is not particularly limited, and is preferably 425 to 1200, more preferably 450 to 900. When the molecular weight is 1200 or less, the vapor deposition temperature does not rise and the decomposition of the compound is unlikely to occur. When the molecular weight is 425 or more, the glass transition point of the vapor-deposited film is not lowered, and the heat resistance of the photoelectric conversion element is improved.
The specific compound may be used alone or in combination of two or more.
　特定化合物は、撮像素子、又は、光センサに用いる光電変換膜の材料として特に有用である。また、特定化合物は、着色材料、液晶材料、有機半導体材料、電荷輸送材料、医薬材料、及び蛍光診断薬材料としても使用できる。 The specific compound is particularly useful as a material for a photoelectric conversion film used in an image sensor or an optical sensor. 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.
　特定化合物は、後述のｎ型半導体材料とのエネルギー準位のマッチングの点で、単独膜でのイオン化ポテンシャルが－５．０～－６．０ｅＶである化合物であるのが好ましい。 The specific compound is preferably a compound having 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.
　特定化合物の極大吸収波長は特に制限されず、例えば、３００～５００ｎｍの範囲にあるのが好ましい。
　なお、上記極大吸収波長は、特定化合物の吸収スペクトルを吸光度が０．５～１になる程度の濃度に調整して溶液状態（溶剤：クロロホルム）で測定した値である。 The maximum absorption wavelength of the specific compound is not particularly limited, and is preferably in the range of, for example, 300 to 500 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.
　光電変換膜の極大吸収波長は特に制限されず、例えば、３００～７００ｎｍの範囲にあるのが好ましい。 The maximum absorption wavelength of the photoelectric conversion film is not particularly limited, and is preferably in the range of, for example, 300 to 700 nm.
＜ｎ型半導体材料＞
　光電変換膜は、上述した特定化合物以外の他の成分として、ｎ型半導体材料を含む。ｎ型半導体材料は、アクセプター性有機半導体材料（化合物）であり、電子を受容しやすい性質がある有機化合物をいう。
　更に詳しくは、ｎ型半導体材料は、上述の特定化合物と接触させて用いた場合に、特定化合物よりも電子親和力の大きい有機化合物をいう。
　本明細書において、電子親和力の値としてＧａｕｓｓｉａｎ‘０９（Ｇａｕｓｓｉａｎ社製ソフトウェア）を用いてＢ３ＬＹＰ／６－３１Ｇ（ｄ）の計算により求められるＬＵＭＯの値の反数の値（マイナス１を掛けた値）を用いる。
　ｎ型半導体材料の電子親和力は、３．０～５．０ｅＶが好ましい。 <N-type semiconductor material>
The photoelectric conversion film contains an n-type semiconductor material as a component other than the above-mentioned specific compound. 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.
More specifically, the n-type semiconductor material refers to an organic compound having a higher electron affinity than the specific compound when used in contact with the above-mentioned specific compound.
In the present specification, the value of the reciprocal of the LUMO value obtained by the calculation of B3LYP / 6-31G (d) using Gaussian '09 (software manufactured by Gaussian) as the electron affinity value (value multiplied by -1). ) Is used.
The electron affinity of the n-type semiconductor material is preferably 3.0 to 5.0 eV.
　ｎ型半導体材料は、例えば、フラーレン及びその誘導体からなる群より選択されるフラーレン類、縮合芳香族炭素環化合物（例えば、ナフタレン誘導体、アントラセン誘導体、フェナントレン誘導体、テトラセン誘導体、ピレン誘導体、ペリレン誘導体、及び、フルオランテン誘導体）；窒素原子、酸素原子、及び、硫黄原子の少なくとも１つを有する５～７員環のヘテロ環化合物（例えば、ピリジン、ピラジン、ピリミジン、ピリダジン、トリアジン、キノリン、キノキサリン、キナゾリン、フタラジン、シンノリン、イソキノリン、プテリジン、アクリジン、フェナジン、フェナントロリン、テトラゾール、ピラゾール、イミダゾール、及び、チアゾール等）；ポリアリーレン化合物；フルオレン化合物；シクロペンタジエン化合物；シリル化合物；１，４，５，８－ナフタレンテトラカルボン酸無水物；１，４，５，８－ナフタレンテトラカルボン酸無水物イミド誘導体、オキサジアゾール誘導体；アントラキノジメタン誘導体；ジフェニルキノン誘導体；バソクプロイン、バソフェナントロリン、及びこれらの誘導体；トリアゾール化合物；ジスチリルアリーレン誘導体；含窒素ヘテロ環化合物を配位子として有する金属錯体；シロール化合物；ならびに、特開２００６－１００７６７号公報の段落［００５６］～［００５７］に記載の化合物が挙げられる。 The n-type semiconductor material includes, for example, fullerenes selected from the group consisting of fullerene and derivatives thereof, condensed aromatic carbocyclic compounds (for example, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and , Fluolanthene derivative); 5- to 7-membered heterocyclic compound having at least one nitrogen atom, oxygen atom, and sulfur atom (eg, pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxalin, quinazoline, phthalazine) , Synnoline, Isoquinolin, Pteridine, Aclysine, Phenazine, Phenantroline, Tetrazole, Pyrazole, Imidazole, and Thiazole, etc.); Polyarylene compounds; Fluorene compounds; Cyclopentadiene compounds; Cyril compounds; Acid anhydrides; 1,4,5,8-naphthalenetetracarboxylic acid anhydride imide derivatives, oxadiazole derivatives; anthracinodimethane derivatives; diphenylquinone derivatives; vasocproin, vasophenantroline, and derivatives thereof; triazole compounds; di Examples thereof include styrylallylen derivatives; metal complexes having a nitrogen-containing heterocyclic compound as a ligand; silol compounds; and the compounds described in paragraphs [0056] to [0057] of JP-A-2006-100767.
　中でも、ｎ型半導体材料は、フラーレン及びその誘導体からなる群より選択されるフラーレン類を含むのが好ましい。
　フラーレンは、例えば、フラーレンＣ６０、フラーレンＣ７０、フラーレンＣ７６、フラーレンＣ７８、フラーレンＣ８０、フラーレンＣ８２、フラーレンＣ８４、フラーレンＣ９０、フラーレンＣ９６、フラーレンＣ２４０、フラーレンＣ５４０、及び、ミックスドフラーレンが挙げられる。
　フラーレン誘導体は、例えば、上記フラーレンに置換基が付加した化合物が挙げられる。置換基は、アルキル基、アリール基、又は、複素環基が好ましい。フラーレン誘導体は、特開２００７－１２３７０７号公報に記載の化合物が好ましい。
　ｎ型半導体材料がフラーレン類を含む場合、光電変換膜中におけるｎ型半導体材料の合計の含有量に対するフラーレン類の含有量（＝（フラーレン類の単層換算での膜厚／全ｎ型半導体材料の単層換算での膜厚）×１００）は、１５～１００体積％が好ましく、３５～１００体積％がより好ましい。 Among them, the n-type semiconductor material preferably contains fullerenes selected from the group consisting of fullerenes and derivatives thereof.
Examples of 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.
Examples of the fullerene derivative include compounds in which a substituent is added to the fullerene. The substituent is preferably an alkyl group, an aryl group, or a heterocyclic group. As the fullerene derivative, the compound described in JP-A-2007-123707 is preferable.
When the n-type semiconductor material contains fullerenes, the content of fullerenes with respect to the total content of the n-type semiconductor materials in the photoelectric conversion film (= (thickness of fullerenes in terms of single layer / total n-type semiconductor material) The thickness) × 100) in terms of a single layer is preferably 15 to 100% by volume, more preferably 35 to 100% by volume.
　上段までに記載したｎ型半導体材料に代えて、又は、上段までに記載したｎ型半導体材料とともに、ｎ型半導体材料として有機色素を使用してもよい。
　ｎ型半導体材料として有機色素を使用することで、光電変換素子の吸収波長（極大吸収波長）を、任意の波長域にコントロールしやすい。
　上記有機色素は、例えば、シアニン色素、スチリル色素、ヘミシアニン色素、メロシアニン色素（ゼロメチンメロシアニン（シンプルメロシアニン）を含む）、ロダシアニン色素、アロポーラー色素、オキソノール色素、ヘミオキソノール色素、スクアリウム色素、クロコニウム色素、アザメチン色素、クマリン色素、アリーリデン色素、アントラキノン色素、トリフェニルメタン色素、アゾ色素、アゾメチン色素、メタロセン色素、フルオレノン色素、フルギド色素、ペリレン色素、フェナジン色素、フェノチアジン色素、キノン色素、ジフェニルメタン色素、ポリエン色素、アクリジン色素、アクリジノン色素、ジフェニルアミン色素、キノフタロン色素、フェノキサジン色素、フタロペリレン色素、ジオキサン色素、ポルフィリン色素、クロロフィル色素、フタロシアニン色素、サブフタロシアニン色素、金属錯体色素、特開２０１４－８２４８３号公報の段落［００８３］～［００８９］に記載の化合物、特開２００９－１６７３４８号公報の段落［００２９］～［００３３］に記載の化合物、特開２０１２－７７０６４号公報の段落［０１９７］～［０２２７］に記載の化合物、ＷＯ２０１８－１０５２６９号公報の段落［００３５］～［００３８］に記載の化合物、ＷＯ２０１８－１８６３８９号公報の段落［００４１］～［００４３］に記載の化合物、ＷＯ２０１８－１８６３９７号公報の段落［００５９］～［００６２］に記載の化合物、ＷＯ２０１９－００９２４９号公報の段落［００７８］～［００８３］に記載の化合物、ＷＯ２０１９－０４９９４６号公報の段落［００５４］～［００５６］に記載の化合物、ＷＯ２０１９－０５４３２７号公報の段落［００５９］～［００６３］に記載の化合物、及び、ＷＯ２０１９－０９８１６１号公報の段落［００８６］～［００８７］に記載の化合物が挙げられる。
　ｎ型半導体材料が有機色素を含む場合、光電変換膜中におけるｎ型半導体材料の合計の含有量に対する有機色素の含有量（＝（有機色素の単層換算での膜厚／全ｎ型半導体材料の単層換算での膜厚）×１００）は、１５～１００体積％が好ましく、３５～１００体積％がより好ましい。 An organic dye may be used as the n-type semiconductor material in place of the n-type semiconductor material described in the upper row or together with the n-type semiconductor material described in the upper row.
By using an organic dye as the n-type semiconductor material, it is easy to control the absorption wavelength (maximum absorption wavelength) of the photoelectric conversion element in an arbitrary wavelength range.
The organic pigments include, for example, cyanine pigments, styryl pigments, hemicyanine pigments, merocyanine pigments (including zero methine merocyanin (simple merocyanin)), rodacianin pigments, allopolar pigments, oxonols pigments, hemioxonor pigments, squalium pigments, croconium pigments, etc. Azamethin dye, coumarin dye, allylidene dye, anthraquinone dye, triphenylmethane dye, azo dye, azomethin dye, metallocene dye, fluorenone dye, flugide dye, perylene dye, phenazine dye, phenothiazine dye, quinone dye, diphenylmethane dye, polyene dye, Aclysin dye, acridinone dye, diphenylamine dye, quinophthalone dye, phenoxazine dye, phthaloperylene dye, dioxane dye, porphyrin dye, chlorophyll dye, phthalocyanine dye, subphthalocyanine dye, metal complex dye, paragraph [0083] of JP2014-82483. ] To [089], the compounds described in JP-A-2009-167348, paragraphs [0029]-[0033], and the compounds described in JP-A-2012-77064, paragraphs [0197]-[0227]. Compounds, compounds described in paragraphs [0035] to [0038] of WO2018-105269, compounds described in paragraphs [0041] to [0043] of WO2018-186389, paragraphs [0059] of WO2018-186397. -[0062], compounds described in paragraphs [0078]-[0083] of WO2019-009249, compounds described in paragraphs [0054]-[0056] of WO2019-049946, WO2019-054327. Examples thereof include the compounds described in paragraphs [0059] to [0063] of JP-A and the compounds described in paragraphs [0086] to [0087] of WO2019-0981661.
When the n-type semiconductor material contains an organic dye, the content of the organic dye relative to the total content of the n-type semiconductor material in the photoelectric conversion film (= (thickness in terms of single layer of organic dye / all n-type semiconductor material) The film thickness) × 100) in terms of a single layer is preferably 15 to 100% by volume, more preferably 35 to 100% by volume.
　ｎ型半導体材料の分子量は、２００～１２００が好ましく、２００～１０００がより好ましい。 The molecular weight of the n-type semiconductor material is preferably 200 to 1200, more preferably 200 to 1000.
