Photoelectric conversion element, imaging element, material for photoelectric conversion element, and compound

Abstract

Provided are a photoelectric conversion element and an imaging element which have excellent response speed and high external quantum yield, and a material for photoelectric conversion elements which contributes to the production of these elements. An image pickup photoelectric conversion element (100) is provided with a layer containing a photoelectric conversion element material represented by formula (1), EWG represents an electron withdrawing group, L represents a C6-30 aromatic hydrocarbon group, n represents 1-8, k represents 0-2, p represents 1-8, and p is 1 when k is 0. [chemical formula 1] # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a photoelectric conversion element, an imaging element, a material for a photoelectric conversion element, and a compound. Background Art

[0002] Photoelectric conversion elements are widely used in solar cells, optical sensors, image sensors, etc., and their applications and markets are constantly expanding, and their development is being actively carried out.

[0003] For example, Patent Document 1 discloses a photoelectric conversion element containing a pyrimidine derivative in a hole blocking layer.

[0004] For example, Patent Document 2 discloses a photoelectric conversion element containing a triazine derivative in a hole blocking layer.

[0005] Prior Art Documents Patent Documents Patent Document 1: Japanese Unexamined Patent Application Publication No. 2022-17302 Patent Document 2: Korean Patent Publication No. 10-2021-053141 Summary of the Invention Technical Problem to be Solved by the Invention For example, in an imaging element as a photoelectric conversion element, an element with excellent response speed and external quantum efficiency is required.

[0006] An object of the invention according to one aspect of the present invention is to provide a photoelectric conversion element and an imaging element having excellent response speed and high external quantum yield, and a material for a photoelectric conversion element and a hole blocking material used in the photoelectric conversion element and the imaging element.

[0007] Technical Solution for Solving the Technical Problem According to one aspect of the present invention, there is provided a photoelectric conversion element including a layer containing a material for a photoelectric conversion element represented by the following formula (1).

[0008] [Chemical Formula 1] In the formula (1), Ar represents a condensed polycyclic 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 of 1 to 8; k represents an integer of 0 to 2; p represents an integer of 1 to 8; When k is 0, p is 1, In the case where there are two or more of the EWGs, the EWGs are the same or different electron-withdrawing groups. The Ar, L, and EWG each have at least one substituent or do not have the substituent.

[0009] According to another aspect of the present invention, the photoelectric conversion element related to the above aspect is an imaging element.

[0010] According to another aspect of the present invention, there is provided a photoelectric conversion element, wherein the layer containing the material for the photoelectric conversion element is a hole-blocking layer.

[0011] According to another aspect of the present invention, there is provided a material for a photoelectric conversion element, which is used to form the above layer included in the photoelectric conversion element related to the above aspect.

[0012] According to another aspect of the present invention, there is provided a material for a photoelectric conversion element, wherein the material for the photoelectric conversion element related to the above aspect is a material for a photoelectric conversion element for an imaging element.

[0013] According to another aspect of the present invention, there is provided the material for a photoelectric conversion element related to the above aspect, which is a hole-blocking material.

[0014] Further, according to another aspect of the present invention, there is provided a compound represented by the following formula (3): [Chemical formula 2] X 1 ~X 5 represents a nitrogen atom or CR 55 ; X 1 ~X 5 in which the number of the nitrogen atoms is an integer of 0 to 3; R 40 ~R 55 each independently selected from a hydrogen atom, a cyano group, a nitro group, a halogen atom, a haloalkyl 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 R 40 ~R 55 in part form a ring by bonding of two adjacent groups to each other; at least one of R 55 is selected from a cyano group, a halogen atom, or a haloalkyl group; In X 1 ~X5 All are CR 55 In the case of, the R 55 Two or more of them are selected from a cyano group, a halogen atom, and a haloalkyl group; The R 40 ~R 55 Each independently further has at least one substituent, or does not have the substituent.

