WO2024122652A1 - 光電変換素子、撮像素子、光電変換素子用材料、および化合物 - Google Patents

光電変換素子、撮像素子、光電変換素子用材料、および化合物 Download PDF

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WO2024122652A1
WO2024122652A1 PCT/JP2023/044249 JP2023044249W WO2024122652A1 WO 2024122652 A1 WO2024122652 A1 WO 2024122652A1 JP 2023044249 W JP2023044249 W JP 2023044249W WO 2024122652 A1 WO2024122652 A1 WO 2024122652A1
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group
carbon atoms
photoelectric conversion
conversion element
aromatic hydrocarbon
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English (en)
French (fr)
Japanese (ja)
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華奈 尾池
裕太 森中
洋平 小野
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Tosoh Corp
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Tosoh Corp
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Priority to EP26153109.9A priority Critical patent/EP4709126A2/en
Priority to EP23900761.0A priority patent/EP4633334A1/en
Priority to KR1020257022755A priority patent/KR20250121565A/ko
Priority to US19/136,089 priority patent/US20260090266A1/en
Priority to CN202380084031.7A priority patent/CN120304040A/zh
Priority to JP2024563013A priority patent/JPWO2024122652A1/ja
Publication of WO2024122652A1 publication Critical patent/WO2024122652A1/ja
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Definitions

  • the present invention relates to photoelectric conversion elements, imaging elements, materials for photoelectric conversion elements, and compounds.
  • Photoelectric conversion elements are widely used in solar cells, optical sensors, image sensors, etc., and their applications and market are expanding, leading to vigorous development.
  • Patent Document 1 discloses a photoelectric conversion element that contains a pyrimidine derivative in the hole blocking layer.
  • Patent Document 2 discloses a photoelectric conversion element that contains a triazine derivative in the hole blocking layer.
  • imaging elements which are photoelectric conversion elements, are required to have excellent response speeds and external quantum efficiency.
  • the object of one aspect of the present invention is to provide a photoelectric conversion element and an image sensor that have an excellent response speed and a high external quantum yield, as well as a photoelectric conversion element material and a hole-blocking material used in the photoelectric conversion element and the image sensor.
  • a photoelectric conversion element having a layer containing a photoelectric conversion element material represented by the following formula (1):
  • Ar represents a fused aromatic hydrocarbon group having 16 to 40 carbon atoms
  • EWG represents an electron withdrawing group
  • L represents an aromatic hydrocarbon group having 6 to 30 carbon atoms
  • n represents an integer from 1 to 8
  • k represents an integer from 0 to 2
  • p represents an integer from 1 to 8; when k is 0, p is 1;
  • the EWGs are the same or different electron-withdrawing groups,
  • Each of the Ar, L, and EWG has at least one substituent or has no substituent.
  • a photoelectric conversion element in which the layer containing the material for the photoelectric conversion element is a hole blocking layer.
  • a material for a photoelectric conversion element is provided for forming the layer provided in the photoelectric conversion element according to the above aspect.
  • the photoelectric conversion element material according to the above aspect is a photoelectric conversion element material for an imaging element.
  • a material for photoelectric conversion elements according to the above aspect, which is a hole-blocking material.
  • X 1 to X 5 each represent a nitrogen atom or CR 55 ;
  • the number of nitrogen atoms is an integer of 0 to 3;
  • R 40 to R 55 are each independently selected from a hydrogen atom, a cyano group, a nitro group, a halogen atom, a halogenated alkyl group, an acyl group, a sulfonyl group, a phosphoryl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, a bicycloalkyl group having 1 to 20 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and a
  • R 61 to R 76 are each independently selected from a hydrogen atom, a cyano group, a nitro group, a halogen atom, a halogenated alkyl group, an acyl group, a sulfonyl group, a phosphoryl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, a bicycloalkyl group having 1 to 20 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, and a group represented by formula (4-2), or two adjacent groups are bonded to form a ring; Any
  • a photoelectric conversion element and an image sensor that have an excellent response speed and a high external quantum yield, as well as a photoelectric conversion element material and a hole blocking material that are used in the photoelectric conversion element and the image sensor.
  • FIG. 1 is a cross-sectional view showing an outline of a layered structure of a photoelectric conversion element for an imaging device, which includes a photoelectric conversion element material according to one embodiment of the present invention.
  • a photoelectric conversion element according to one embodiment of the present invention includes a layer of a material for a photoelectric conversion element represented by the following formula (1).
  • Ar represents a fused aromatic hydrocarbon group having 16 to 40 carbon atoms
  • EWG represents an electron withdrawing group
  • L represents an aromatic hydrocarbon group having 6 to 30 carbon atoms
  • n represents an integer from 1 to 8
  • k represents an integer of 0 to 2
  • p represents an integer from 1 to 8; when k is 0, p is 1;
  • the EWGs are the same or different electron-withdrawing groups,
  • Each of the Ar, L, and EWG has at least one substituent or has no substituent.
  • L, EWG, k, and p shown in formula (1') are the same as those of L, EWG, k, and p shown in formula (1).
  • the compound represented by the formula (1) is an electron transport material that has excellent charge, i.e., electron transport properties, and is a hole blocking material that has excellent reverse charge, i.e., hole blocking properties, and can be suitably used as a material for photoelectric conversion elements.
  • Ar is a fused aromatic hydrocarbon group formed by condensing aromatic rings, and the fused aromatic hydrocarbon group may have a substituent.
  • the fused aromatic hydrocarbon group of Ar has a carbon number in the range of 16 to 40, and preferably in the range of 20 to 40.
  • the range of 16 to 40 carbon numbers when Ar is larger, high thermal stability can be imparted to the material for photoelectric conversion elements, and when Ar is smaller, the LUMO level in the material for photoelectric conversion elements can be prevented from becoming excessively shallow.
  • Ar is preferably a fused aromatic hydrocarbon group containing four or more six-membered rings.
  • Ar is a fused aromatic hydrocarbon group in which four or more six-membered rings are fused, the Tg of the material for photoelectric conversion elements can be increased, and thus the thermal stability of the material for photoelectric conversion elements can be improved.