　光電変換膜は、特定化合物とｎ型半導体材料とが混合された状態で形成されるバルクヘテロ構造を有するのが好ましい。バルクヘテロ構造は、光電変換膜内で、特定化合物とｎ型半導体材料とが混合、分散している層である。なお、バルクへテロ構造については、特開２００５－３０３２６６号公報の段落［００１３］～［００１４］等において詳細に説明されている。 The photoelectric conversion film preferably has a bulk heterostructure formed in a state where a specific compound and an n-type semiconductor material are mixed. The bulk heterostructure is a layer in which a specific compound and an n-type semiconductor material are mixed and dispersed in a photoelectric conversion film. The bulk heterostructure is described in detail in paragraphs [0013] to [0014] of JP-A-2005-303266.
　光電変換素子の応答性の点から、特定化合物とｎ型半導体材料との合計の含有量に対する特定化合物の含有量（＝特定化合物の単層換算での膜厚／（特定化合物の単層換算での膜厚＋ｎ型半導体材料の単層換算での膜厚）×１００）は、１５～７５体積％が好ましく、３５～７５体積％がより好ましい。
　なお、光電変換膜は、実質的に、特定化合物とｎ型半導体材料とから構成されるのが好ましい。実質的とは、光電変換膜全質量に対して、特定化合物及びｎ型半導体材料の合計含有量が９５質量％以上であることを意味する。 From the viewpoint of the responsiveness of the photoelectric conversion element, the content of the specific compound relative to the total content of the specific compound and the n-type semiconductor material (= film thickness of the specific compound in terms of single layer / (in terms of single layer of the specific compound) The film thickness of the n-type semiconductor material (thickness in terms of a single layer) × 100) is preferably 15 to 75% by volume, more preferably 35 to 75% by volume.
It is preferable that the photoelectric conversion film is substantially composed of a specific compound and an n-type semiconductor material. Substantially means that the total content of the specific compound and the n-type semiconductor material is 95% by mass or more with respect to the total mass of the photoelectric conversion film.
　なお、光電変換膜中に含まれるｎ型半導体材料は、１種単独で使用してもよいし、２種以上を併用してもよい。 The n-type semiconductor material contained in the photoelectric conversion film may be used alone or in combination of two or more.
　特定化合物を含む光電変換膜は非発光性膜であり、有機電界発光素子（ＯＬＥＤ：Ｏｒｇａｎｉｃ　Ｌｉｇｈｔ　Ｅｍｉｔｔｉｎｇ　Ｄｉｏｄｅ）とは異なる特徴を有する。非発光性膜とは発光量子効率が１％以下の膜を意図し、発光量子効率は０．５％以下が好ましく、０．１％以下がより好ましい。 The photoelectric conversion film containing a specific compound is a non-luminescent film, and has characteristics different from those of an organic electroluminescent device (OLED: Organic Light Emitting Diode). The non-emission film is intended to be a film having an emission quantum efficiency of 1% or less, and an emission quantum efficiency of 0.5% or less is preferable, and 0.1% or less is more preferable.
＜成膜方法＞
　光電変換膜は、主に、乾式成膜法により成膜できる。乾式成膜法は、例えば、蒸着法（特に、真空蒸着法）、スパッタ法、イオンプレーティング法、及び、ＭＢＥ（Ｍｏｌｅｃｕｌａｒ　Ｂｅａｍ　Ｅｐｉｔａｘｙ）法等の物理気相成長法、並びに、プラズマ重合等のＣＶＤ（Ｃｈｅｍｉｃａｌ　Ｖａｐｏｒ　Ｄｅｐｏｓｉｔｉｏｎ）法が挙げられる。なかでも、真空蒸着法が好ましい。真空蒸着法により光電変換膜を成膜する場合、真空度及び蒸着温度等の製造条件は常法に従って設定できる。 <Film formation method>
The photoelectric conversion film can be formed mainly by a dry film forming method. The dry film forming method includes, for example, a physical vapor deposition method such as a vapor deposition method (particularly a vacuum vapor deposition method), a sputtering method, an ion plating method, an MBE (Molecular Beam Epitaxy) method, and a CVD method such as plasma polymerization. (Chemical Vapor Deposition) method can be mentioned. Of these, the vacuum deposition method is preferable. When the photoelectric conversion film is formed by the vacuum vapor deposition method, the manufacturing conditions such as the degree of vacuum and the vapor deposition temperature can be set according to a conventional method.
　光電変換膜の厚みは、１０～１０００ｎｍが好ましく、５０～８００ｎｍがより好ましく、５０～５００ｎｍが更に好ましく、５０～３００ｎｍが特に好ましい。 The thickness of the photoelectric conversion film is preferably 10 to 1000 nm, more preferably 50 to 800 nm, further preferably 50 to 500 nm, and particularly preferably 50 to 300 nm.
＜電極＞
　電極（上部電極（透明導電性膜）１５と下部電極（導電性膜）１１）は、導電性材料から構成される。導電性材料は、金属、合金、金属酸化物、電気伝導性化合物、及びこれらの混合物等が挙げられる。
　上部電極１５から光が入射されるため、上部電極１５は検知したい光に対し透明であるのが好ましい。上部電極１５を構成する材料は、例えば、アンチモン又はフッ素等をドープした酸化錫（ＡＴＯ：Ａｎｔｉｍｏｎｙ　Ｔｉｎ　Ｏｘｉｄｅ、ＦＴＯ：Ｆｌｕｏｒｉｎｅ　ｄｏｐｅｄ　Ｔｉｎ　Ｏｘｉｄｅ）、酸化錫、酸化亜鉛、酸化インジウム、酸化インジウム錫（ＩＴＯ：Ｉｎｄｉｕｍ　Ｔｉｎ　Ｏｘｉｄｅ）、及び、酸化亜鉛インジウム（ＩＺＯ：Ｉｎｄｉｕｍ　ｚｉｎｃ　ｏｘｉｄｅ）等の導電性金属酸化物；金、銀、クロム、及び、ニッケル等の金属薄膜；これらの金属と導電性金属酸化物との混合物又は積層物；ならびに、ポリアニリン、ポリチオフェン、及び、ポリピロール等の有機導電性材料、等が挙げられる。なかでも、高導電性及び透明性等の点から、導電性金属酸化物が好ましい。 <Electrode>
The electrodes (upper electrode (transparent conductive film) 15 and lower electrode (conductive film) 11) are made of a conductive material. Examples of 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 is, for example, antimony or fluorine-doped tin oxide (ATO: Antimony Tin Oxide, FTO: Fluorine topped Tin Oxide), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO: Conductive metal oxides such as Indium Tin Oxide) and indium zinc oxide (IZO); metal thin films such as gold, silver, chromium, and nickel; these metals and conductive metal oxides Mixtures or laminates; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and the like. Of these, conductive metal oxides are preferable from the viewpoints of high conductivity and transparency.
　通常、導電性膜をある範囲より薄くすると、急激な抵抗値の増加をもたらすが、本実施形態にかかる光電変換素子を組み込んだ固体撮像素子では、シート抵抗は、好ましくは１００～１００００Ω／□でよく、薄膜化できる膜厚の範囲の自由度は大きい。また、上部電極（透明導電性膜）１５は厚みが薄いほど吸収する光の量は少なくなり、一般に光透過率が増す。光透過率の増加は、光電変換膜での光吸収を増大させ、光電変換能を増大させるため、好ましい。薄膜化に伴う、リーク電流の抑制、薄膜の抵抗値の増大、及び、透過率の増加を考慮すると、上部電極１５の膜厚は、５～１００ｎｍが好ましく、５～２０ｎｍがより好ましい。 Normally, if the conductive film is made thinner than a certain range, the resistance value increases sharply. However, in the solid-state imaging device incorporating the photoelectric conversion element according to the present embodiment, the sheet resistance is preferably 100 to 10000 Ω / □. Well, the degree of freedom in the range of film thickness that can be thinned is large. Further, the thinner the upper electrode (transparent conductive film) 15, the smaller the amount of light absorbed, and the light transmittance generally increases. Increasing the light transmittance is preferable because it increases the light absorption in the photoelectric conversion film and increases the photoelectric conversion ability. Considering the suppression of leak current, the increase in the resistance value of the thin film, and the increase in the transmittance accompanying the thinning, the film thickness of the upper electrode 15 is preferably 5 to 100 nm, more preferably 5 to 20 nm.
　下部電極１１は、用途に応じて、透明性を持たせる場合と、逆に透明性を持たせず光を反射させる場合とがある。下部電極１１を構成する材料は、例えば、アンチモン又はフッ素等をドープした酸化錫（ＡＴＯ、ＦＴＯ）、酸化錫、酸化亜鉛、酸化インジウム、酸化インジウム錫（ＩＴＯ）、及び、酸化亜鉛インジウム（ＩＺＯ）等の導電性金属酸化物；金、銀、クロム、ニッケル、チタン、タングステン、及び、アルミ等の金属、これらの金属の酸化物又は窒化物等の導電性化合物（一例として窒化チタン（ＴｉＮ）を挙げる）；これらの金属と導電性金属酸化物との混合物又は積層物；並びに、ポリアニリン、ポリチオフェン、及び、ポリピロール、等の有機導電性材料等が挙げられる。 The lower electrode 11 may be transparent or may reflect light without being transparent, depending on the intended use. The materials constituting the lower electrode 11 are, for example, antimony or fluorine-doped tin oxide (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). Conductive metal oxides such as gold, silver, chromium, nickel, titanium, tungsten, and metals such as aluminum, oxides of these metals, or conductive compounds such as nitrides (as an example, titanium nitride (TiN)). ); Mixtures or laminates of these metals and conductive metal oxides; and organic conductive materials such as polyaniline, polythiophene, and polypyrrole.
　電極を形成する方法は特に制限されず、電極材料に応じて適宜選択できる。具体的には、印刷方式、及び、コーティング方式等の湿式方式；真空蒸着法、スパッタ法、及び、イオンプレーティング法等の物理的方式；並びに、ＣＶＤ、及び、プラズマＣＶＤ法等の化学的方式、等が挙げられる。
　電極の材料がＩＴＯの場合、電子ビーム法、スパッタ法、抵抗加熱蒸着法、化学反応法（ゾル－ゲル法等）、及び、酸化インジウムスズの分散物の塗布等の方法が挙げられる。 The method for forming the electrode is not particularly limited and can be appropriately selected depending on the electrode material. Specifically, a wet method such as a printing method and a coating method; a physical method such as a vacuum deposition method, a sputtering method, and an ion plating method; and a chemical method such as CVD and a plasma CVD method. , Etc. can be mentioned.
When the electrode material is ITO, methods such as 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 can be mentioned.
＜電荷ブロッキング膜：電子ブロッキング膜、正孔ブロッキング膜＞
　本発明の光電変換素子は、導電性膜と透明導電性膜との間に、光電変換膜の他に１種以上の中間層を有しているのも好ましい。上記中間層は、電荷ブロッキング膜が挙げられる。光電変換素子がこの膜を有することにより、得られる光電変換素子の特性（光電変換効率及び応答性等）がより優れる。電荷ブロッキング膜は、電子ブロッキング膜と正孔ブロッキング膜とが挙げられる。以下に、それぞれの膜について詳述する。 <Charge blocking film: electron blocking film, hole blocking film>
The photoelectric conversion element of the present invention preferably has one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film. Examples of the intermediate layer include a charge blocking film. When the photoelectric conversion element has this film, the characteristics (photoelectric conversion efficiency, responsiveness, etc.) of the obtained photoelectric conversion element are more excellent. Examples of the charge blocking film include an electron blocking film and a hole blocking film. Each film will be described in detail below.
（電子ブロッキング膜）
　電子ブロッキング膜は、ドナー性有機半導体材料（化合物）であり、例えば、下記のｐ型有機半導体を使用できる。ｐ型有機半導体は１種単独で使用してもよく、２種以上を使用してもよい。 (Electronic blocking film)
The electron blocking film is a donor organic semiconductor material (compound), and for example, the following p-type organic semiconductors can be used. One type of p-type organic semiconductor may be used alone, or two or more types may be used.