[0015] In addition, according to another aspect of the present invention, a compound represented by the following formula (4-1) is provided: [Chemical formula 3] In the formula (4-1), R 61 ~R 76 Each independently is selected from a hydrogen atom, a cyano group, a nitro group, a halogen atom, a haloalkyl 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 the formula (4-2), or forms a ring by bonding of two adjacent groups; R 61 ~R 64 Any one of them is a group represented by the formula (4-2); L represents a direct bond or an aromatic hydrocarbon group having 6 to 16 carbon atoms; X 6 ~X 10 represents a nitrogen atom, C(CN), or CR 77 ; X 9 ~X 10 In, X 9 is C(CN), or X 10 is a nitrogen atom or C(CN); X 6 ~X 10 In, the number of the nitrogen atoms is 0 or 1. In the case where the number of the nitrogen atoms is 0, the number of the C(CN) is any one of 2 to 3. In the case where the number of the nitrogen atoms is 1, the number of the C(CN) is 2; R 77Each independently selected from a hydrogen atom, a nitro group, a halogen atom, a haloalkyl 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; Said R 61 ~R 77 and said L have at least one substituent or do not have said substituent.

[0016] Advantages of the Invention According to one aspect of the present invention, there can be provided a photoelectric conversion element and an imaging element having excellent response speed and high external quantum yield, and a material for a photoelectric conversion element and a hole blocking material for a photoelectric conversion element and an imaging element. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 is a schematic cross-sectional view showing the stacked structure of a photoelectric conversion element for an imaging element including a material for a photoelectric conversion element according to one aspect of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0018] Hereinafter, the material for a photoelectric conversion element contained in the layer included in the photoelectric conversion element according to one aspect of the present invention will be described in detail.

[0019] <Material for Photoelectric Conversion Element (1)> The photoelectric conversion element according to one aspect of the present invention includes a layer of a material for a photoelectric conversion element represented by the following formula (1).

[0020] [Chemical Formula 4] In the formula (1), Ar represents a condensed polycyclic 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 of 1 to 8; k represents an integer of 0 to 2; p represents an integer of 1 to 8; When k is 0, p is 1, When there are two or more of said EWGs, said EWGs are the same or different electron-withdrawing groups, Said Ar, L and EWG each have at least one substituent or do not have said substituent.

[0021] That is, in the present specification, a group other than the group represented by the following formula (1') in the material for a photoelectric conversion element represented by formula (1) is described as a "substituent".

[0022] [Chemical formula 5] The definitions of L and EWG and k and p in formula (1') are the same as those of L and EWG and k and p in formula (1).

[0023] The compound represented by the above formula (1) is an electron transport material having excellent charge, i.e., electron, transport properties and a hole blocking material having excellent opposite charge, i.e., hole, blocking properties, and can be suitably used as a material for a photoelectric conversion element.

[0024] The definitions of the respective groups in the above formula (1) and formula (1') and their preferred specific examples are as follows.

[0025] <Regarding Ar> Ar is a polycyclic aromatic hydrocarbon group formed by condensation of aromatic rings, and the polycyclic aromatic hydrocarbon group may have a substituent. The number of carbon atoms in the polycyclic aromatic hydrocarbon group of Ar is in the range of 16 to 40, preferably in the range of 20 to 40. Here, when Ar has a larger number of carbon atoms in the range of 16 to 40, high thermal stability can be imparted to the material for a photoelectric conversion element, and when Ar is made smaller, the LUMO level in the material for a photoelectric conversion element can be prevented from becoming too shallow.

[0026] Ar is preferably, for example, a polycyclic aromatic hydrocarbon group containing 4 or more 6-membered rings. By making Ar a polycyclic aromatic hydrocarbon group formed by condensation of 4 or more 6-membered rings, the Tg of the material for a photoelectric conversion element can be increased, and thus the thermal stability of the material for a photoelectric conversion element can be improved.

[0027] Hereinafter, preferred specific examples of Ar are shown, but are not limited thereto.