  • the Ar is, for example, a fused aromatic hydrocarbon group selected from a triphenylene group (A2), a fluoranthene group (A15), and a spirofluorene group (A21), or a fused aromatic hydrocarbon group selected from a triphenylene group (A3) to (A14), a fused aromatic hydrocarbon group (A16) to (A20) containing a fluoranthene group, and a spirofluorene group (A22) to (A25).
  • a fused aromatic hydrocarbon group selected from a triphenylene group (A2), a fluoranthene group (A15), and a spirofluorene group (A21)
  • a fused aromatic hydrocarbon group selected from a triphenylene group (A3) to (A14) a fused aromatic hydrocarbon group (A16) to (A20) containing a fluoranthene group, and a spirofluorene group (A22) to
  • Ar may have a substituent, and may have a structure represented by, for example, the following formulas (2-1), (2-2), and (2-3).
  • R 1 to R 38 are each independently at least one substituent selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, a bicycloalkyl group having 1 to 20 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and a heteroaryl group having 3 to 30 carbon atoms.
  • the aromatic hydrocarbon group having 6 to 30 carbon atoms is the same as the group represented by L described below.
  • the heteroaryl group having 3 to 30 carbon atoms is preferably selected from the heteroaryl groups having 3 to 30 carbon atoms and containing a nitrogen atom represented by EWG described below.
  • R 1 to R 38 may be a ring formed by bonding two adjacent groups as a substituent, and the ring may be a hydrocarbon ring. More specifically, two adjacent groups among R 1 to R 12 shown in formula (2-1) may be bonded to form a ring. This allows the compound to have a structure represented by formula (2-1) and, for example, any fused aromatic hydrocarbon group selected from the above-mentioned fused aromatic hydrocarbon groups (A4) to (A14). In addition, two adjacent groups among R 12 to R 22 shown in formula (2-2) may be bonded to form a ring.
  • R 1 to R 38 may be substituted with the group shown in formula (1'), or the hydrogen atoms of R 1 to R 38 may be substituted with the group shown in formula (1').
  • each of R 1 to R 35 may independently further have at least one substituent, or may not have any substituent.
  • EWG EWG represents an electron-withdrawing group.
  • these EWGs may be the same electron-withdrawing group or may be different electron-withdrawing groups.
  • the electron-withdrawing group is preferably at least one group selected from a cyano group, a nitro group, a halogen atom, a halogenated alkyl group, an acyl group, a sulfonyl group, a phosphoryl group, and a nitrogen atom-containing heteroaryl group having 3 to 30 carbon atoms, and the nitrogen atom-containing heteroaryl group having 3 to 30 carbon atoms may have at least one substituent or may not have the aforementioned substituent.
  • the halogen atom represented by EWG is preferably a fluorine atom.
  • the halogenated alkyl group represented by EWG is preferably a halogenated alkyl group having 1 to 5 carbon atoms, more preferably a halogenated alkyl group having 1 to 3 carbon atoms.
  • the halogenated alkyl group is preferably a fluorinated alkyl group, more preferably a perfluoroalkyl group.
  • the fluorinated alkyl group is preferably a perfluorobutyl group, a perfluoropropyl group, a perfluoroethyl group, or a trifluoromethyl group, more preferably a trifluoromethyl group.
  • Acyl groups represented by EWG include alkyl acyl groups and arylacyl groups, with alkyl acyl groups having 2 to 5 carbon atoms and arylacyl groups having 7 to 15 carbon atoms being preferred.
  • alkyl acyl groups include acetyl groups, propionyl groups, and trifluoroacetyl groups.
  • arylacyl groups include benzoyl groups, cyanobenzoyl groups, fluorobenzoyl groups, and trifluoromethylbenzoyl groups.
  • the sulfonyl group represented by EWG includes alkylsulfonyl groups and arylsulfonyl groups, with alkylsulfonyl groups having 1 to 5 carbon atoms and arylsulfonyl groups having 6 to 15 carbon atoms being preferred.
  • alkylsulfonyl group include methylsulfonyl groups, ethylsulfonyl groups, n-propylsulfonyl groups, and isopropylsulfonyl groups.
  • Examples of the arylsulfonyl group include phenylsulfonyl groups, cyanophenylsulfonyl groups, and fluorophenylsulfonyl groups.
  • the phosphoryl group represented by EWG includes dialkylphosphoryl groups and diarylphosphoryl groups, with dialkylphosphoryl groups having 2 to 10 carbon atoms and diarylphosphonyl groups having 12 to 30 carbon atoms being preferred.
  • dialkylphosphoryl groups include dimethylphosphoryl groups, diethylphosphoryl groups, and dipropylphosphoryl groups.
  • diarylphosphoryl groups include diphenylphosphoryl groups and di(fluorophenyl)phosphoryl groups.
  • heteroaryl groups containing a nitrogen atom and having 3 to 30 carbon atoms include pyridyl, pyrimidyl, pyrazyl, triazyl, imidazolyl, quinolyl, isoquinolyl, azaanthryl, diazaanthryl, triazanthryl, tetraazaanthryl, azaphenanthryl, diazaphenanthryl, triazaphenanthryl, tetraazaphenanthryl, azapyrenyl, diazapyrenyl, triazapyrenyl, tetraazapyrenyl, azafluoranthenyl, and diaza.
  • Examples of such groups include fluoranthenyl, triazafluoranthenyl, tetraazafluoranthenyl, azatriphenylenyl, diazatriphenylenyl, triazatriphenylenyl, tetraazatriphenylenyl, pentaazatriphenylenyl, hexaazatriphenylenyl, oxazolyl, pyrrolyl, imidazolyl, triazolyl, thiadiazolyl, oxadiazolyl, benzothiazolyl, benzoxazolyl, benzothiadiazolyl, and benzoxadiazolyl groups.
  • cyano group, halogen atom, halogenated alkyl group, acyl group, sulfonyl group, phosphoryl group, aromatic hydrocarbon group having 6 to 30 carbon atoms, and heteroaryl group having 3 to 30 carbon atoms are preferred, cyano group, halogen atom, halogenated alkyl group, and heteroaryl group having 3 to 30 carbon atoms are more preferred, cyano group, fluorine atom, and fluorinated alkyl group are further preferred, and cyano group, fluorine atom, and trifluoromethyl group are particularly preferred.