　ｐ型有機半導体は、例えば、トリアリールアミン化合物（例えば、Ｎ，Ｎ’－ビス(３－メチルフェニル)－(１，１’－ビフェニル)－４，４’－ジアミン（ＴＰＤ）、４，４’－ビス［Ｎ－(ナフチル)－Ｎ－フェニル－アミノ］ビフェニル（α－ＮＰＤ）、特開２０１１－２２８６１４号公報の段落[０１２８]～［０１４８］に記載の化合物、特開２０１１－１７６２５９号公報の段落［００５２］～［００６３］に記載の化合物、特開２０１１－２２５５４４号公報の段落［０１１９］～［０１５８］に記載の化合物、特開２０１５－１５３９１０号公報の［００４４］～［００５１］に記載の化合物、及び、特開２０１２－９４６６０号公報の段落［００８６］～［００９０］に記載の化合物等）、ピラゾリン化合物、スチリルアミン化合物、ヒドラゾン化合物、ポリシラン化合物、チオフェン化合物（例えば、チエノチオフェン誘導体、ジベンゾチオフェン誘導体、ベンゾジチオフェン誘導体、ジチエノチオフェン誘導体、［１］ベンゾチエノ［３，２－ｂ］チオフェン（ＢＴＢＴ）誘導体、チエノ［３，２－ｆ：４，５－ｆ´］ビス［１］ベンゾチオフェン（ＴＢＢＴ）誘導体、特開２０１８－１４４７４号の段落［００３１］～［００３６］に記載の化合物、ＷＯ２０１６－１９４６３０号の段落［００４３］～［００４５］に記載の化合物、ＷＯ２０１７－１５９６８４号の段落［００２５］～［００３７］、［００９９］～［０１０９］に記載の化合物、特開２０１７－０７６７６６号公報の段落［００２９］～［００３４］に記載の化合物、ＷＯ２０１８－２０７７２２の段落［００１５］～［００２５］に記載の化合物、特開２０１９－５４２２８の段落［００４５］～［００５３］に記載の化合物、ＷＯ２０１９－０５８９９５の段落［００４５］～［００５５］に記載の化合物、ＷＯ２０１９－０８１４１６の段落［００６３］～［００８９］に記載の化合物、特開２０１９－８００５２の段落［００３３］～［００３６］に記載の化合物等）、シアニン化合物、オキソノール化合物、ポリアミン化合物、インドール化合物、ピロール化合物、ピラゾール化合物、ポリアリーレン化合物、縮合芳香族炭素環化合物（例えば、ナフタレン誘導体、アントラセン誘導体、フェナントレン誘導体、テトラセン誘導体、ペンタセン誘導体、ピレン誘導体、ペリレン誘導体、及び、フルオランテン誘導体）、ポルフィリン化合物、フタロシアニン化合物、トリアゾール化合物、オキサジアゾール化合物、イミダゾール化合物、ポリアリールアルカン化合物、ピラゾロン化合物、アミノ置換カルコン化合物、オキサゾール化合物、フルオレノン化合物、シラザン化合物、並びに、含窒素ヘテロ環化合物を配位子として有する金属錯体が挙げられる。
　ｐ型有機半導体は、ｎ型半導体材料よりもイオン化ポテンシャルが小さい化合物が挙げられ、この条件を満たせば、ｎ型半導体材料として例示した有機色素も使用し得る。 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. '-Bis [N- (naphthyl) -N-phenyl-amino] biphenyl (α-NPD), a compound described in paragraphs [0128] to [0148] of JP2011-228614A, JP-A-2011-176259. The compounds described in paragraphs [0052] to [0063] of JP. 2011, the compounds described in paragraphs [0119] to [0158] of JP2011-225544, and [0044] to [0051] of JP2015-153910. ], And the compounds described in paragraphs [0086] to [0090] of JP2012-94660A), pyrazoline compounds, styrylamine compounds, hydrazone compounds, polysilane compounds, thiophene compounds (for example, thieno). Thiophen derivative, dibenzothiophene derivative, benzodithiophene derivative, dithienothiophene derivative, [1] benzothieno [3,2-b] thiophene (BTBT) derivative, thieno [3,2-f:4,5-f'] bis [1] Benzothiophene (TBBT) derivative, the compound described in paragraphs [0031] to [0036] of JP-A-2018-14474, the compound described in paragraphs [0043] to [0045] of WO2016-194630, WO2017- Compounds described in paragraphs 159,684 [0025] to [0037] and [0099] to [0109], compounds described in paragraphs [0029] to [0034] of JP-A-2017-07766, paragraphs WO2018-207722. Compounds described in [0015] to [0025], compounds described in paragraphs [0045] to [0053] of JP-A-2019-54228, compounds described in paragraphs [0045] to [0055] of WO2019-058995, WO2019- Compounds described in paragraphs [0063] to [089] of 081416, compounds described in paragraphs [0033] to [0036] of JP-A-2019-80052), cyanine compounds, oxonor compounds, polyamine compounds, indol compounds, pyrrole compounds. , Pyrazole compounds, polyarylene compounds, condensed aromatic carbocyclic compounds (eg, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pentacene derivatives, pyrene derivatives, perylene derivatives, and fluorantene derivatives. Body), porphyrin compounds, phthalocyanine compounds, triazole compounds, oxadiazole compounds, imidazole compounds, polyarylalkane compounds, pyrazolone compounds, amino-substituted calcon compounds, oxazole compounds, fluorenone compounds, silazane compounds, and nitrogen-containing heterocyclic compounds. Examples thereof include a metal complex having as a ligand.
Examples of the p-type organic semiconductor include compounds having a smaller ionization potential than the n-type semiconductor material, and if this condition is satisfied, the organic dye exemplified as the n-type semiconductor material can also be used.
　また、電子ブロッキング膜として、高分子材料も使用できる。
　高分子材料は、例えば、フェニレンビニレン、フルオレン、カルバゾール、インドール、ピレン、ピロール、ピコリン、チオフェン、アセチレン、及び、ジアセチレン等の重合体、並びに、その誘導体が挙げられる。 Further, a polymer material can also be used as the electron blocking film.
Examples of the polymer material include polymers such as phenylene vinylene, fluorene, carbazole, indole, pyrrole, pyrrole, picolin, thiophene, acetylene, and diacetylene, and derivatives thereof.
　なお、電子ブロッキング膜は、複数膜で構成してもよい。
　電子ブロッキング膜は、無機材料で構成されていてもよい。一般的に、無機材料は有機材料よりも誘電率が大きいため、無機材料を電子ブロッキング膜に用いた場合に、光電変換膜に電圧が多くかかるようになり、光電変換効率が高くなる。電子ブロッキング膜となりうる無機材料は、例えば、酸化カルシウム、酸化クロム、酸化クロム銅、酸化マンガン、酸化コバルト、酸化ニッケル、酸化銅、酸化ガリウム銅、酸化ストロンチウム銅、酸化ニオブ、酸化モリブデン、酸化インジウム銅、酸化インジウム銀、及び、酸化イリジウムが挙げられる。 The electron blocking film may be composed of a plurality of films.
The electron blocking film may be made of an inorganic material. In general, since an inorganic material has a higher dielectric constant than an organic material, when an inorganic material is used for an electron blocking film, a large voltage is applied to the photoelectric conversion film, and the photoelectric conversion efficiency becomes high. Inorganic materials that can serve as electron blocking films include, 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, and indium copper oxide. , Indium silver oxide, and iridium oxide.
（正孔ブロッキング膜）
　正孔ブロッキング膜は、アクセプター性有機半導体材料（化合物）であり、上述のｎ型半導体材料を利用できる。 (Hole blocking membrane)
The hole blocking film is an acceptor-type organic semiconductor material (compound), and the above-mentioned n-type semiconductor material can be used.
　電荷ブロッキング膜の製造方法は特に制限されず、例えば、乾式成膜法及び湿式成膜法が挙げられる。乾式成膜法は、例えば、蒸着法及びスパッタ法が挙げられる。蒸着法は、物理蒸着（ＰＶＤ：Ｐｈｙｓｉｃａｌ　Ｖａｐｏｒ　Ｄｅｐｏｓｉｔｉｏｎ）法及び化学蒸着（ＣＶＤ）法のいずれでもよく、真空蒸着法等の物理蒸着法が好ましい。湿式成膜法は、例えば、インクジェット法、スプレー法、ノズルプリント法、スピンコート法、ディップコート法、キャスト法、ダイコート法、ロールコート法、バーコート法、及び、グラビアコート法が挙げられ、高精度パターニングの点からは、インクジェット法が好ましい。 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. Examples of 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. Examples of 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. From the viewpoint of precision patterning, the inkjet method is preferable.
　電荷ブロッキング膜（電子ブロッキング膜及び正孔ブロッキング膜）の厚みは、それぞれ、３～２００ｎｍが好ましく、５～１００ｎｍがより好ましく、５～３０ｎｍが更に好ましい。 The thickness of the charge blocking film (electron blocking film and hole blocking film) is preferably 3 to 200 nm, more preferably 5 to 100 nm, and even more preferably 5 to 30 nm, respectively.
＜基板＞
　光電変換素子は、更に基板を有してもよい。使用される基板の種類は特に制限されず、例えば、半導体基板、ガラス基板、及び、プラスチック基板が挙げられる。
　なお、基板の位置は特に制限されず、通常、基板上に導電性膜、光電変換膜、及び透明導電性膜をこの順で積層する。 <Board>
The photoelectric conversion element may further have a substrate. The type of substrate used is not particularly limited, and examples thereof include a semiconductor substrate, a glass substrate, and a plastic substrate.
The position of the substrate is not particularly limited, and usually, a conductive film, a photoelectric conversion film, and a transparent conductive film are laminated on the substrate in this order.
＜封止層＞
　光電変換素子は、更に封止層を有してもよい。光電変換材料は水分子等の劣化因子の存在で顕著にその性能が劣化してしまうことがある。そこで、水分子を浸透させない緻密な金属酸化物、金属窒化物、もしくは、金属窒化酸化物等のセラミクス、又は、ダイヤモンド状炭素（ＤＬＣ：Ｄｉａｍｏｎｄ－ｌｉｋｅ　Ｃａｒｂｏｎ）等の封止層で光電変換膜全体を被覆して封止することで、上記劣化を防止できる。
　なお、封止層は、特開２０１１－０８２５０８号公報の段落［０２１０］～［０２１５］に記載に従って、材料の選択及び製造を行ってもよい。 <Encapsulation layer>
The photoelectric conversion element may further have a sealing layer. The performance of the photoelectric conversion material may be significantly deteriorated due to the presence of deterioration factors such as water molecules. Therefore, the entire photoelectric conversion film is coated with a ceramic such as a dense metal oxide, metal nitride, or metal nitride that does not allow water molecules to permeate, or a sealing layer such as diamond-like carbon (DLC: Diamond-like Carbon). The above deterioration can be prevented by coating and sealing.
The sealing layer may be selected and manufactured as a material in accordance with paragraphs [0210] to [0215] of JP2011-082508.
＜撮像素子＞
　光電変換素子の用途として、例えば、撮像素子が挙げられる。撮像素子とは、画像の光情報を電気信号に変換する素子であり、通常、複数の光電変換素子が同一平面状でマトリクス上に配置されており、各々の光電変換素子（画素）において光信号を電気信号に変換し、その電気信号を画素ごとに逐次撮像素子外に出力できるものをいう。そのために、画素ひとつあたり、一つ以上の光電変換素子、一つ以上のトランジスタから構成される。
　図３は、本発明の一実施形態を説明するための撮像素子の概略構成を示す断面模式図である。この撮像素子は、デジタルカメラ及びデジタルビデオカメラ等の撮像素子、電子内視鏡、ならびに、携帯電話機等の撮像モジュール等に搭載される。
　図３に示す撮像素子２０ａは、本発明の光電変換素子１０ａ（緑色光電変換素子１０ａ）と、青色光電変換素子２２と、赤色光電変換素子２４とを含み、これらは光が入射する方向に沿って積層されている。光電変換素子１０ａは、本発明の光電変換素子であり、主に、緑色光を受光できるように吸収波長をコントロールして、緑色光電変換素子としている。本発明の光電変換素子の吸収波長をコントロールする方法は、例えば、ｎ型半導体材料として適当な有機色素を使用する方法が挙げられる。
　撮像素子２０ａは、いわゆる積層体型の色分離撮像素子である。光電変換素子１０ａ、青色光電変換素子２２、及び、赤色光電変換素子２４は、それぞれ検出する波長スペクトルが異なる。つまり、青色光電変換素子２２及び赤色光電変換素子２４は、光電変換素子１０ａが受光（吸収）する光とは異なる波長の光を受光する光電変換素子に該当する。光電変換素子１０ａでは主に緑色光を受光でき、青色光電変換素子２２では主に青色光を受光でき、赤色光電変換素子では主に赤色光を受光できる。
　なお、緑色光とは波長５００～６００ｎｍの範囲の光を、青色光とは波長４００～５００ｎｍの範囲の光を、赤色光とは波長６００～７００ｎｍの範囲の光を意図する。
　撮像素子２０ａに矢印の方向から光が入射すると、まず、光電変換素子１０ａにおいて主に緑色光が吸収されるが、青色光及び赤色光に関しては光電変換素子１０ａを透過する。光電変換素子１０ａを透過した光が青色光電変換素子２２に進んだ際には、主に青色光が吸収されるが、赤色光に関しては青色光電変換素子２２を透過する。その後、青色光電変換素子２２を透過した光は、赤色光電変換素子２４によって吸収される。このように積層型の色分離撮像素子である撮像素子２０ａにおいては、緑、青、及び、赤の３つの受光部で１つの画素を構成でき、受光部の面積を大きく取れる。 <Image sensor>
Examples of applications of the photoelectric conversion element include an image sensor. An image sensor is an element that converts optical information of an image into an electric signal. Normally, a plurality of photoelectric conversion elements are arranged on a matrix in the same plane, and each photoelectric conversion element (pixel) has an optical signal. Is converted into an electric signal, and the electric signal can be sequentially output to the outside of the image sensor for each pixel. Therefore, each pixel is composed of one or more photoelectric conversion elements and one or more transistors.