[0028] [Chemical formula 6] Among the above-mentioned Ar, for example, more preferably, a polycyclic aromatic hydrocarbon group selected from: a polycyclic aromatic hydrocarbon group selected from triphenylenyl (A2), fluoranthenyl (A15), spirofluorene (A21), a polycyclic aromatic hydrocarbon group containing triphenylenyl (A3) to (A14), a polycyclic aromatic hydrocarbon group containing fluoranthenyl (A16) to (A20), and a polycyclic aromatic hydrocarbon group containing spirofluorene (A22) to (A25).

[0029] Ar may have a substituent and may have, for example, structures represented by the following formulas (2-1), (2-2), and (2-3).

[0030] [Chemical formula 7] In Formula (2-1), Formula (2-2), and Formula (2-3), R 1 to R 38 are each independently preferably 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.

[0031] The aromatic hydrocarbon group having 6 to 30 carbon atoms is the same as these groups represented by L described later. In addition, the heteroaryl group having 3 to 30 carbon atoms is preferably selected from the heteroaryl groups having 3 to 30 carbon atoms containing a nitrogen atom represented by EWG described later.

[0032] In addition, a part of R 1 to R 38 may also form a ring as a substituent by bonding of two adjacent groups, and the ring may be a hydrocarbon ring. More specifically, it may also form a ring by bonding of two adjacent groups among R 1 to R 12 shown in Formula (2-1). Thus, a structure shown in Formula (2-1) can have, for example, any of the condensed polycyclic aromatic hydrocarbon groups (A4) to (A14) selected from the above. In addition, it may also form a ring by bonding of two adjacent groups among R 12 to R 22 shown in Formula (2-2). Thus, a structure shown in Formula (2-2) can have, for example, any of the condensed polycyclic aromatic hydrocarbon groups (A16) to (A20) selected from the above. In addition, it may also form a ring by bonding of two adjacent groups among R 23 to R 38 shown in Formula (2-3). Thus, a structure shown in Formula (2-3) can have, for example, any of the condensed polycyclic aromatic hydrocarbon groups (A22) to (A25) selected from the above.

[0033] A part of R 1 to R 38 in Ar shown in the above Formula (2-1), (2-2), or (2-3) is substituted with the group shown in Formula (1'), or it is sufficient that a hydrogen atom of R 1 to R 38 is substituted with the group shown in Formula (1').

[0034] In addition, the above R 1~R 35 Each may independently further have at least one substituent, or may not have the above-mentioned substituents.

[0035] <Regarding EWG> EWG represents an electron-withdrawing group. When the material for a photoelectric conversion element of formula (1) has a plurality of EWGs, these EWGs may be the same electron-withdrawing group or may be different electron-withdrawing groups.

[0036] As the electron-withdrawing group, it is preferably at least one group selected from a cyano group, a nitro group, a halogen atom, a haloalkyl group, an acyl group, a sulfonyl group, a phosphoryl group, and a heteroaryl group having 3 to 30 carbon atoms containing a nitrogen atom. The heteroaryl group having 3 to 30 carbon atoms containing a nitrogen atom may have at least one substituent or may not have the above-mentioned substituents.

[0037] As the halogen atom represented by EWG, a fluorine atom is preferred.

[0038] As the haloalkyl group represented by EWG, a haloalkyl group having 1 to 5 carbon atoms is preferred, and a haloalkyl group having 1 to 3 carbon atoms is more preferred. In addition, as the haloalkyl group, a fluorinated alkyl group is preferred, and a perfluoroalkyl group is preferred. As the fluorinated alkyl group, perfluorobutyl, perfluoropropyl, perfluoroethyl, and trifluoromethyl are preferred, and trifluoromethyl is more preferred.