  • the halogenated alkyl group, acyl group, sulfonyl group, phosphoryl group, and heteroaryl group having 3 to 30 carbon atoms in the substituents of EWG are the same as those explained for these groups represented by EWG.
  • the aromatic hydrocarbon group having 6 to 30 carbon atoms is the same as those described below for these groups represented by L.
  • a cyano group, a fluorine atom, a fluoroalkyl group, or a heteroaryl group having 3 to 30 carbon atoms and containing a nitrogen atom is preferred, and a cyano group, a fluorine atom, a fluoroalkyl group, or a heteroaryl group having 3 to 30 carbon atoms and containing a nitrogen atom and having at least one group selected from a cyano group, a fluorine atom, and a fluoroalkyl group as a substituent of EWG is more preferred.
  • L represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, and the aromatic hydrocarbon group having 6 to 30 carbon atoms may have a substituent.
  • aromatic hydrocarbon groups having 6 to 30 carbon atoms include phenyl, naphthyl, phenanthryl, anthryl, fluorenyl, dimethylfluorenyl, spirofluorenyl, pyrenyl, fluoranthenyl, triphenylenyl, tetracenyl, and chrysenyl groups. Of these, phenyl and naphthyl groups are preferred.
  • Substituents on aromatic hydrocarbon groups having 6 to 30 carbon atoms are the same as those described as EWG substituents, such as nitrogen atom-containing heteroaryl groups having 3 to 30 carbon atoms, and so a description thereof will be omitted.
  • n preferably represents an integer of 1 to 8.
  • k is an integer between 0 and 2, and is preferably an integer of 0 or 1.
  • EWG is a cyano group, a fluorine atom, or a fluoroalkyl group, which can deepen the LUMO level of the material for photoelectric conversion elements while preventing the Tg of the material for photoelectric conversion elements from becoming lower, thereby increasing the response speed of the photoelectric conversion elements.
  • p represents an integer from 1 to 8, and when k is 0, p is preferably 1.
  • the photoelectric conversion element material represented by the above formula (1) has a higher glass transition temperature Tg due to the above Ar structure, as described below, and this prevents a decrease in external quantum efficiency and dark current due to heating in a photoelectric conversion element having a layer formed from the photoelectric conversion element material.
  • the photoelectric conversion element material represented by the above formula (1) has an increased response speed to light due to the above EWG. Therefore, it can be suitably used in photoelectric conversion elements that require both response speed and external quantum efficiency.
  • the photoelectric conversion element material provided in the photoelectric conversion element according to one embodiment of the present invention is not limited to the above embodiment.
  • Ar represented by formula (1) is a fused aromatic hydrocarbon group represented by (A12), (A20), (A21), (A-22) to (A-25).
  • the compound according to one embodiment of the present invention is a compound provided with a fused aromatic hydrocarbon group, and may be a compound selected from the compound represented by the following formula (3) and the compounds represented by the following formulas (4-1) and (4-2).
  • the photoelectric conversion element material included in the photoelectric conversion element according to one embodiment of the present invention is not limited to the above embodiment.
  • a compound represented by the following formula (3) described below is also included in the scope of the present invention according to one embodiment.
  • X 1 to X 5 each represent a nitrogen atom or CR 55 ;
  • the number of nitrogen atoms is an integer of 0 to 3;
  • R 40 to R 55 are each independently selected from a hydrogen atom, a cyano group, a nitro group, a halogen atom, a halogenated alkyl group, an acyl group, a sulfonyl group, a phosphoryl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, a bicycloalkyl group having 1 to 20 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and a heteroaryl group having 3 to 30 carbon atoms, or
  • the compound represented by formula (3) has a fused aromatic hydrocarbon group, and the fused aromatic hydrocarbon group can be (A12), which is exemplified as Ar in formula (1).
  • X 1 to X 5 each represent a nitrogen atom or CR 55 , and among X 1 to X 5 , the number of nitrogen atoms is an integer of 0 to 3.
  • R40 to R55 The substituents represented by R 40 to R 55 and preferred specific examples thereof are the same as the examples of the substituents represented by formula (1). In addition, preferred specific examples of the further substituents carried by R 40 to R 55 are the same as the substituents of EWG represented by formula (1).
  • R 55 may be selected from a hydrogen atom, a cyano group, a nitro group, a halogen atom, a halogenated alkyl group, an acyl group, a sulfonyl group, a phosphoryl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, a bicycloalkyl group having 1 to 20 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and a heteroaryl group having 3 to 30 carbon atoms. Any one of R 55 is a cyano group, a halogen atom, or a halogenated alkyl group, and adjacent R 55 may be bonded to each other to form a ring.
  • the halogen atom is a fluorine atom
  • the aromatic hydrocarbon group having 6 to 30 carbon atoms may or may not be substituted with a group selected from a cyano group, a fluorine group, and a fluoroalkyl group.
  • the photoelectric conversion element material included in the photoelectric conversion element according to one embodiment of the present invention is not limited to the above embodiment.
  • a compound represented by the following formula (4-1) described below is also included in the scope of the present invention according to one embodiment.
  • R 61 to R 76 are each independently selected from a hydrogen atom, a cyano group, a nitro group, a halogen atom, a halogenated alkyl group, an acyl group, a sulfonyl group, a phosphoryl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, a bicycloalkyl group having 1 to 20 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, and a group represented by formula (4-2), or two adjacent groups are bonded to form a ring; Any one of R 61 to R 64 is a group represented by formula (4-2); L represents a direct bond
  • R 61 to R 76 may be selected from the same groups as R 40 to R 55 in the compound of formula (3) above, except when selected from the group represented by formula (4-2).