FIG. 3 is a schematic cross-sectional view showing a schematic configuration of an image pickup device for explaining an embodiment of the present invention. This image pickup element is mounted on an image pickup element such as a digital camera and a digital video camera, an electronic endoscope, and an image pickup module such as a mobile phone.
The imaging element 20a shown in FIG. 3 includes a photoelectric conversion element 10a (green photoelectric conversion element 10a) of the present invention, a blue photoelectric conversion element 22, and a red photoelectric conversion element 24, and these include a direction in which light is incident. Are laminated. The photoelectric conversion element 10a is the photoelectric conversion element of the present invention, and is mainly used as a green photoelectric conversion element by controlling the absorption wavelength so that green light can be received. Examples of the method of controlling the absorption wavelength of the photoelectric conversion element of the present invention include a method of using an organic dye suitable as an n-type semiconductor material.
The image sensor 20a is a so-called laminated body type color-separated image sensor. The wavelength spectra detected by the photoelectric conversion element 10a, the blue photoelectric conversion element 22, and the red photoelectric conversion element 24 are different from each other. That is, the blue photoelectric conversion element 22 and the red photoelectric conversion element 24 correspond to photoelectric conversion elements that receive light having a wavelength different from the light received (absorbed) by the photoelectric conversion element 10a. The photoelectric conversion element 10a can mainly receive green light, the blue photoelectric conversion element 22 can mainly receive blue light, and the red photoelectric conversion element can mainly receive red light.
The green light is intended to be light having a wavelength in the range of 500 to 600 nm, the blue light is intended to be light in the wavelength range of 400 to 500 nm, and the red light is intended to be light in the wavelength range of 600 to 700 nm.
When light is incident on the image pickup device 20a from the direction of the arrow, first, the photoelectric conversion element 10a mainly absorbs green light, but blue light and red light pass through the photoelectric conversion element 10a. When the light transmitted through the photoelectric conversion element 10a advances to the blue photoelectric conversion element 22, the blue light is mainly absorbed, but the red light is transmitted through the blue photoelectric conversion element 22. After that, the light transmitted through the blue photoelectric conversion element 22 is absorbed by the red photoelectric conversion element 24. In the image sensor 20a, which is a laminated color-separated image sensor, one pixel can be composed of three light receiving units of green, blue, and red, and a large area of the light receiving unit can be obtained.
　青色光電変換素子２２、及び、赤色光電変換素子２４の構成は特に制限されない。
　例えば、シリコンを用いて光吸収長の差により色を分離する構成の光電変換素子でもよい。より具体的には、例えば、青色光電変換素子２２と、赤色光電変換素子２４とが、ともにシリコンからなっていてもよい。この場合、撮像素子２０ａに矢印の方向から入射した青色光と緑色光と赤色光とからなる光は、光電変換素子１０ａによって真ん中の波長の光である緑色光が主に受光され、残る青色光と赤色光とを色分離しやすくなる。青色光と赤色光とは、シリコンに対する光吸収長に差（シリコンに対する吸収係数の波長依存性）があり、青色光はシリコンの表面近傍で吸収されやすく、赤色光はシリコンの比較的深い位置まで侵入できる。このような光吸収長に差に基づき、より浅い位置に存在する青色光電変換素子２２によって主に青色光が受光され、より深い位置に存在する赤色光電変換素子２４によって主に赤色光が受光される。
　また、青色光電変換素子２２、及び、赤色光電変換素子２４は、導電性膜、青色光又は赤色光に吸収極大を有する有機の光電変換膜、及び、透明導電成膜をこの順で有する構成の光電変換素子（青色光電変換素子２２、又は、赤色光電変換素子２４）でもよい。例えば、青色光電変換素子２２は、青色光に吸収極大を有するように吸収波長をコントロールした本発明の光電変換素子でもよい。同様に、赤色光電変換素子２４は、赤色光に吸収極大を有するように吸収波長をコントロールした本発明の光電変換素子でもよい。 The configurations of the blue photoelectric conversion element 22 and the red photoelectric conversion element 24 are not particularly limited.
For example, a photoelectric conversion element having a configuration in which silicon is used to separate colors according to the difference in light absorption length may be used. More specifically, for example, the blue photoelectric conversion element 22 and the red photoelectric conversion element 24 may both be made of silicon. In this case, as for the light composed of blue light, green light, and red light incident on the image pickup element 20a from the direction of the arrow, the photoelectric conversion element 10a mainly receives the green light having the middle wavelength, and the remaining blue light. And red light can be easily separated. There is a difference in the light absorption length for silicon between blue light and red light (wavelength dependence of the absorption coefficient for silicon), blue light is easily absorbed near the surface of silicon, and red light reaches a relatively deep position in silicon. Can invade. Based on such a difference in light absorption length, blue light is mainly received by the blue photoelectric conversion element 22 existing at a shallower position, and red light is mainly received by the red photoelectric conversion element 24 existing at a deeper position. To.
Further, the blue photoelectric conversion element 22 and the red photoelectric conversion element 24 have a conductive film, an organic photoelectric conversion film having a maximum absorption maximum for blue light or red light, and a transparent conductive film formation in this order. A photoelectric conversion element (blue photoelectric conversion element 22 or red photoelectric conversion element 24) may be used. For example, the blue photoelectric conversion element 22 may be the photoelectric conversion element of the present invention in which the absorption wavelength is controlled so that the blue light has an absorption maximum. Similarly, the red photoelectric conversion element 24 may be the photoelectric conversion element of the present invention in which the absorption wavelength is controlled so that the red light has an absorption maximum.
　図３においては、光の入射側から本発明の光電変換素子、青色光電変換素子、及び、赤色光電変換素子の順に配置されていたが、この態様には限定されず、他の配置順であってもよい。例えば、光の入射する側から青色光電変換素子、本発明の光電変換素子、及び、赤色光電変換素子の順に配置されていてもよい。
　また、緑色光電変換素子を本発明の光電変換素子以外の光電変換素子として、青色光電変換素子及び／又は赤色光電変換素子を本発明の光電変換素子としてもよい。 In FIG. 3, the photoelectric conversion element, the blue photoelectric conversion element, and the red photoelectric conversion element of the present invention are arranged in this order from the incident side of the light, but the present invention is not limited to this, and the arrangement is not limited to this. You may. For example, the blue photoelectric conversion element, the photoelectric conversion element of the present invention, and the red photoelectric conversion element may be arranged in this order from the side where the light is incident.
Further, the green photoelectric conversion element may be used as a photoelectric conversion element other than the photoelectric conversion element of the present invention, and the blue photoelectric conversion element and / or the red photoelectric conversion element may be used as the photoelectric conversion element of the present invention.
　撮像素子として、上述のように、青色、緑色、及び、赤色の三原色の光電変換素子を積み上げた構成を説明したが、２層（２色）、又は、４層（４色）以上であってもかまわない。
　たとえば、配列した青色光電変換素子２２と赤色光電変換素子２４の上に本発明の光電変換素子１０ａを配置する態様であってもよい。なお、必要に応じて、光の入射側に更に所定の波長の光を吸収するカラーフィルタを配置してもよい。 As the image pickup device, as described above, the configuration in which the photoelectric conversion elements of the three primary colors of blue, green, and red are stacked has been described, but the number of layers (2 colors) or 4 layers (4 colors) or more is large. It doesn't matter.
For example, the photoelectric conversion element 10a of the present invention may be arranged on the arranged blue photoelectric conversion element 22 and the red photoelectric conversion element 24. If necessary, a color filter that further absorbs light having a predetermined wavelength may be arranged on the incident side of the light.
　撮像素子の形態は図３及び上述の形態に限定されず、他の形態であってもよい。
　例えば、同一面内位置に、本発明の光電変換素子、青色光電変換素子、及び、赤色光電変換素子が配置された態様であってもよい。 The form of the image sensor is not limited to that shown in FIG. 3 and the above-mentioned form, and may be another form.
For example, the photoelectric conversion element, the blue photoelectric conversion element, and the red photoelectric conversion element of the present invention may be arranged at the same in-plane position.
　また、光電変換素子を単層で用いる構成であってもよい。例えば、本発明の光電変換素子１０ａのうえに、青、赤、緑のカラーフィルタを配置して色を分離する構成であってもよい。 Further, the photoelectric conversion element may be used in a single layer. For example, a blue, red, and green color filters may be arranged on the photoelectric conversion element 10a of the present invention to separate colors.
　本発明の光電変換素子は光センサとして用いるのも好ましい。光センサは、上記光電変換素子単独で用いてもよいし、上記光電変換素子を直線状に配したラインセンサ、又は平面上に配した２次元センサとして用いてもよい。 It is also preferable to use the photoelectric conversion element of the present invention as an optical sensor. The optical sensor may be used by the photoelectric conversion element alone, or may be used as a line sensor in which the photoelectric conversion element is arranged in a straight line, or a two-dimensional sensor in which the photoelectric conversion element is arranged on a plane.
＜光電変換素子用材料＞
　本発明は、光電変換素子用材料の発明をも含む。
　本発明の光電変換素子用材料は、式（１）で表される化合物（特定化合物）を含む、光電変換素子（好ましくは撮像素子用又は光センサ用の光電変換素子）の製造に用いられる材料である。
　光電変換素子用材料における式（１）で表される化合物は、上述の式（１）で表される化合物と同様であり、好ましい条件も同様である。
　光電変換素子用材料に含まれる特定化合物は、それぞれ、光電変換素子に含まれる光電変換膜の、光電変換膜の作製に用いられるのが好ましい。
　光電変換素子用材料に含まれる特定化合物の含有量は、それぞれ、光電変換素子用材料の全質量の、３０～１００質量％が好ましく、７０～１００質量％がより好ましく、９９～１００質量％が更に好ましい。
　光電変換素子用材料が含む特定化合物は、１種単独でもよく、２種以上でもよい。 <Material for photoelectric conversion element>
The present invention also includes the invention of a material for a photoelectric conversion element.
The material for a photoelectric conversion element of the present invention is a material used for manufacturing a photoelectric conversion element (preferably a photoelectric conversion element for an image sensor or an optical sensor) containing a compound (specific compound) represented by the formula (1). Is.
The compound represented by the formula (1) in the material for a photoelectric conversion element is the same as the compound represented by the above formula (1), and the preferable conditions are also the same.
It is preferable that each of the specific compounds contained in the material for the photoelectric conversion element is used for producing the photoelectric conversion film of the photoelectric conversion film contained in the photoelectric conversion element.
The content of the specific compound contained in the material for the photoelectric conversion element is preferably 30 to 100% by mass, more preferably 70 to 100% by mass, and 99 to 100% by mass, respectively, of the total mass of the material for the photoelectric conversion element. More preferred.
The specific compound contained in the material for the photoelectric conversion element may be one kind alone or two or more kinds.
　以下に実施例に基づいて本発明を更に詳細に説明する。以下の実施例に示す材料、使用量、割合、処理内容、及び、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更できる。したがって、本発明の範囲は以下に示す実施例により限定的に解釈されるべきものではない。 The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below.