[0039] Examples of the acyl group represented by EWG include an alkyl acyl group and an aryl acyl group. Preferred are an alkyl acyl group having 2 to 5 carbon atoms and an aryl acyl group having 7 to 15 carbon atoms. Examples of the alkyl acyl group include an acetyl group, a propionyl group, and a trifluoroacetyl group. Examples of the aryl acyl group include a benzoyl group, a cyanobenzoyl group, a fluorobenzoyl group, and a trifluoromethylbenzoyl group.

[0040] Examples of the sulfonyl group represented by EWG include an alkyl sulfonyl group and an aryl sulfonyl group. Preferred are an alkyl sulfonyl group having 1 to 5 carbon atoms and an aryl sulfonyl group having 6 to 15 carbon atoms. Examples of the alkyl sulfonyl group include a methyl sulfonyl group, an ethyl sulfonyl group, a n-propyl sulfonyl group, and an isopropyl sulfonyl group. Examples of the aryl sulfonyl group include a phenyl sulfonyl group, a cyanophenyl sulfonyl group, and a fluorophenyl sulfonyl group.

[0041] Examples of the phosphoryl group represented by EWG include a dialkyl phosphoryl group and a diaryl phosphoryl group. Preferred are a dialkyl phosphoryl group having 2 to 10 carbon atoms and a diaryl phosphoryl group having 12 to 30 carbon atoms. Examples of the dialkyl phosphoryl group include a dimethyl phosphoryl group, a diethyl phosphoryl group, and a dipropyl phosphoryl group. Examples of the diaryl phosphoryl group include a diphenyl phosphoryl group and a bis(fluorophenyl) phosphoryl group.

[0042] As a heteroaryl group having 3 to 30 carbon atoms containing a nitrogen atom, examples thereof include pyridyl, pyrimidinyl, pyrazinyl, triazinyl, imidazolyl, quinolinyl, isoquinolinyl, azanthryl, diazanthryl, triazanthryl, tetrazanthryl, azaphenanthrenyl, diazaphenanthrenyl, triazaphenanthrenyl, tetrazaphenanthrenyl, azapyrenyl, diazapyrenyl, triazapyrenyl, tetrazapyrenyl, azaperyleneyl, diazaperyleneyl, triazaperyleneyl, tetrazaperyleneyl, azatriphenylenyl, diazatriphenylenyl, triazatriphenylenyl, tetrazatriphenylenyl, pentazatriphenylenyl, hexazatriphenylenyl, oxazolyl, pyrrolyl, imidazolyl, triazolyl, thiadiazolyl, oxadiazolyl, benzothiazolyl, benzoxazolyl, benzothiadiazolyl and benzoxadiazolyl.

[0043] As substituents of the EWG which are substituents of the heteroaryl group having 3 to 30 carbon atoms containing a nitrogen atom, examples thereof include a deuterium atom, a cyano group, a halogen atom, a haloalkyl group, an acyl group, a nitro group, a sulfonyl group, a phosphoryl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group and a cycloalkyl group, an alkoxy group having 1 to 10 carbon atoms, a group represented by -P(=O)(Ar')2, a group represented by -OSO2Ar', a group represented by -S(=O)Ar', a group represented by -B(Ar')2, a group represented by -B(OAr')2, a group represented by -Si(Ar')3, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and a heteroaryl group having 3 to 30 carbon atoms (Ar' represents an aryl group). Among these substituents of the EWG, a cyano group, a halogen atom, a haloalkyl group, an acyl group, a sulfonyl group, a phosphoryl group, an aromatic hydrocarbon group having 6 to 30 carbon atoms and a heteroaryl group having 3 to 30 carbon atoms are preferred, a cyano group, a halogen atom, a haloalkyl group and a heteroaryl group having 3 to 30 carbon atoms are more preferred, a cyano group, a fluorine atom and a fluoroalkyl group are further preferred, and a cyano group, a fluorine atom and a trifluoromethyl group are particularly preferred. The haloalkyl group, the acyl group, the sulfonyl group, the phosphoryl group and the heteroaryl group having 3 to 30 carbon atoms in the substituents of the EWG are the same as the groups described in these groups represented by the EWG. The aromatic hydrocarbon group having 6 to 30 carbon atoms is the same as the groups represented by L and the groups described later.