  • R 61 to R 76 may be selected from (a) a cyano group, a nitro group, a halogen atom, a halogenated alkyl group, an acyl group, a sulfonyl group, a phosphoryl group, a heteroaryl group having 3 to 30 carbon atoms, and a group represented by formula (4-2), or (b) a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, a bicycloalkyl group having 1 to 20 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an alkoxy
  • R 61 to R 76 are preferably selected from the above (a) from the viewpoint of deepening the LUMO level of the compound, and may be selected from the groups represented by EWG in formula (1) above, and are more preferably selected from a cyano group, a heteroaryl group having 3 to 16 carbon atoms, and a group represented by formula (4-2). However, when R 61 to R 76 are selected from heteroaryl groups having 3 to 16 carbon atoms, the heteroaryl group may or may not contain a carbazolyl group.
  • R 61 to R 76 are preferably selected from the above-mentioned (b), and more preferably selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 16 carbon atoms.
  • the ring when two adjacent groups in R 61 to R 76 are bonded to form a ring, the ring may constitute a part of the fused aromatic hydrocarbon group exemplified as Ar in formula (1). That is, the compound represented by formula (4-1) has a fused aromatic hydrocarbon group, and the fused aromatic hydrocarbon group may be (A21) exemplified as Ar in formula (1), and when R 61 to R 76 form a ring, the fused aromatic hydrocarbon group may be the fused aromatic hydrocarbon group exemplified as (A-22) to (A-25). In formula (4-1), it is preferable that R 61 to R 76 form a ring, from the viewpoint of further increasing the Tg of the compound.
  • L is selected from the aromatic hydrocarbon groups having 6 to 16 carbon atoms among the specific examples of L represented by formula (1), and may be a phenyl group, naphthyl group, phenanthryl group, anthryl group, fluorenyl group, dimethylfluorenyl group, etc., and the aromatic hydrocarbon group having 6 to 16 carbon atoms may have a substituent.
  • the substituent of the aromatic hydrocarbon group having 6 to 16 carbon atoms may be selected from those described as the substituent of EWG, such as a heteroaryl group having 3 to 30 carbon atoms containing a nitrogen atom.
  • the ring structure having X 6 to X 10 is selected from a phenyl group substituted with 2 to 3 nitrile groups and a pyridyl group substituted with two nitrile groups, has R 77 as a group other than the nitrile group, and is an electron-withdrawing group like EWG represented by formula (1).
  • X 10 is a nitrogen atom or C(CN)
  • X 7 and X 8 are C(CN) or CR 77
  • X 6 and X 9 are CR 77 .
  • R 77 is each independently selected from a hydrogen atom, a nitro group, a halogen atom, a halogenated alkyl group, an acyl group, a sulfonyl group, a phosphoryl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, a bicycloalkyl group having 1 to 20 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, and more preferably each independently selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 1 to 20 carbon atoms.
  • substituents represented by R 61 to R 77 each have at least one substituent, or each does not have the above-mentioned substituent, and when each has a substituent, the substituent may be selected from those explained as the substituents represented by EWG, such as a nitrogen atom-containing heteroaryl group having 3 to 30 carbon atoms.
  • the compounds represented by formula (3) and formula (4-1) can be suitably used, for example, as materials for photoelectric conversion elements.
  • Photoelectric conversion element materials, hole-blocking materials for photoelectric conversion elements The applications of the material for photoelectric conversion elements according to one embodiment of the present invention will be described below.
  • the material for photoelectric conversion elements can be suitably used for layers included in photoelectric conversion elements, such as a photoelectric conversion layer and a hole blocking layer, due to the compatibility of response speed and external quantum efficiency.
  • the photoelectric conversion element material has a high Tg, changes in the film state, such as crystallization, caused by annealing during the manufacture of the photoelectric conversion element are prevented. This prevents a decrease in the external quantum efficiency and dark current in the photoelectric conversion element formed from the photoelectric conversion element material. Therefore, the photoelectric conversion element material can be suitably used as a photoelectric conversion element material for image sensors, which require resistance to annealing after the photoelectric conversion layer is formed, and as a hole blocking material.
  • the photoelectric conversion material can be used, for example, as a material for a photoelectric conversion layer in an image sensor, or as a hole blocking material that is a material for a hole blocking layer in the image sensor.
  • the photoelectric conversion element material according to one embodiment of the present invention contains a skeleton represented by the above formula (1) or formula (3), or formula (4-1).
  • the photoelectric conversion element material and hole blocking material contained in a layer of an imaging element, which contain a skeleton represented by formula (1) or (3), or formula (4-1), contribute to the production of a photoelectric conversion element material for an imaging element having excellent response speed and external quantum efficiency characteristics.
  • the material for the photoelectric conversion element may need to rapidly move the charge generated in the photoelectric conversion layer.
  • the LUMO levels of the n-type semiconductor material of the photoelectric conversion layer and the material used in the hole blocking layer are close to each other.
  • the LUMO level of the hole blocking layer is preferably -2.2 eV or less, more preferably -2.3 eV or less, as a quantum calculation value obtained by density functional theory (DFT) as described later.
  • DFT density functional theory
  • the LUMO level of the hole blocking layer is not limited, but may be -5.0 eV or more, and is preferably -4.0 eV or more.
  • the LUMO levels of the materials for photoelectric conversion elements represented by formulas (1) and (3) are not particularly limited, but from the viewpoint of compatibility with imaging elements, the LUMO level is preferably -2.2 eV or less, and more preferably -2.3 eV or less.
  • the LUMO level of the material for the photoelectric conversion element is a value calculated by quantum chemical calculation, and the molecular structure is optimized and the LUMO level is calculated by density functional theory (DFT) using a Gaussian program under the calculation conditions of the B3LYP functional and the 6-31G(d) basis set.
  • DFT density functional theory
  • the photoelectric conversion element material used for forming a layer included in the imaging element according to one embodiment of the present invention is a photoelectric conversion element material represented by formula (1) or formula (3)
  • the glass transition temperature of the photoelectric conversion element material represented by formulas (1) and (3) is not particularly limited, but from the viewpoint of compatibility with the imaging element, i.e., the photoelectric conversion element for the imaging element, the glass transition temperature is preferably 140° C. or higher, and more preferably 150° C. or higher. Note that this glass transition temperature is a value obtained by differential scanning calorimetry.
  • the differential scanning calorimeter and test conditions are as follows: Differential scanning calorimeter model: Hitachi High-Tech DSC702; Operating conditions: Heating rate, 10°C/min, temperature range, 40°C to 380°C. The glass transition temperature was determined from the peak after two scans.