＜化合物（Ｄ－７）の合成＞
　以下のスキームに従って、化合物（Ｄ－７）を合成した。 <Synthesis of compound (D-7)>
Compound (D-7) was synthesized according to the following scheme.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
・中間体７ｂの合成
　窒素雰囲気下、１０００ｍＬ三口フラスコで四塩化チタン（１２．４ｇ、６５．３ｍｍｏｌ）をＴＨＦ（テトラヒドロフラン、４５５ｍＬ）に溶解した。更に、上記フラスコ内の液温を－１０℃としてから、上記フラスコに亜鉛粉末（８．５４ｇ、１３１ｍｍｏｌ）を添加した。得られた混合物を加熱還流させながら、中間体７ａ（２．４２ｇ、１０．９ｍｍｏｌ；　Ｃｈｅｍｉｓｔｒｙ　Ａ　Ｅｕｒｏｐｅａｎ　Ｊｏｕｒｎａｌ　２０１５，　２１，　１２８７１－１２８７５文献のＳｕｐｐｏｒｔｉｎｇ　ｉｎｆｏｒｍａｔｉｏｎに記載のＳ４ｊの合成法に従って合成した）のＴＨＦ（２００ｍＬ）溶液を、５時間かけて添加した。添加後、上記混合物を、更に１．５時間加熱還流させて反応混合液を得た。上記反応混合液を室温まで冷却した後、上記反応混合液を氷水に加えた。得られた液体を、重曹水で中性にしてから、酢酸エチルを用いて液体中に含まれる反応生成物を抽出した。得られた粗生成物（反応生成物）をシリカゲルカラムクロマトグラフィーで精製して、中間体７ｂを１．７３ｇ得た。収率８４％。
　中間体７ｂのＥＳＩ－ＭＳ（エレクトロスプレーイオン化法による質量分析）による測定結果は次の通りであった。
　　ｍ／ｚ＝１８９．９９　（Ｍ＋）
　中間体７ｂの１Ｈ　ＮＭＲ（Ｎｕｃｌｅａｒ　Ｍａｇｎｅｔｉｃ　Ｒｅｓｏｎａｎｃｅ）及び１３Ｃ　ＮＭＲによる測定結果は次の通りであった。
　　１Ｈ　ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ３）δ７．４４（ｄｄ、Ｊ＝４．４　ａｎｄ　９．６Ｈｚ、２Ｈ）、７．５７（ｓ、２Ｈ）、７．７６（ｄ、Ｊ＝８．４Ｈｚ、２Ｈ）、７．８２（ｄ、Ｊ＝８．４Ｈｚ、２Ｈ）。
　　１３Ｃ　ＮＭＲ（１２５ＭＨｚ、ＣＤＣｌ３）δ１１８．９３、１２０．１４、１２１．６４、１２４．２０、１２４．６６、１２７．１５、１３３．６３、１３４．４８、１３６．３０、１３６．８４。 -Synthesis of Intermediate 7b Titanium tetrachloride (12.4 g, 65.3 mmol) was dissolved in THF (tetrahydrofuran, 455 mL) in a 1000 mL three-necked flask under a nitrogen atmosphere. Further, after the liquid temperature in the flask was set to −10 ° C., zinc powder (8.54 g, 131 mmol) was added to the flask. THF of intermediate 7a (2.42 g, 10.9 mmol; synthesized according to the synthetic method of S4j described in Supporting information of Chemistry A European Journal 2015, 21, 12871-12875) while heating and refluxing the obtained mixture. The (200 mL) solution was added over 5 hours. After the addition, the above mixture was further heated to reflux for 1.5 hours to obtain a reaction mixture. After cooling the reaction mixture to room temperature, the reaction mixture was added to ice water. The obtained liquid was neutralized with aqueous sodium hydrogen carbonate, and then the reaction product contained in the liquid was extracted using ethyl acetate. The obtained crude product (reaction product) was purified by silica gel column chromatography to obtain 1.73 g of Intermediate 7b. Yield 84%.
The measurement results of the intermediate 7b by ESI-MS (mass spectrometry by electrospray ionization) were as follows.
m / z = 189.99 (M + )
The measurement results of the intermediate 7b by 1H NMR (Nuclear Magnetic Resonance) and 13C NMR were as follows.
1H NMR (400MHz, CDCl3) δ7.44 (dd, J = 4.4 and 9.6Hz, 2H), 7.57 (s, 2H), 7.76 (d, J = 8.4Hz, 2H), 7.82 (d, J = 8.4Hz, 2H).
13C NMR (125 MHz, CDCl3) δ118.93,120.14, 121.64, 124.20, 124.66, 127.15, 133.63, 134.48, 136.30, 136.84.
・中間体７ｃの合成
　窒素雰囲気下にて、５０ｍＬ三口フラスコで中間体７ｂ（０．５０ｇ、２．６ｍｍｏｌ）を脱水ＴＨＦ（１８ｍＬ）に溶解させた。得られた溶解液を、ドライアイス－アセトン浴で冷却した後、上記溶解液にｎ－ブチルリチウム（１．６Ｍヘキサン溶液、３．９ｍＬ、６．３ｍｍｏｌ）を、上記溶解液の内温を－６５℃以下に維持しながら滴下した。滴下後、上記溶解液を、内温－７０℃以下に維持しながら３．５時間撹拌した。上記溶解液に塩化トリブチルスズ（２．６ｇ、７．９ｍｍｏｌ）の脱水ＴＨＦ（７ｍＬ）溶液を、上記溶解液の内温を－６６℃以下に維持しながら滴下し、その後、上記溶解液を室温（２３℃）に戻して、室温で１時間反応させ、反応液を得た。３００ｍＬ三角フラスコに水（５０ｍＬ）を測り取り、これに得られた反応液を添加して反応を停止させた。得られた液体に含まれる反応生成物を、酢酸エチルで抽出した。抽出処理によって得られた反応生成物を含む有機相を硫酸ナトリウムで乾燥し、減圧濃縮した。得られた粗生成物（反応生成物）をアミノ修飾型シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン）で精製して、中間体７ｃを１．５０ｇ得た。収率７４％。
　中間体７ｃのＥＳＩ－ＭＳによる測定結果は次の通りであった。
　　ｍ／ｚ＝７７０．２０　（Ｍ＋）
　中間体７ｃの１Ｈ　ＮＭＲによる測定結果は次の通りであった。
　　１Ｈ　ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ３）δ０．７０－１．７０（ｍ、５４Ｈ）７．４８（ｓ、１Ｈ）、７．６２（ｄ、Ｊ＝０．８Ｈｚ、１Ｈ）、７．７０（ｄ、Ｊ＝８．４Ｈｚ、１Ｈ）、７．７９（ｄｄ、Ｊ＝０．８　ａｎｄ　８．４Ｈｚ、１Ｈ）。 -Synthesis of Intermediate 7c Under a nitrogen atmosphere, Intermediate 7b (0.50 g, 2.6 mmol) was dissolved in dehydrated THF (18 mL) in a 50 mL three-necked flask. After cooling the obtained solution in a dry ice-acetone bath, n-butyllithium (1.6 M hexane solution, 3.9 mL, 6.3 mmol) was added to the solution, and the internal temperature of the solution was changed to-. The mixture was added dropwise while maintaining the temperature below 65 ° C. After the dropping, the solution was stirred for 3.5 hours while maintaining the internal temperature at −70 ° C. or lower. A dehydrated THF (7 mL) solution of tributyltin chloride (2.6 g, 7.9 mmol) was added dropwise to the solution while maintaining the internal temperature of the solution at −66 ° C. or lower, and then the solution was added to room temperature (7 mL). The temperature was returned to 23 ° C.) and reacted at room temperature for 1 hour to obtain a reaction solution. Water (50 mL) was measured in a 300 mL Erlenmeyer flask, and the obtained reaction solution was added thereto to stop the reaction. The reaction product contained in the obtained liquid was extracted with ethyl acetate. The organic phase containing the reaction product obtained by the extraction treatment was dried over sodium sulfate and concentrated under reduced pressure. The obtained crude product (reaction product) was purified by amino-modified silica gel column chromatography (developing solvent: hexane) to obtain 1.50 g of Intermediate 7c. Yield 74%.
The measurement results of the intermediate 7c by ESI-MS were as follows.
m / z = 770.20 (M + )
The measurement results of the intermediate 7c by 1H NMR were as follows.
1H NMR (400MHz, CDCl3) δ0.70-1.70 (m, 54H) 7.48 (s, 1H), 7.62 (d, J = 0.8Hz, 1H), 7.70 (d, J) = 8.4Hz, 1H), 7.79 (dd, J = 0.8 and 8.4Hz, 1H).
・化合物（Ｄ－７）の合成
　５０ｍＬ三口フラスコに、中間体７ｃ（０．７５ｇ、０．９８ｍｍｏｌ）、４－ブロモ－ｐ－テルフェニル（０．７３ｇ、２．３５ｍｍｏｌ）、トリス（ジベンジリデンアセトン）二パラジウム（０．０１８ｇ、０．０２ｍｍｏｌ）、トリ（ｏ－トリル）ホスフィン（０．０２５ｇ、０．０７８ｍｍｏｌ）、及び、Ｎ，Ｎ－ジメチルホルムアミド（１２ｍＬ）を加えて混合し、その後、上記フラスコ内の減圧脱気と窒素置換を３回繰り返した。上記フラスコ内の混合物を、窒素雰囲気下１００℃で６時間反応させた後、析出した固体（粗成生物）を濾別した。得られた粗生成物をクロロベンゼン中にて１４０℃１時間加熱してから熱時濾過し、得られた固体（濾物）を減圧下昇華精製することで、化合物（Ｄ－７）を得た。
　化合物（Ｄ－７）のＥＳＩ－ＭＳによる測定結果は次の通りであった。
　　ｍ／ｚ＝６４６．１８　（Ｍ＋） -Synthesis of compound (D-7) Intermediate 7c (0.75 g, 0.98 mmol), 4-bromo-p-terphenyl (0.73 g, 2.35 mmol), tris (dibenzylideneacetone) in a 50 mL three-necked flask. ) Dipalladium (0.018 g, 0.02 mmol), tri (o-tolyl) phosphine (0.025 g, 0.078 mmol), and N, N-dimethylformamide (12 mL) were added and mixed, and then the above. Degassing under reduced pressure and nitrogen substitution in the flask were repeated 3 times. The mixture in the flask was reacted at 100 ° C. for 6 hours in a nitrogen atmosphere, and then the precipitated solid (crude organism) was filtered off. The obtained crude product was heated in chlorobenzene at 140 ° C. for 1 hour and then filtered by heat, and the obtained solid (filter) was sublimated and purified under reduced pressure to obtain compound (D-7). ..
The measurement results of compound (D-7) by ESI-MS were as follows.
m / z = 646.18 (M + )
＜化合物（Ｄ－２）の合成＞
　化合物（Ｄ－７）の合成における４－ブロモ－ｐ－テルフェニルを２－（４－ブロモフェニル）ナフタレンに変えたこと以外は、化合物（Ｄ－７）の合成と同様にして、化合物（Ｄ－２）を得た。
　化合物（Ｄ－２）のＥＳＩ－ＭＳによる測定結果は次の通りであった。
　　ｍ／ｚ＝５９４．１５　（Ｍ＋） <Synthesis of compound (D-2)>
Compound (D-7) was synthesized in the same manner as compound (D-7), except that 4-bromo-p-terphenyl was converted to 2- (4-bromophenyl) naphthalene in the synthesis of compound (D-7). -2) was obtained.
The measurement results of compound (D-2) by ESI-MS were as follows.
m / z = 594.15 (M + )
＜化合物（Ｄ－５）の合成＞
　化合物（Ｄ－７）の合成における４－ブロモ－ｐ－テルフェニルを４－ブロモビフェニルに変えたこと以外は、化合物（Ｄ－７）の合成と同様にして、化合物（Ｄ－５）を得た。
　化合物（Ｄ－５）のＥＳＩ－ＭＳによる測定結果は次の通りであった。
　　ｍ／ｚ＝４９４．１２　（Ｍ＋） <Synthesis of compound (D-5)>
Compound (D-5) was obtained in the same manner as compound (D-7) except that 4-bromo-p-terphenyl was changed to 4-bromobiphenyl in the synthesis of compound (D-7). It was.
The measurement results of compound (D-5) by ESI-MS were as follows.
m / z = 494.12 (M + )
＜化合物（Ｄ－９）の合成＞
　化合物（Ｄ－７）の合成における４－ブロモ－ｐ－テルフェニルを２－（４－ブロモフェニル）－９，９－ジメチル－９Ｈ－フルオレンに変えたこと以外は、化合物（Ｄ－７）の合成と同様にして、化合物（Ｄ－９）を得た。
　化合物（Ｄ－９）のＥＳＩ－ＭＳによる測定結果は次の通りであった。
　　ｍ／ｚ＝７２６．２４　（Ｍ＋） <Synthesis of compound (D-9)>
Of compound (D-7), except that 4-bromo-p-terphenyl in the synthesis of compound (D-7) was changed to 2- (4-bromophenyl) -9,9-dimethyl-9H-fluorene. Compound (D-9) was obtained in the same manner as in the synthesis.
The measurement results of compound (D-9) by ESI-MS were as follows.
m / z = 726.24 (M + )
＜化合物（Ｄ－１）の合成＞
　以下のスキームに従って、化合物（Ｄ－１）を合成した。 <Synthesis of compound (D-1)>
Compound (D-1) was synthesized according to the following scheme.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
・中間体１ｂの合成
　中間体７ｃの合成における中間体７ｂを中間体１ａ（Ｊｏｕｒｎａｌ　ｏｆ　Ｏｒｇａｎｉｃ　Ｃｈｅｍｉｓｔｒｙ　１９９４，　５９，　３０７７－３０８１の化合物１１の合成例に従って合成した）に変えたこと以外は、中間体７ｃの合成と同様にして、中間体１ｂを得た。
　中間体１ｂのＥＳＩ－ＭＳによる測定結果は次の通りであった。
　　ｍ／ｚ＝７７０．２０　（Ｍ＋） -Synthesis of Intermediate 1b Intermediate 7b in the synthesis of Intermediate 7c was changed to Intermediate 1a (synthesized according to the synthesis example of Compound 11 of Journal of Organic Chemistry 1994, 59, 3077-3081). Intermediate 1b was obtained in the same manner as in the synthesis of 7c.
The measurement results of Intermediate 1b by ESI-MS were as follows.
m / z = 770.20 (M + )
・化合物（Ｄ－１）の合成
　化合物（Ｄ－５）の合成における中間体７ｃを中間体１ｂに変えたこと以外は、化合物（Ｄ－５）の合成と同様にして、化合物（Ｄ－１）を得た。
　化合物（Ｄ－１）のＥＳＩ－ＭＳによる測定結果は次の通りであった。
　　ｍ／ｚ＝４９４．１２　（Ｍ＋） -Synthesis of compound (D-1) Compound (D-1) was synthesized in the same manner as compound (D-5), except that the intermediate 7c in the synthesis of compound (D-5) was changed to intermediate 1b. ) Was obtained.