[0044] As the EWG, a cyano group, a fluorine atom, a fluoroalkyl group and a heteroaryl group having 3 to 30 carbon atoms containing a nitrogen atom are preferred, and a cyano group, a fluorine atom, a fluoroalkyl group, and a heteroaryl group having 3 to 30 carbon atoms containing a nitrogen atom having at least one group selected from a cyano group, a fluorine atom and a fluoroalkyl group as a substituent of the EWG are more preferred.

[0045] <Regarding L> 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.

[0046] As the aromatic hydrocarbon group having 6 to 30 carbon atoms, for example, phenyl, naphthyl, phenanthryl, anthryl, fluorenyl, dimethylfluorenyl, spirofluorenyl, pyrenyl, fluoranthenyl, triphenylenyl, tetraphenylenyl, chrysenyl and the like can be mentioned. Among them, phenyl and naphthyl are preferred. The substituents of the aromatic hydrocarbon group having 6 to 30 carbon atoms are the same as the groups described in the substituents of the EWG such as the heteroaryl group having 3 to 30 carbon atoms containing a nitrogen atom, and thus the description is omitted.

[0047] <Regarding n, k and p> n preferably represents an integer of 1 to 8. By optimizing the material for the photoelectric conversion element shown in formula (1) within the range of n being 1 to 8, the decrease in Tg of the material for the photoelectric conversion element can be suppressed, the LUMO level of the material for the photoelectric conversion element can be deepened, and the response speed in the photoelectric conversion element can be increased.

[0048] k represents an integer of 0 to 2, preferably an integer of 0 or 1. When k is 1, the EWG is more preferably a cyano group, a fluorine atom, or a fluoroalkyl group, whereby the decrease in Tg of the material for the photoelectric conversion element can be suppressed, the LUMO level of the material for the photoelectric conversion element can be deepened, and the response speed in the photoelectric conversion element can be increased.

[0049] p represents an integer of 1 to 8. When k is 0, p can be 1.

[0050] The material for the photoelectric conversion element shown in the above formula (1) increases the glass transition temperature Tg through the above Ar structure as described later, thereby preventing the decrease in the external quantum efficiency and the dark current in the photoelectric conversion element having a layer formed of the material for the photoelectric conversion element caused by heating. In addition, the material for the photoelectric conversion element shown in the above formula (1) has improved the response speed to light by having the above EWG. Therefore, it can be suitably used for a photoelectric conversion element that requires both response speed and external quantum efficiency.

[0051] The material for the photoelectric conversion element included in one embodiment of the present invention is not limited to the above embodiment. Ar shown in formula (1) is a condensed polycyclic aromatic hydrocarbon group shown in (A12), (A20), (A21), (A-22) to (A-25), and is preferred from the viewpoint of further increasing the Tg of the compound having the condensed polycyclic aromatic hydrocarbon group. More preferably, the compound according to one embodiment of the present invention is a compound having a condensed polycyclic aromatic hydrocarbon group, and can be a compound selected from the compounds shown in the following formula (3), and the compounds shown in the following formula (4-1) and formula (4-2).

[0052] <Compound (material for photoelectric conversion element (2))> The material for a photoelectric conversion element included in one aspect of the present invention is not limited to the above aspect. For example, the compound represented by the following formula (3) is also within the scope of the present invention according to one aspect.

[0053] [Chemical Formula 8] In formula (3), X 1 ~X 5 represents a nitrogen atom or CR 55 ; X 1 ~X 5 Among them, the number of the nitrogen atoms is an integer of 0 to 3; R 40 ~R 55 each independently selected from a hydrogen atom, a cyano group, a nitro group, a halogen atom, a haloalkyl 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 R 40 ~R 55 a part of them form a ring by bonding of two adjacent groups to each other; R 55 at least one of them is selected from a cyano group, a halogen atom or a haloalkyl group; when X 1 ~X 5 are all CR 55 in the case of, two or more of the R 55 are selected from a cyano group, a halogen atom and a haloalkyl group; the R 40 ~R 55 each independently further has at least one substituent, or does not have the substituent.