  • the photoelectric conversion element material as the imaging element according to one embodiment of the present invention or the photoelectric conversion element material represented by formula (1) and formula (3) is preferably one in which the evaporated film of the material forms an amorphous layer. If the evaporated film is a crystalline layer, the interface with the adjacent layer will not be uniform, which will cause defects in the element.
  • Whether or not the deposited film is an amorphous layer can be confirmed by, but not limited to, visual inspection to see if there is crystallization, or by XRD measurement of the deposited film to see if no sharp diffraction peaks are observed.
  • the photoelectric conversion element according to an aspect of the present invention is preferably an imaging element, and includes a layer containing the material for a photoelectric conversion element according to an aspect of the present invention.
  • the configuration of the imaging element is not particularly limited, but examples include the following configurations (i) to (vi).
  • FIG. 1 is a schematic cross-sectional view showing an example of a laminated configuration of an imaging element including a layer containing a material for a photoelectric conversion element according to one embodiment of the present invention.
  • the imaging element 100 comprises a first electrode 1, a hole blocking layer 2, a photoelectric conversion layer 3, an electron blocking layer 4, a hole transport layer 5, and a second electrode 6, in this order. However, some of these layers may be omitted, or other layers may be added. Of the above layers, the hole blocking layer 2, the photoelectric conversion layer 3, the electron blocking layer 4, and the hole transport layer 5 constitute the organic layer 10.
  • the imaging element 100 shown in FIG. 1 may specifically be a photoelectric conversion element for imaging.
  • light is incident from below the transparent first electrode 1, and is received by the photoelectric conversion layer 3, which is a light receiving layer.
  • the direction of incidence of light is not particularly limited, and the second electrode 6 may be transparent and light may be incident from the second electrode 6 side.
  • the imaging element 100 due to an internal electric field caused by the difference in concentration of carriers constituting each layer and the difference in work function between the first electrode 1 and the second electrode 6, among the charges (holes and electrons) generated by the light received by the photoelectric conversion layer 3, the electrons move to the first electrode 1 and the holes move to the second electrode 6.
  • the charges can also be moved by applying a voltage between the first electrode 1 and the second electrode 6. In this way, the first electrode 1 serves as an electron collecting electrode and the second electrode 6 serves as a hole collecting electrode.
  • each layer may be replaced with a layer having a different name or function as necessary.
  • layers having a different name or function include a hole injection layer, a work function adjustment layer, and a hole transport promotion layer.
  • the substrate provided on the lower surface of the first electrode 1 is omitted.
  • the substrate here is not particularly limited, and examples thereof include a glass plate, a quartz plate, a plastic plate, and the like.
  • the substrate in a configuration in which light is incident from the substrate side, the substrate is transparent to the wavelength of light.
  • the substrate may be provided on the second electrode 6 side.
  • An imaging element which is one embodiment of a photoelectric conversion element, may contain the material for a photoelectric conversion element represented by the above formula (1) or (3), or formula (4-1), in one or more layers selected from the group consisting of a photoelectric conversion layer and a layer between the photoelectric conversion layer and a second electrode.
  • the imaging element 100 contains the material for a photoelectric conversion element in at least one layer selected from the group consisting of the hole blocking layer 2 and the photoelectric conversion layer 3.
  • the material for a photoelectric conversion element is contained in the hole blocking layer 2. This has the effect of quickly transferring required charges while controlling the reverse transfer of holes.
  • the photoelectric conversion element material represented by the above formula (1) or (3), or formula (4-1) may be contained in multiple layers of the photoelectric conversion element, and if an electron transport layer is provided, the electron transport layer may contain the photoelectric conversion element material.
  • the following describes an imaging photoelectric conversion element 100 in which the hole blocking layer 2 contains a photoelectric conversion element material.
  • a first electrode 1 is provided on the substrate.
  • the first electrode 1 is preferably made of a transparent material that transmits or substantially transmits the light.
  • the transparent material used for the lower electrode, which is the first electrode 1 is not particularly limited, but examples include indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide, aluminum-doped tin oxide, magnesium indium oxide, nickel tungsten oxide, other metal oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, and metal sulfides such as zinc sulfide.
  • ITO indium tin oxide
  • IZO indium zinc oxide
  • tin oxide aluminum-doped tin oxide
  • magnesium indium oxide nickel tungsten oxide
  • other metal oxides metal nitrides
  • metal selenides such as zinc selenide
  • metal sulfides such as zinc sulfide.
  • the imaging element 100 is configured so that light enters the photoelectric conversion layer 3 only from the second electrode 6 side, the light transmission characteristics of the first electrode 1 are not important. Therefore, examples of materials that can be used for the first electrode 1 in this case include gold, iridium, molybdenum, palladium, platinum, etc.
  • a hole blocking layer 2 is provided between the first electrode 1 and a photoelectric conversion layer 3 which is a light receiving layer described below.
  • the hole blocking layer 2 has the role of transporting electrons generated in the photoelectric conversion layer 3 to the first electrode 1, and the role of blocking the movement of holes from the photoelectric conversion layer 3 to the first electrode 1 to which the electrons are transported. Depending on the application, it may also have the role of blocking hole injection from the first electrode 1.
  • the hole blocking layer 2 may contain, in addition to the photoelectric conversion element material represented by the above-mentioned formula (1) and formula (3), or formula (4-1), a conventionally known hole blocking material (electron transport material).
  • conventional hole blocking materials include bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis(2-methyl-8-quinolinolato)-4-(phenylphenolato)aluminum), 4,6-bis(3,5-di(pyridin-4-yl)phenyl)-2-methylpyrimidine, N,N'-diphenyl-1,4,5,8-naphthalenetetracarboxylic acid diimide, and N,N,N
  • the hole blocking layer 2 may be a single layer structure made of one or more materials, or a laminate structure made of multiple layers of the same or different compositions.
  • a photoelectric conversion layer 3 which is a light receiving layer, is provided between the hole blocking layer 2 and an electron blocking layer 4 described below.