The measurement results of compound (D-1) by ESI-MS were as follows.
m / z = 494.12 (M + )
＜化合物（Ｄ－３）の合成＞
　化合物（Ｄ－１）の合成における４－ブロモビフェニルを４－ブロモ－ｐ－テルフェニルに変えたこと以外は、化合物（Ｄ－１）の合成と同様にして、化合物（Ｄ－３）を得た。
　化合物（Ｄ－３）のＥＳＩ－ＭＳによる測定結果は次の通りであった。
　　ｍ／ｚ＝６４６．１８　（Ｍ＋） <Synthesis of compound (D-3)>
Compound (D-3) was obtained in the same manner as in compound (D-1) except that 4-bromobiphenyl was changed to 4-bromo-p-terphenyl in the synthesis of compound (D-1). It was.
The measurement results of compound (D-3) by ESI-MS were as follows.
m / z = 646.18 (M + )
＜化合物（Ｄ－４）の合成＞
　以下のスキームに従って、化合物（Ｄ－４）を合成した。 <Synthesis of compound (D-4)>
Compound (D-4) was synthesized according to the following scheme.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
・中間体４ｂの合成
　中間体７ｃの合成における中間体７ｂを中間体４ａ（Ｊｏｕｒｎａｌ　ｏｆ　Ｈｅｔｅｒｏｃｙｃｌｉｃ　Ｃｈｅｍｉｓｔｒｙ　２０１３，　５０，　１０２１－１０２４の化合物１の合成例に従って合成した）に変えたこと以外は、中間体７ｃの合成と同様にして、中間体４ｂを得た。
　中間体４ｂのＥＳＩ－ＭＳによる測定結果は次の通りであった。
　　ｍ／ｚ＝７７０．２０　（Ｍ＋） -Synthesis of Intermediate 4b Intermediate 7b in the synthesis of Intermediate 7c was changed to Intermediate 4a (synthesized according to the synthetic example of Compound 1 of Journal of Heterocyclic Chemistry 2013, 50, 1021-1024). Intermediate 4b was obtained in the same manner as in the synthesis of 7c.
The measurement results of the intermediate 4b by ESI-MS were as follows.
m / z = 770.20 (M + )
・化合物（Ｄ－４）の合成
　化合物（Ｄ－５）の合成における中間体７ｃを中間体４ｂに変えたこと以外は、化合物（Ｄ－５）の合成と同様にして、化合物（Ｄ－４）を得た。
　化合物（Ｄ－４）のＥＳＩ－ＭＳによる測定結果は次の通りであった。
　　ｍ／ｚ＝４９４．１２　（Ｍ＋） -Synthesis of compound (D-4) Compound (D-4) was synthesized in the same manner as compound (D-5), except that the intermediate 7c in the synthesis of compound (D-5) was changed to intermediate 4b. ) Was obtained.
The measurement results of compound (D-4) by ESI-MS were as follows.
m / z = 494.12 (M + )
＜化合物（Ｄ－６）の合成＞
　化合物（Ｄ－７）の合成における中間体７ｃを中間体４ｂに変えたこと以外は、化合物（Ｄ－７）の合成と同様にして、化合物（Ｄ－６）を得た。
　化合物（Ｄ－６）のＥＳＩ－ＭＳによる測定結果は次の通りであった。
　　ｍ／ｚ＝６４６．１８　（Ｍ＋） <Synthesis of compound (D-6)>
Compound (D-6) was obtained in the same manner as in the synthesis of compound (D-7), except that the intermediate 7c in the synthesis of compound (D-7) was changed to intermediate 4b.
The measurement results of compound (D-6) by ESI-MS were as follows.
m / z = 646.18 (M + )
＜化合物（Ｄ－８）の合成＞
　化合物（Ｄ－４）の合成における４－ブロモビフェニルを２－（４－ブロモフェニル）ベンゾ［ｂ］チオフェンに変えたこと以外は、化合物（Ｄ－４）の合成と同様にして、化合物（Ｄ－８）を得た。
　化合物（Ｄ－８）のＥＳＩ－ＭＳによる測定結果は次の通りであった。
　　ｍ／ｚ＝６０６．０６　（Ｍ＋） <Synthesis of compound (D-8)>
Compound (D-4) was synthesized in the same manner as compound (D-4), except that 4-bromobiphenyl was changed to 2- (4-bromophenyl) benzo [b] thiophene in the synthesis of compound (D-4). -8) was obtained.
The measurement results of compound (D-8) by ESI-MS were as follows.
m / z = 606.06 (M + )
＜化合物（Ｄ－１０）の合成＞
　以下のスキームに従って、化合物（Ｄ－１０）を合成した。 <Synthesis of compound (D-10)>
Compound (D-10) was synthesized according to the following scheme.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
・中間体１０ｂの合成
　中間体７ｃの合成における中間体７ｂを中間体１０ａ（Ｔｅｔｒａｈｅｄｒｏｎ　２０１６，　７２，　４１５９－４１６８の化合物３Ｏの合成例に従って合成した）に変えたこと以外は、中間体７ｃの合成と同様にして、中間体１０ｂを得た。
　中間体１０ｂのＥＳＩ－ＭＳによる測定結果は次の通りであった。
　　ｍ／ｚ＝７３８．２５　（Ｍ＋） -Synthesis of Intermediate 10b Synthesis of Intermediate 7c, except that Intermediate 7b in the synthesis of Intermediate 7c was changed to Intermediate 10a (synthesized according to the synthesis example of Compound 3O of Tetrahedron 2016, 72, 4159-4168). In the same manner as above, intermediate 10b was obtained.
The measurement results of the intermediate 10b by ESI-MS were as follows.
m / z = 738.25 (M + )
・化合物（Ｄ－１０）の合成
　化合物（Ｄ－５）の合成における中間体７ｃを中間体１０ｂに変えたこと以外は、化合物（Ｄ－５）の合成と同様にして、化合物（Ｄ－１０）を得た。
　化合物（Ｄ－１０）のＥＳＩ－ＭＳによる測定結果は次の通りであった。
　　ｍ／ｚ＝４６２．１６　（Ｍ＋） -Synthesis of compound (D-10) Compound (D-10) was synthesized in the same manner as compound (D-5), except that the intermediate 7c in the synthesis of compound (D-5) was changed to intermediate 10b. ) Was obtained.
The measurement results of compound (D-10) by ESI-MS were as follows.
m / z = 462.16 (M + )
＜化合物（Ｒ－１）の合成＞
　化合物（Ｄ－１）の合成における４－ブロモビフェニルをブロモベンゼンに変えたこと以外は、化合物（Ｄ－１）の合成と同様にして、化合物（Ｒ－１）を得た。
　化合物（Ｒ－１）のＥＳＩ－ＭＳによる測定結果は次の通りであった。
　　ｍ／ｚ＝３４２．０５　（Ｍ＋） <Synthesis of compound (R-1)>
Compound (R-1) was obtained in the same manner as in the synthesis of compound (D-1) except that 4-bromobiphenyl was converted to bromobenzene in the synthesis of compound (D-1).
The measurement results of compound (R-1) by ESI-MS were as follows.
m / z = 342.05 (M + )
＜化合物（Ｒ－２）の合成＞
　特開２０１７－３９６６２の実施例１に記載の化合物（１１１）の合成法に従って合成した。 <Synthesis of compound (R-2)>
It was synthesized according to the method for synthesizing compound (111) described in Example 1 of JP-A-2017-39662.
　以下に、特定化合物である化合物（Ｄ－１）～（Ｄ－１０）と、比較用の化合物（Ｒ－１）～（Ｒ－２）を示す。 The compounds (D-1) to (D-10), which are specific compounds, and the compounds (R-1) to (R-2) for comparison are shown below.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　上記化合物（Ｄ－１）～（Ｄ－１０）、（Ｒ－１）～（Ｒ－２）と、フラーレン（Ｃ６０）のＬＵＭＯの値を、それぞれ、Ｇａｕｓｓｉａｎ‘０９（Ｇａｕｓｓｉａｎ社製ソフトウェア）を用いてＢ３ＬＹＰ／６－３１Ｇ（ｄ）の計算により求めた。得られたＬＵＭＯの値の反数の値を化合物の電子親和力の値として採用した。
　その結果、フラーレン（Ｃ６０）の電子親和力は、化合物（Ｄ－１）～（Ｄ－１０）、（Ｒ－１）～（Ｒ－２）のいずれの電子親和力よりも大きいことが確認された。つまり、フラーレン（Ｃ６０）は、化合物（Ｄ－１）～（Ｄ－１０）、（Ｒ－１）～（Ｒ－２）との関係で、ｎ型半導体材料に該当することが確認された。 The above compound (D-1) ~ (D -10), and (R-1) ~ (R -2), the value of the LUMO of fullerene (C 60), respectively, Gaussian'09 the (Gaussian, Inc. software) It was calculated using B3LYP / 6-31G (d). The value of the reciprocal of the obtained LUMO value was adopted as the value of the electron affinity of the compound.
As a result, it was confirmed that the electron affinity of fullerene (C 60 ) is larger than the electron affinity of any of the compounds (D-1) to (D-10) and (R-1) to (R-2). .. That is, it was confirmed that fullerene (C 60 ) corresponds to an n-type semiconductor material in relation to the compounds (D-1) to (D-10) and (R-1) to (R-2). ..
＜実施例及び比較例：光電変換素子の作製＞
　得られた化合物を用いて図２の形態の光電変換素子を作製した。ここで、光電変換素子は、下部電極１１、電子ブロッキング膜１６Ａ、光電変換膜１２、正孔ブロッキング膜１６Ｂ、及び、上部電極１５からなる。
　具体的には、ガラス基板上に、アモルファス性ＩＴＯをスパッタ法により成膜して、下部電極１１（厚み：３０ｎｍ）を形成し、更に下部電極１１上に下記の化合物（Ｂ－１）を真空加熱蒸着法により成膜して、電子ブロッキング膜１６Ａ（厚み：１０ｎｍ）を形成した。
　更に、基板の温度を２５℃に制御した状態で、電子ブロッキング膜１６Ａ上に化合物（Ｄ－１）とフラーレン（Ｃ６０）とを２．０Å／秒の蒸着レートに設定し、それぞれ単層換算で１００ｎｍ、１００ｎｍとなるように真空蒸着法により共蒸着して成膜し、２００ｎｍのバルクヘテロ構造を有する光電変換膜１２を形成した（光電変換膜形成工程）。
　更に光電変換膜１２上に下記の化合物（Ｂ－２）を成膜して正孔ブロッキング膜１６Ｂ（厚み：１０ｎｍ）を形成した。
　更に、正孔ブロッキング膜１６Ｂ上に、アモルファス性ＩＴＯをスパッタ法により成膜して、上部電極１５（透明導電性膜）（厚み：１０ｎｍ）を形成した。上部電極１５上に、真空蒸着法により封止層としてＳｉＯ膜を形成した後、その上にＡＬＣＶＤ（Ａｔｏｍｉｃ　Ｌａｙｅｒ　Ｃｈｅｍｉｃａｌ　Ｖａｐｏｒ　Ｄｅｐｏｓｉｔｉｏｎ）法により酸化アルミニウム（Ａｌ２Ｏ３）層を形成し、光電変換素子を作製し、この素子を、素子（Ａ）とした。
　上述の製造方法と同様にして、化合物（Ｄ－２）～（Ｄ－１０）又は（Ｒ－１）～（Ｒ－２）を使用した素子（Ａ）をそれぞれ作製した。 <Examples and Comparative Examples: Fabrication of Photoelectric Conversion Element>
Using the obtained compound, a photoelectric conversion element having the form shown in FIG. 2 was produced. Here, 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.
Specifically, an 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 (B-1) is further vacuumed on the lower electrode 11. An electron blocking film 16A (thickness: 10 nm) was formed by forming a film by a heat vapor deposition method.
Further, while controlling the temperature of the substrate 25 ° C., and set compound on the electron blocking layer 16A and a (D-1) and fullerene (C 60) to the evaporation rate of 2.0 Å / sec, respectively monolayer terms A photoelectric conversion film 12 having a bulk heterostructure of 200 nm was formed by co-depositing and forming a film by a vacuum vapor deposition method so as to have a temperature of 100 nm and 100 nm (photoelectric conversion film forming step).
Further, the following compound (B-2) was formed on the photoelectric conversion film 12 to form a hole blocking film 16B (thickness: 10 nm).
Further, an 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). A SiO film is formed on the upper electrode 15 as a sealing layer by a vacuum vapor deposition method, and then an aluminum oxide (Al 2 O 3 ) layer is formed on the SiO film by an ALCVD (Atomic Layer Chemical Vapor Deposition) method to form a photoelectric conversion element. Was produced, and this element was designated as the element (A).
In the same manner as in the above-mentioned production method, devices (A) using compounds (D-2) to (D-10) or (R-1) to (R-2) were produced, respectively.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
＜駆動の確認（光電変換効率、暗電流の評価）＞
　得られた各素子（Ａ）の駆動の確認をした。各素子（Ａ）に１．０×１０５Ｖ／ｃｍの電界強度となるように電圧を印加した。その後、上部電極（透明導電性膜）側から光を照射して４００ｎｍでの光電変換効率（外部量子効率）を評価した。外部量子効率は、オプテル製定エネルギー量子効率測定装置を用いて測定した。照射した光量は５０μＷ／ｃｍ２であった。いずれの素子（Ａ）も３０％以上の光電変換効率と１０ｎＡ／ｃｍ２以下の暗電流を示し、問題なく駆動することを確認した。 <Confirmation of drive (photoelectric conversion efficiency, evaluation of dark current)>
The drive of each of the obtained elements (A) was confirmed. A voltage was applied so that the electric field intensity of 1.0 × 10 5 V / cm in each element (A). Then, light was irradiated from the upper electrode (transparent conductive film) side, and the photoelectric conversion efficiency (external quantum efficiency) at 400 nm was evaluated. The external quantum efficiency was measured using an Optel constant energy quantum efficiency measuring device. The amount of light irradiated was 50 μW / cm 2 . It was confirmed that all the elements (A) showed a photoelectric conversion efficiency of 30% or more and a dark current of 10 nA / cm 2 or less, and could be driven without any problem.
＜応答性の評価＞
　得られた各素子（Ａ）の応答性の評価を行った。各素子（Ａ）に１．０×１０５Ｖ／ｃｍの電界強度となるように電圧を印加し、上部電極（透明導電性膜）側から４００ｎｍの光を照射した。照射開始から１０ミリ秒後の光電流の値を１００％とした場合に、光電流が９７％以上になるまでにかかった時間を算出した。実施例１の素子（Ａ）の値（光電流が９７％以上になるまでにかかった時間）を１とした場合の相対値で、各素子（Ａ）の応答性を評価した。相対値が０．５以下のものをＡ、０．５より大きく１以下のものをＢ、１より大きく２以下のものをＣ、２よりも大きいものをＤとして評価を行った。実用上、Ａ又はＢが好ましく、Ａがより好ましい。結果を表１に示す。 <Evaluation of responsiveness>
The responsiveness of each of the obtained elements (A) was evaluated. A voltage is applied so that the electric field intensity of 1.0 × 10 5 V / cm in each element (A), was irradiated with light of 400nm from the upper electrode (transparent conductive film) side. Assuming that the value of the photocurrent 10 milliseconds after the start of irradiation was 100%, the time required for the photocurrent to reach 97% or more was calculated. The responsiveness of each element (A) was evaluated by a relative value when the value of the element (A) of Example 1 (the time required for the photocurrent to reach 97% or more) was set to 1. Evaluation was performed with a relative value of 0.5 or less as A, a value larger than 0.5 and 1 or less as B, a value larger than 1 and 2 or less as C, and a value larger than 2 as D. Practically, A or B is preferable, and A is more preferable. The results are shown in Table 1.
＜耐熱性の評価＞
　得られた各素子（Ａ）をグローブボックス中で１６０℃、２時間加熱処理した。その後に上述の＜駆動の確認（光電変換効率、暗電流の評価）＞と同様の方法で、暗電流の評価を行った。加熱処理前の暗電流値を１とした場合の相対値で評価を行い、相対値が、２以下であればＡ、２より大きく５以下であればＢ、５より大きく１０以下であればＣ、１０よりも大きければＤとして評価を行った。実用上、Ａ又はＢが好ましく、Ａがより好ましい。結果を表１に示す。 <Evaluation of heat resistance>
Each of the obtained elements (A) was heat-treated in a glove box at 160 ° C. for 2 hours. After that, the dark current was evaluated by the same method as the above-mentioned <Confirmation of drive (photoelectric conversion efficiency, evaluation of dark current)>. Evaluation is performed using the relative value when the dark current value before heat treatment is 1, and if the relative value is 2 or less, it is A, if it is larger than 2 and 5 or less, it is B, and if it is larger than 5, it is C. If it was larger than 10, it was evaluated as D. Practically, A or B is preferable, and A is more preferable. The results are shown in Table 1.
　各化合物を用いて作製した光電変換素子を使用して行った試験の結果を下記表１に示す。 Table 1 below shows the results of tests conducted using photoelectric conversion elements manufactured using each compound.
　各化合物を用いて作製した光電変換素子を使用して行った試験の結果を下記表１に示す。
　表１中、「式（３）」欄は、使用した特定化合物が、式（３）で表される化合物に該当するか否かを示す。本要件を満たす場合はＡとし、満たさない場合はＢとした。
　「Ａｒ１、Ａｒ４＝多環芳香族／式（Ｒ）」欄は、特定化合物中における式（１）中のＡｒ１、Ａｒ４で表される基に相当する基が、置換基を有してもよい多環の芳香環基、又は、式（Ｒ）で表される基であるか否かを示す。本要件を満たす場合はＡとし、満たさない場合はＢとした。 Table 1 below shows the results of tests conducted using photoelectric conversion elements manufactured using each compound.
In Table 1, the column "Formula (3)" indicates whether or not the specific compound used corresponds to the compound represented by the formula (3). If this requirement is met, it is designated as A, and if it is not met, it is designated as B.
In the "Ar 1 , Ar 4 = polycyclic aromatic / formula (R)" column, the group corresponding to the group represented by Ar 1 or Ar 4 in the formula (1) in the specific compound has a substituent. It indicates whether or not it is a polycyclic aromatic ring group which may be used, or a group represented by the formula (R). If this requirement is met, it is designated as A, and if it is not met, it is designated as B.
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000018
　表１に示す結果より、光電変換膜に特定化合物を使用する本発明の光電変換素子は、応答性にすぐれることが確認された。また、本発明の光電変換素子は、耐熱性にも優れることが確認された。
　一方で、式（１）におけるＡｒ１及びＡｒ４に相当する芳香環基が存在しない化合物Ｒ－１を使用した光電変換素子は、応答性が不十分であった。また、耐熱性も、本発明の光電変換素子と比べて劣っていた。
　また、特定化合物とは異なる構造の母核を有する化合物Ｒ－２を使用した光電変換素子は、応答性が不十分であった。また、耐熱性も、本発明の光電変換素子と比べて劣っていた。 From the results shown in Table 1, it was confirmed that the photoelectric conversion element of the present invention using a specific compound for the photoelectric conversion film has excellent responsiveness. It was also confirmed that the photoelectric conversion element of the present invention is also excellent in heat resistance.
On the other hand, the photoelectric conversion element using the compound R-1 in which the aromatic ring group corresponding to Ar 1 and Ar 4 in the formula (1) does not exist has insufficient responsiveness. Moreover, the heat resistance was also inferior to that of the photoelectric conversion element of the present invention.
In addition, the photoelectric conversion element using the compound R-2 having a mother nucleus having a structure different from that of the specific compound had insufficient responsiveness. Moreover, the heat resistance was also inferior to that of the photoelectric conversion element of the present invention.
　また、特定化合物が、式（３）で表される化合物に該当する場合、得られる光電変換素子の応答性がより優れることが確認された（実施例２、５、７、９の結果等を参照）。 Further, it was confirmed that when the specific compound corresponds to the compound represented by the formula (3), the responsiveness of the obtained photoelectric conversion element is more excellent (results of Examples 2, 5, 7, 9 and the like). reference).
　特定化合物中における式（１）中のＡｒ１、Ａｒ４で表される基に相当する基が、置換基を有してもよい多環の芳香環基、又は、式（Ｒ）で表される基である場合、得られる光電変換素子の耐熱性がより優れることが確認された（実施例２、３、６、７、８の結果等を参照）。 The group corresponding to the group represented by Ar 1 or Ar 4 in the formula (1) in the specific compound is represented by a polycyclic aromatic ring group which may have a substituent or a formula (R). It was confirmed that the obtained photoelectric conversion element has more excellent heat resistance in the case of a group (see the results of Examples 2, 3, 6, 7, 8 and the like).
　１０ａ，１０ｂ　　光電変換素子
　１１　　導電性膜（下部電極）
　１２　　光電変換膜
　１５　　透明導電性膜（上部電極）
　１６Ａ　　電子ブロッキング膜
　１６Ｂ　　正孔ブロッキング膜
　２０ａ　　撮像素子
　２２　　青色光電変換素子
　２４　　赤色光電変換素子 10a, 10b Photoelectric conversion element 11 Conductive film (lower electrode)
12 Photoelectric conversion film 15 Transparent conductive film (upper electrode)
16A Electron blocking film 16B Hole blocking film 20a Imaging element 22 Blue photoelectric conversion element 24 Red photoelectric conversion element

Claims (10)

  1. 　導電性膜、光電変換膜、及び、透明導電性膜をこの順で有する光電変換素子であって、
    　前記光電変換膜が、式（１）で表される化合物、及び、ｎ型半導体材料を含む、光電変換素子。
    Figure JPOXMLDOC01-appb-C000001
    　式（１）中、Ｘ１及びＹ１の一方が、－ＣＲａ１＝又は－Ｎ＝を表し、他方が、－Ｏ－、－Ｓ－、－Ｓｅ－、－Ｔｅ－、又は、－ＮＲａ２－を表す。
    　Ｘ２及びＹ２の一方が、－ＣＲａ１＝又は－Ｎ＝を表し、他方が、－Ｏ－、－Ｓ－、－Ｓｅ－、－Ｔｅ－、又は、－ＮＲａ２－を表す。
    　Ｒａ１及びＲａ２は、それぞれ独立に、水素原子又は置換基を表す。
    　Ｚ１及びＺ２は、それぞれ独立に、－ＣＲａ３＝又は－Ｎ＝を表す。
    　Ｒａ３は、水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいシリル基、置換基を有してもよいアリール基、又は、置換基を有してもよいヘテロアリール基を表す。
    　Ａｒ１～Ａｒ４は、それぞれ独立に、置換基を有してもよい芳香環基を表す。
    　ｍ１及びｍ２は、それぞれ独立に、０又は１を表す。
    　Ｌ１及びＬ２は、それぞれ独立に、－Ｓ－、－Ｏ－、－Ｓｅ－、－ＳｉＲａ４Ｒａ５－、－ＮＲａ６－、又は、－ＣＲａ７Ｒａ８－を表す。
    　Ｒａ４～Ｒａ８は、それぞれ独立に、水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいシリル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアリール基、又は、置換基を有してもよいヘテロアリール基を表す。
    　ただし、ｍ１が０を表す場合、Ｌ１は存在せず、Ａｒ１とＡｒ２とは、前記式（１）中に明示された単結合のみで連結する。ｍ２が０を表す場合、Ｌ２は存在せず、Ａｒ３とＡｒ４とは、前記式（１）中に明示された単結合のみで連結する。     A photoelectric conversion element having a conductive film, a photoelectric conversion film, and a transparent conductive film in this order.
    A photoelectric conversion element in which the photoelectric conversion film contains a compound represented by the formula (1) and an n-type semiconductor material.
    Figure JPOXMLDOC01-appb-C000001
    In formula (1), one of X 1 and Y 1 represents -CR a1 = or -N =, and the other represents -O-, -S-, -Se-, -Te-, or -NR a2. -Represents.
    One of X 2 and Y 2 represents -CR a1 = or -N =, and the other represents -O-, -S-, -Se-, -Te-, or -NR a2- .
    R a1 and R a2 independently represent a hydrogen atom or a substituent.
    Z 1 and Z 2 independently represent -CR a3 = or -N =, respectively.
    Ra3 may have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and a substituent. Represents a good silyl group, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.
    Ar 1 to Ar 4 each independently represent an aromatic ring group which may have a substituent.
    m1 and m2 independently represent 0 or 1, respectively.
    L 1 and L 2 independently represent -S-, -O-, -Se- , -SiR a4 R a5- , -NR a6- , or -CR a7 R a8- , respectively.
    R a4 to R a8 are independently hydrogen atom, halogen atom, alkyl group which may have a substituent, alkoxy group which may have a substituent, and an alkylthio group which may have a substituent. It has a silyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents a optionally heteroaryl group.
    However, when m1 represents 0, L 1 does not exist, and Ar 1 and Ar 2 are connected only by the single bond specified in the above equation (1). When m2 represents 0, L 2 does not exist, and Ar 3 and Ar 4 are connected only by the single bond specified in the above equation (1).