  • Examples of materials for the photoelectric conversion layer 3 include materials having a photoelectric conversion function.
  • the photoelectric conversion layer 3 may be a single layer structure made of one or more materials, or a laminate structure made of multiple layers of the same or different compositions. In particular, in order to increase the photoelectric conversion efficiency, it is preferable that the photoelectric conversion layer 3 be made of a layer containing at least two types of materials (organic components).
  • Examples of materials used for the photoelectric conversion layer 3, which has a single-layer structure made of one type of material, include (i) coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, etc.
  • Materials used for the photoelectric conversion layer 3, which has a single layer structure made of two types of materials include, for example, the above-mentioned combinations of (i) coumarin and its derivatives, quinacridone and its derivatives, and phthalocyanine and its derivatives, and (ii) fullerene and its derivatives.
  • the photoelectric conversion layer 3 made of these materials may be formed by depositing a mixture of powders in advance, or by co-deposition in any ratio.
  • the materials used for the photoelectric conversion layer 3, which has a single layer structure made of three materials, include the above-mentioned combinations of (i) coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, (ii) fullerene and its derivatives, and (iii) hole transport materials.
  • the photoelectric conversion layer 3 made of these materials may be formed by depositing a mixture of powders in advance, or by co-deposition in any ratio.
  • coumarin derivatives include coumarin 6 and coumarin 30.
  • quinacridone derivatives include N,N-dimethylquinacridone.
  • phthalocyanine derivatives include boron subphthalocyanine chloride and boron subnaphthalocyanine chloride (SubNC).
  • fullerenes and their derivatives include [60]fullerene, [70]fullerene, and [6,6]-phenyl-C61-methyl butyrate ([60]PCBM).
  • the hole transport material may be a known hole transport material.
  • the hole transport material include aromatic tertiary amine compounds, naphthalene compounds, anthracene compounds, tetracene compounds, pentacene compounds, phenanthrene compounds, pyrene compounds, perylene compounds, fluorene compounds, carbazole compounds, indole compounds, pyrrole compounds, picene compounds, thiophene compounds, benzotrifuran compounds, benzotrithiophene compounds, naphthodithiophene compounds, naphthothienothiophene compounds, benzodifuran compounds, benzodithiophene compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, chrysenodithiophene compounds, benzothienobenzothiophene compounds, and indolocarbazole compounds.
  • fluorene compounds are preferred, and fluorene compounds, chrysenodithiophene compounds, benzothienobenzothiophene compounds, and indolocarbazole compounds are more preferred.
  • hole transport materials include 9,9'-(9,9'-spirobi[9H-fluorene]-2,7'-diyl)bis[9H-carbazole], 2,7-diphenyl[1]benzothieno[3,2-b][1]benzothiophene (DiPh-BTBT), benzo[1,2-b:3,4-b':5,6-b'']trifuran compounds, benzo[1,2-b:3,4-b':5,6-b'']trithiophene compounds, naphtho[1,2-b:5,6-b']dithiophene, naphtho[2,3-b]naphtho[2' ,3':4,5]thieno[2,3-d]thiophene, benzo[1,2-b:4,5-b']difuran, benzo[1,2-b:4,5-b']dithiophene, benzo[1,2-b:4,5-b']bis[1]benzo
  • the photoelectric conversion element material is not limited to being contained only in the photoelectric conversion layer.
  • the photoelectric conversion element material may be contained in a layer adjacent to the photoelectric conversion layer 3 (hole blocking layer 2 or electron blocking layer 4).
  • the electron blocking layer 4 is provided between the photoelectric conversion layer 3 and the hole transport layer 5 .
  • the electron blocking layer 4 has the role of transporting holes generated in the photoelectric conversion layer 3 from the photoelectric conversion layer 3 to the second electrode 6, and the role of blocking the movement of electrons generated in the photoelectric conversion layer 3 toward the second electrode 6. Depending on the application, it may also have the role of blocking electron injection from the second electrode 6.
  • the electron blocking layer 4 may be a single layer structure made of one or more materials, or a laminate structure made of multiple layers of the same or different compositions.
  • it may be a two-layer structure including a layer adjacent to the photoelectric conversion layer 3 made of a material specialized for electron blocking properties, and a layer adjacent to the hole transport layer 5 made of a material specialized for hole transport properties.
  • the electron blocking layer 4 preferably contains a known hole transport material.
  • known hole transport materials include the same materials as those used in the photoelectric conversion layer 3 described above.
  • a hole transport layer 5 is provided between the electron blocking layer 4 and a second electrode 6 described later.
  • the hole transport layer 5 is provided to promote hole transport from the electron blocking layer 4 to the second electrode 6.
  • the promotion of hole transport is brought about by changing the internal electric field due to the interaction of the hole transport material with the surrounding materials.
  • the hole transport layer 5 plays a role in reducing damage to an organic layer (e.g., the electron blocking layer 4) during sputtering.
  • the hole transport layer 5 may be a known material, such as naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN), etc.
  • NTCDA naphthalene-1,4,5,8-tetracarboxylic dianhydride
  • HTCN 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene
  • the hole transport layer 5 may have a single layer structure made of one or more materials, and may, for example, have the above-mentioned material and a conventionally known hole transport material. Conventionally known hole transport materials may be used, and examples of such materials include the same materials as those used in the photoelectric conversion layer 3 described above.
  • a second electrode 6 is provided on the electron blocking layer 4 .
  • Examples of materials for the second electrode 6 include sodium, sodium-potassium alloy, magnesium, lithium, a magnesium/copper mixture, a magnesium/silver mixture, a magnesium/aluminum mixture, a magnesium/indium mixture, an aluminum/aluminum oxide (Al 2 O 3 ) mixture, indium, a lithium/aluminum mixture, gold, and rare earth metals.
  • Each layer except for the first electrode 1 and the first electrode 6 described above can be formed by forming a thin film of the material of each layer (together with a material such as a binder resin and a solvent, if necessary) by a known method such as a vacuum deposition method, a spin coating method, a casting method, or an LB (Langmuir-Blodgett) method.
  • each layer thus formed there are no particular limitations on the thickness of each layer thus formed, and it can be selected appropriately depending on the situation, but it is usually in the range of 5 nm to 5 ⁇ m.
  • the first electrode 1, which is the lower electrode, and the second electrode 6, which is the upper electrode, can be formed by thinning the electrode material by a method such as vapor deposition or sputtering.
  • a pattern may be formed through a mask of the desired shape during vapor deposition or sputtering, or a pattern of the desired shape may be formed by photolithography after forming a thin film by vapor deposition or sputtering.
  • the film thickness of the first electrode 1 and the second electrode 6 is preferably 1 ⁇ m or less, and more preferably 10 nm or more and 200 nm or less.
  • An imaging element equipped with a photoelectric conversion element can be used, for example, as an imaging element in a digital camera or digital video camera, and as an imaging element built into a mobile phone, etc.
  • the photoelectric conversion element according to aspect 1 of the present invention is a photoelectric conversion element including a layer containing a material for a photoelectric conversion element,
  • the photoelectric conversion element material is represented by the following formula (1):
  • EWG represents an electron withdrawing group
  • Ar represents a fused aromatic hydrocarbon group having 16 to 40 carbon atoms
  • L represents an aromatic hydrocarbon group having 6 to 30 carbon atoms
  • n represents an integer from 1 to 8
  • k represents an integer from 0 to 2
  • p represents an integer from 1 to 8; when k is 0, p is 1;
  • the compound has two or more EWGs, the EWGs are the same or different electron-withdrawing groups,
  • Each of the Ar, L, and EWG has at least one substituent or has no substituent.
  • the photoelectric conversion element according to aspect 2 of the present invention is preferably such that in aspect 1, the EWG is selected from a cyano group, a fluorine atom, a fluoroalkyl group, and a heteroaryl group having 3 to 30 carbon atoms and including a nitrogen atom.
  • the photoelectric conversion element according to aspect 3 of the present invention is preferably the same as that according to aspect 1 or 2, in which the nitrogen atom-containing heteroaryl group having 3 to 30 carbon atoms is substituted with a group selected from a cyano group, a fluorine atom, and a fluoroalkyl group.
  • k is an integer of 0 or 1.
  • the photoelectric conversion element according to aspect 5 of the present invention is any one of aspects 1 to 4, in which k is 1 and EWG is at least one group selected from a cyano group, a fluorine group, and a fluoroalkyl group.
  • a photoelectric conversion element according to a sixth aspect of the present invention is any one of the first to fifth aspects,
  • the Ar group is preferably a fused aromatic hydrocarbon group containing four or more six-membered rings.
  • the photoelectric conversion element according to aspect 7 of the present invention is preferably such that in any one of aspects 1 to 6, the Ar is selected from a fused aromatic hydrocarbon group selected from a triphenylene group, a fluoranthene group, and a spirofluorene group, and a fused aromatic hydrocarbon group containing a triphenylene group, a fluoranthene group, or a spirofluorene group.
  • the photoelectric conversion element according to aspect 8 of the present invention is preferably any of aspects 1 to 7, in which Ar represents a fused aromatic hydrocarbon group having 20 to 40 carbon atoms, with or without the substituent.
  • the photoelectric conversion element according to a ninth aspect of the present invention is the photoelectric conversion element according to any one of the first to eighth aspects, wherein the Ar is represented by the following formula (2-1), (2-2), or (2-3):
  • R 1 to R 38 are each independently selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, a bicycloalkyl group having 1 to 20 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and a heteroaryl group having 3 to 30 carbon atoms, or Some of R 1 to R 38 form a ring by bonding two adjacent groups to each other, Here, it is preferable that R 1 to R 35 each independently have at least one substituent or have
  • the photoelectric conversion element according to aspect 10 of the present invention is preferably any one of aspects 1 to 9, in which the material for the photoelectric conversion element has a quantum calculation value of the LUMO level calculated by density functional theory (DFT) using the B3LYP functional and the 6-31G(d) basis set of -2.2 eV or less.
  • DFT density functional theory
  • the photoelectric conversion element according to aspect 11 of the present invention is preferably any of aspects 1 to 10, in which the glass transition temperature of the material for the photoelectric conversion element is 140°C or higher.
  • the layer containing the photoelectric conversion element material according to any one of aspects 1 to 11 is a hole blocking layer.
  • the photoelectric conversion element according to any one of aspects 1 to 13 of the present invention is preferably an imaging element.
  • the photoelectric conversion element material according to aspect 14 of the present invention is a photoelectric conversion element material represented by formula (1) and may be a photoelectric conversion element material for forming the layer provided in the photoelectric conversion element according to any one of aspects 1 to 13.
  • the photoelectric conversion element material according to aspect 15 of the present invention may be a photoelectric conversion element material for an imaging device.
  • the photoelectric conversion element material according to aspect 16 of the present invention may be a hole-blocking material, which is the photoelectric conversion element material according to aspect 14.
  • the photoelectric conversion element according to aspect 17 of the present invention preferably includes a layer containing fullerene between the hole blocking layer and the electrode, as in the photoelectric conversion element according to aspect 12.
  • a photoelectric conversion element is a photoelectric conversion element comprising a layer containing a material for a photoelectric conversion element,
  • the photoelectric conversion element material is a compound represented by the following formula (3):
  • X 1 to X 5 each represent a nitrogen atom or CR 55 ;
  • the number of nitrogen atoms is an integer of 0 to 3;
  • R 40 to R 55 are each independently selected from a hydrogen atom, a cyano group, a nitro group, a halogen atom, a halogenated alkyl group, an acyl group, a sulfonyl group, a phosphoryl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, a bicycloalkyl group having 1 to 20 carbon atoms, a tricycloalky
  • each of the R 55 is independently selected from a hydrogen atom, a cyano group, a halogen atom, a halogenated alkyl group, an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 1 to 20 carbon atoms.
  • any one of the R 55 is a cyano group.
  • the compound according to aspect 21 of the present invention is the compound according to any one of aspects 18 to 20, the halogen atom is a fluorine atom, It is preferable that either the aromatic hydrocarbon group having 6 to 30 carbon atoms or the heteroaryl group having 3 to 30 carbon atoms is unsubstituted or substituted with a group selected from a cyano group, a fluorine group, and a fluoroalkyl group.