  2. 　前記式（１）で表される化合物が、式（２）で表される化合物、式（３）で表される化合物、又は、式（４）で表される化合物である、請求項１に記載の光電変換素子。
    Figure JPOXMLDOC01-appb-C000002
    　式（２）中、Ｙ３及びＹ４は、それぞれ独立に、－Ｏ－、－Ｓ－、又は、－Ｓｅ－を表す。
    　Ｒ１～Ｒ４は、それぞれ独立に、水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいシリル基、置換基を有してもよいアリール基、又は、置換基を有してもよいヘテロアリール基を表す。
    　Ａｒ１～Ａｒ４は、それぞれ独立に、置換基を有してもよい芳香環基を表す。
    　ｍ１及びｍ２は、それぞれ独立に、０又は１を表す。
    　Ｌ１及びＬ２は、それぞれ独立に、－Ｓ－、－Ｏ－、－Ｓｅ－、－ＳｉＲａ４Ｒａ５－、－ＮＲａ６－、又は、－ＣＲａ７Ｒａ８－を表す。
    　Ｒａ４～Ｒａ８は、それぞれ独立に、水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいシリル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアリール基、又は、置換基を有してもよいヘテロアリール基を表す。
    　ただし、ｍ１が０を表す場合、Ｌ１は存在せず、Ａｒ１とＡｒ２とは、前記式（２）中に明示された単結合のみで連結する。ｍ２が０を表す場合、Ｌ２は存在せず、Ａｒ３とＡｒ４とは、前記式（２）中に明示された単結合のみで連結する。
    Figure JPOXMLDOC01-appb-C000003
    　式（３）中、Ｙ３及びＸ３は、それぞれ独立に、－Ｏ－、－Ｓ－、又は、－Ｓｅ－を表す。
    　Ｒ１～Ｒ３及びＲ５は、それぞれ独立に、水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいシリル基、置換基を有してもよいアリール基、又は、置換基を有してもよいヘテロアリール基を表す。
    　Ａｒ１～Ａｒ４は、それぞれ独立に、置換基を有してもよい芳香環基を表す。
    　ｍ１及びｍ２は、それぞれ独立に、０又は１を表す。
    　Ｌ１及びＬ２は、それぞれ独立に、－Ｓ－、－Ｏ－、－Ｓｅ－、－ＳｉＲａ４Ｒａ５－、－ＮＲａ６－、又は、－ＣＲａ７Ｒａ８－を表す。
    　Ｒａ４～Ｒａ８は、それぞれ独立に、水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいシリル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアリール基、又は、置換基を有してもよいヘテロアリール基を表す。
    　ただし、ｍ１が０を表す場合、Ｌ１は存在せず、Ａｒ１とＡｒ２とは、前記式（３）中に明示された単結合のみで連結する。ｍ２が０を表す場合、Ｌ２は存在せず、Ａｒ３とＡｒ４とは、前記式（３）中に明示された単結合のみで連結する。
    Figure JPOXMLDOC01-appb-C000004
    　式（４）中、Ｘ３及びＸ４は、それぞれ独立に、－Ｏ－、－Ｓ－、又は、－Ｓｅ－を表す。
    　Ｒ１～Ｒ２及びＲ５～Ｒ６は、それぞれ独立に、水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいシリル基、置換基を有してもよいアリール基、又は、置換基を有してもよいヘテロアリール基を表す。
    　Ａｒ１～Ａｒ４は、それぞれ独立に、置換基を有してもよい芳香環基を表す。
    　ｍ１及びｍ２は、それぞれ独立に、０又は１を表す。
    　Ｌ１及びＬ２は、それぞれ独立に、－Ｓ－、－Ｏ－、－Ｓｅ－、－ＳｉＲａ４Ｒａ５－、－ＮＲａ６－、又は、－ＣＲａ７Ｒａ８－を表す。
    　Ｒａ４～Ｒａ８は、それぞれ独立に、水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいシリル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアリール基、又は、置換基を有してもよいヘテロアリール基を表す。
    　ただし、ｍ１が０を表す場合、Ｌ１は存在せず、Ａｒ１とＡｒ２とは、前記式（４）中に明示された単結合のみで連結する。ｍ２が０を表す場合、Ｌ２は存在せず、Ａｒ３とＡｒ４とは、前記式（４）中に明示された単結合のみで連結する。     According to claim 1, the compound represented by the formula (1) is a compound represented by the formula (2), a compound represented by the formula (3), or a compound represented by the formula (4). The photoelectric conversion element described.
    Figure JPOXMLDOC01-appb-C000002
    In formula (2), Y 3 and Y 4 independently represent -O-, -S-, or -Se-, respectively.
    R 1 to R 4 are independently hydrogen atom, halogen atom, alkyl group which may have a substituent, alkoxy group which may have a substituent, and an alkylthio group which may have a substituent. Represents a silyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.
    Ar 1 to Ar 4 each independently represent an aromatic ring group which may have a substituent.
    m1 and m2 independently represent 0 or 1, respectively.
    L 1 and L 2 independently represent -S-, -O-, -Se- , -SiR a4 R a5- , -NR a6- , or -CR a7 R a8- , respectively.
    R a4 to R a8 are independently hydrogen atom, halogen atom, alkyl group which may have a substituent, alkoxy group which may have a substituent, and an alkylthio group which may have a substituent. It has a silyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents a optionally heteroaryl group.
    However, if m1 represents 0, L 1 is absent, and Ar 1 and Ar 2, are connected only by a single bond which is expressly in the formula (2). When m2 represents 0, L 2 does not exist, and Ar 3 and Ar 4 are connected only by the single bond specified in the above equation (2).
    Figure JPOXMLDOC01-appb-C000003
    In formula (3), Y 3 and X 3 independently represent -O-, -S-, or -Se-, respectively.
    R 1 to R 3 and R 5 may independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. Represents an alkylthio group, a silyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.
    Ar 1 to Ar 4 each independently represent an aromatic ring group which may have a substituent.
    m1 and m2 independently represent 0 or 1, respectively.
    L 1 and L 2 independently represent -S-, -O-, -Se- , -SiR a4 R a5- , -NR a6- , or -CR a7 R a8- , respectively.
    R a4 to R a8 are independently hydrogen atom, halogen atom, alkyl group which may have a substituent, alkoxy group which may have a substituent, and an alkylthio group which may have a substituent. It has a silyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents a optionally heteroaryl group.
    However, if m1 represents 0, L 1 is absent, and Ar 1 and Ar 2, are connected only by a single bond which is expressly in the formula (3). When m2 represents 0, L 2 does not exist, and Ar 3 and Ar 4 are connected only by the single bond specified in the above equation (3).
    Figure JPOXMLDOC01-appb-C000004
    In formula (4), X 3 and X 4 independently represent -O-, -S-, or -Se-, respectively.
    R 1 to R 2 and R 5 to R 6 each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. It represents an alkylthio group which may have a substituent, a silyl group which may have a substituent, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.
    Ar 1 to Ar 4 each independently represent an aromatic ring group which may have a substituent.
    m1 and m2 independently represent 0 or 1, respectively.
    L 1 and L 2 independently represent -S-, -O-, -Se- , -SiR a4 R a5- , -NR a6- , or -CR a7 R a8- , respectively.
    R a4 to R a8 are independently hydrogen atom, halogen atom, alkyl group which may have a substituent, alkoxy group which may have a substituent, and an alkylthio group which may have a substituent. It has a silyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents a optionally heteroaryl group.
    However, if m1 represents 0, L 1 is absent, and Ar 1 and Ar 2, are connected only by a single bond which is expressly in the formula (4). When m2 represents 0, L 2 does not exist, and Ar 3 and Ar 4 are connected only by the single bond specified in the above equation (4).
  3. 　Ａｒ２及びＡｒ３が、置換基を有してもよい単環の芳香環基を表す、請求項１又は２に記載の光電変換素子。 The photoelectric conversion element according to claim 1 or 2, wherein Ar 2 and Ar 3 represent a monocyclic aromatic ring group which may have a substituent.
  4. 　前記式（１）で表される化合物の分子量が４５０～９００である、請求項１～３のいずれか１項に記載の光電変換素子。 The photoelectric conversion element according to any one of claims 1 to 3, wherein the compound represented by the formula (1) has a molecular weight of 450 to 900.
  5. 　前記光電変換膜が、前記式（１）で表される化合物と前記ｎ型半導体材料とが混合された状態で形成されるバルクへテロ構造を有する、請求項１～４のいずれか１項に記載の光電変換素子。 According to any one of claims 1 to 4, the photoelectric conversion film has a bulk heterostructure formed in a state where the compound represented by the formula (1) and the n-type semiconductor material are mixed. The photoelectric conversion element described.
  6. 　前記導電性膜と前記透明導電性膜との間に、前記光電変換膜の他に１種以上の中間層を有する、請求項１～５のいずれか１項に記載の光電変換素子。 The photoelectric conversion element according to any one of claims 1 to 5, which has one or more intermediate layers in addition to the photoelectric conversion film between the conductive film and the transparent conductive film.
  7. 　前記ｎ型半導体材料が、フラーレン及びその誘導体からなる群より選択されるフラーレン類を含む、請求項１～６のいずれか１項に記載の光電変換素子。 The photoelectric conversion element according to any one of claims 1 to 6, wherein the n-type semiconductor material contains fullerenes selected from the group consisting of fullerenes and derivatives thereof.
  8. 　請求項１～７のいずれか１項に記載の光電変換素子を有する、撮像素子。 An image pickup device having the photoelectric conversion element according to any one of claims 1 to 7.
  9. 　請求項１～７のいずれか１項に記載の光電変換素子を有する、光センサ。 An optical sensor having the photoelectric conversion element according to any one of claims 1 to 7.
  10. 　式（１）で表される化合物を含む、光電変換素子用材料。
    Figure JPOXMLDOC01-appb-C000005
    　式（１）中、Ｘ１及びＹ１の一方が、－ＣＲａ１＝又は－Ｎ＝を表し、他方が、－Ｏ－、－Ｓ－、－Ｓｅ－、－Ｔｅ－、又は、－ＮＲａ２－を表す。
    　Ｘ２及びＹ２の一方が、－ＣＲａ１＝又は－Ｎ＝を表し、他方が、－Ｏ－、－Ｓ－、－Ｓｅ－、－Ｔｅ－、又は、－ＮＲａ２－を表す。
    　Ｒａ１及びＲａ２は、それぞれ独立に、水素原子又は置換基を表す。
    　Ｚ１及びＺ２は、それぞれ独立に、－ＣＲａ３＝又は－Ｎ＝を表す。
    　Ｒａ３は、水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいシリル基、置換基を有してもよいアリール基、又は、置換基を有してもよいヘテロアリール基を表す。
    　Ａｒ１～Ａｒ４は、それぞれ独立に、置換基を有してもよい芳香環基を表す。
    　ｍ１及びｍ２は、それぞれ独立に、０又は１を表す。
    　Ｌ１及びＬ２は、それぞれ独立に、－Ｓ－、－Ｏ－、－Ｓｅ－、－ＳｉＲａ４Ｒａ５－、－ＮＲａ６－、又は、－ＣＲａ７Ｒａ８－を表す。
    　Ｒａ４～Ｒａ８は、それぞれ独立に、水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいシリル基、置換基を有してもよいアルケニル基、置換基を有してもよいアルキニル基、置換基を有してもよいアリール基、又は、置換基を有してもよいヘテロアリール基を表す。
    　ただし、ｍ１が０を表す場合、Ｌ１は存在せず、Ａｒ１とＡｒ２とは、前記式（１）中に明示された単結合のみで連結する。ｍ２が０を表す場合、Ｌ２は存在せず、Ａｒ３とＡｒ４とは、前記式（１）中に明示された単結合のみで連結する。     A material for a photoelectric conversion element containing a compound represented by the formula (1).
    Figure JPOXMLDOC01-appb-C000005
    In formula (1), one of X 1 and Y 1 represents -CR a1 = or -N =, and the other represents -O-, -S-, -Se-, -Te-, or -NR a2. -Represents.
    One of X 2 and Y 2 represents -CR a1 = or -N =, and the other represents -O-, -S-, -Se-, -Te-, or -NR a2- .
    R a1 and R a2 independently represent a hydrogen atom or a substituent.
    Z 1 and Z 2 independently represent -CR a3 = or -N =, respectively.
    Ra3 may have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and a substituent. Represents a good silyl group, an aryl group which may have a substituent, or a heteroaryl group which may have a substituent.
    Ar 1 to Ar 4 each independently represent an aromatic ring group which may have a substituent.
    m1 and m2 independently represent 0 or 1, respectively.
    L 1 and L 2 independently represent -S-, -O-, -Se- , -SiR a4 R a5- , -NR a6- , or -CR a7 R a8- , respectively.
    R a4 to R a8 are independently hydrogen atom, halogen atom, alkyl group which may have a substituent, alkoxy group which may have a substituent, and an alkylthio group which may have a substituent. It has a silyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents a optionally heteroaryl group.
    However, when m1 represents 0, L 1 does not exist, and Ar 1 and Ar 2 are connected only by the single bond specified in the above equation (1). When m2 represents 0, L 2 does not exist, and Ar 3 and Ar 4 are connected only by the single bond specified in the above equation (1).
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