  • the compound according to aspect 22 of the present invention is any of aspects 18 to 21, and the photoelectric conversion element material preferably has a quantum calculation value of the LUMO level calculated by density functional theory (DFT) using the B3LYP functional and the 6-31G(d) basis set of -2.2 eV or less.
  • DFT density functional theory
  • the glass transition temperature of the material for the photoelectric conversion element is preferably 140°C or higher.
  • the photoelectric conversion element material according to aspect 24 of the present invention preferably contains a compound according to any one of aspects 18 to 23.
  • the photoelectric conversion element material according to aspect 25 of the present invention is preferably a hole-blocking material in aspect 24.
  • the photoelectric conversion element material according to aspect 26 of the present invention preferably comprises a layer containing the photoelectric conversion element material according to aspect 24 or 25.
  • the photoelectric conversion element according to aspect 27 of the present invention may be an imaging element in aspect 26.
  • R 61 to R 76 are each independently selected from a hydrogen atom, a cyano group, a nitro group, a halogen atom, a halogenated alkyl group, an acyl group, a sulfonyl group, a phosphoryl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, a bicycloalkyl group having 1 to 20 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, and a group represented by formula (4-2), or two adjacent groups are bonded to form a ring; Any one
  • each of the R 77 's is independently selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 1 to 20 carbon atoms.
  • R 61 to R 76 are preferably selected from a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 16 carbon atoms, a heteroaryl group having 3 to 16 carbon atoms, and a group represented by formula (4-2), or two adjacent groups are bonded to form an aromatic hydrocarbon ring.
  • X10 is a nitrogen atom or C(CN)
  • X7 and X8 are C(CN) or CR77
  • X6 and X9 are CR77 .
  • the compound according to aspect 32 of the present invention is preferably any of aspects 28 to 31, in which the quantum calculation value of the LUMO level calculated by density functional theory (DFT) using the B3LYP functional and the 6-31G(d) basis set is -2.2 eV or less.
  • DFT density functional theory
  • the compound according to aspect 33 of the present invention in any of aspects 28 to 32, preferably has a glass transition temperature of 140°C or higher.
  • the photoelectric conversion element material according to aspect 34 of the present invention preferably contains a compound according to any one of aspects 28 to 33.
  • the photoelectric conversion element material according to aspect 35 of the present invention is preferably a hole-blocking material in aspect 34.
  • the photoelectric conversion element according to aspect 36 of the present invention preferably has a layer containing the material for photoelectric conversion elements according to aspect 34.
  • the photoelectric conversion element according to aspect 37 of the present invention may be an imaging element in aspect 36.
  • an imaging element 100 was fabricated as a photoelectric conversion element having a layered structure consisting of a first electrode 1, a hole blocking layer 2, a photoelectric conversion layer 3, an electron blocking layer 4, a hole transport layer 5, and a second electrode 6, and the dark current, external quantum efficiency, and responsiveness of the imaging element were evaluated.
  • ITO indium-tin oxide
  • each layer was deposited by vacuum deposition on the substrate by vacuum deposition, so that each layer was laminated.
  • each layer was prepared according to the film formation conditions in the following order.
  • the sublimation purified compound (B408) was formed into a film having a thickness of 10 nm at a rate of 0.03 nm/sec to prepare a hole blocking layer 2.
  • a film of 120 nm was formed by mixing N,N-dimethylquinacridone and C60 in a ratio of 4:1 (mass ratio) to prepare photoelectric conversion layer 3.
  • the film formation rate was 0.15 nm/sec.
  • (Fabrication of Electron Blocking Layer 4) The compound (ic-3) was deposited at a rate of 0.10 nm/sec to a thickness of 10 nm to prepare an electron blocking layer 4. Note that (ic-3) was synthesized by the method described in JP-A-2018-193371.
  • a film of the compound 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN) was formed to a thickness of 10 nm at a rate of 0.10 nm/sec to prepare a hole transport layer 5.
  • an imaging photoelectric conversion element 100 having an area of 4 mm2 was produced as shown in Figure 1.
  • the thickness of each film was measured using a stylus film thickness gauge (DEKTAK, manufactured by Bruker).
  • this element was sealed in a nitrogen atmosphere glove box with oxygen and moisture concentrations of 1 ppm or less.
  • the glass sealing cap and the film-formed substrate (element) were sealed using bisphenol F type epoxy resin (manufactured by Nagase ChemteX Corporation).
  • the current in the dark (dark current), external quantum efficiency, and response time were evaluated when a voltage of 2.6 V was applied to the image sensor fabricated as described above.
  • the dark current was measured using a Keithley Source Measure Unit 2636B.
  • the external quantum efficiency was measured using a solar cell spectral response measurement device (Soma Optical Co., Ltd.).
  • the wavelength of the irradiated light was 560 nm, and the intensity was 50 ⁇ W/ cm2 .
  • the response time was measured by irradiating a light pulse and measuring the time until the current value returned to the value before irradiation.
  • the dark current, external quantum efficiency, and response time are relative values with the result of comparative element example 1 set as the reference value (1.0).
  • the measurement results are shown in Table 1.
  • Element Examples 2 to 7 Element Comparative Examples 1 to 2 An imaging photoelectric conversion element was prepared and evaluated in the same manner as in Element Example-1, except that, instead of compound (B408), compound (B395), compound (B499), compound (B509), compound (B426), compound (B577), compound (B104), or comparative compound 1 were used, respectively. The measurement results obtained are shown in Table 1.
  • Table 1 show that forming a layer using a compound represented by formula (1) or formula (3), or formula (4-1) as a material for an image sensor or photoelectric conversion element provides superior dark current, external quantum efficiency, and response compared to forming a layer using a comparative example compound.
  • An imaging element equipped with a photoelectric conversion element can be used, for example, as an imaging element in a digital camera or digital video camera, as an imaging element built into a mobile phone, or as an image input device for a driving assistance system.

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PCT/JP2023/044249 2022-12-09 2023-12-11 光電変換素子、撮像素子、光電変換素子用材料、および化合物 Ceased WO2024122652A1 (ja)

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