[0054] The compound represented by formula (3) has a condensed polycyclic aromatic hydrocarbon group, and the condensed polycyclic aromatic hydrocarbon group can be (A12) exemplified as Ar represented by formula (1).

[0055] <Regarding X 1 ~X 5 > X 1 ~X 5 represents a nitrogen atom or CR 55 , and among X 1 ~X 5 the number of nitrogen atoms is an integer of 0 to 3.

[0056] Preferably X 1 ~X 5 All are CR 55 , or X 2 ~X 4 Any one of them is a nitrogen atom.

[0057] <Regarding R 40 ~R 55 > R 40 ~R 55 The substituents represented by and the preferred specific examples are the same as those of the substituents shown in formula (1). In addition, R 40 ~R 55 The preferred specific examples of the further substituents possessed are the same as those of the substituents of EWG shown in formula (1).

[0058] <Regarding R 55 > R 55 may be selected from a hydrogen atom, a cyano group, a nitro group, a halogen atom, a haloalkyl 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.

[0059] R 55 Any one of them is a cyano group, a halogen atom or a haloalkyl group, and adjacent R 55 may also bond to each other to form a ring.

[0060] In addition, in the compound shown in formula (3), the above-mentioned halogen atom is a fluorine atom, and the above-mentioned aromatic hydrocarbon group having 6 to 30 carbon atoms may be substituted with a group selected from a cyano group, a fluorine group and a fluoroalkyl group, or may be unsubstituted.

[0061] <Compound (Material for Photoelectric Conversion Element (3))> The material for a photoelectric conversion element included in one embodiment of the present invention is not limited to the above embodiment. For example, the compound represented by the following formula (4-1) described below is also within the scope of the present invention according to one embodiment.

[0062] [Chemical Formula 9] In the formula (4-1), R 61 ~R 76Each independently selected from a hydrogen atom, a cyano group, a nitro group, a halogen atom, a haloalkyl 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 the formula (4-2), or a ring is formed by bonding two adjacent groups to each other; R 61 ~R 64 Any one of them is a group represented by the formula (4-2); L represents a direct bond or an aromatic hydrocarbon group having 6 to 16 carbon atoms; X 6 ~X 10 represents a nitrogen atom, C(CN), or CR 77 ; X 9 and X 10 Among them, X 9 is C(CN), or X 10 is a nitrogen atom or C(CN); X 6 ~X 10 Among them, the number of the nitrogen atoms is 0 or 1. When the number of the nitrogen atoms is 0, the number of the C(CN) is any one of 2 to 3. When the number of the nitrogen atoms is 1, the number of the C(CN) is 2; R 77 Each independently selected from a hydrogen atom, a nitro group, a halogen atom, a haloalkyl 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.

[0063] <Regarding R 61 ~R 76 > In the formula (4-1), R 61 ~R 76 Except for the case of being selected from the group represented by the formula (4-2), it can be selected from the same groups as R 40 ~R 55 in the compound of the above formula (3). Among them, in the formula (4-1), R 61 ~R 76It can be selected from (a) a cyano group, a nitro group, a halogen atom, a haloalkyl group, an acyl group, a sulfonyl group, a phosphoryl group, a heteroaryl group having 3 to 30 carbon atoms, and a group represented by the formula (4-2), or can be selected from (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 group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and can form a ring by bonding of two adjacent groups to each other.

[0064] In formula (4-1), from the viewpoint of deepening the LUMO energy level of the compound, R 61 ~R 76 is preferably selected from the above (a), more preferably can be selected from the groups represented by the EWG shown in the above formula (1), and is selected from a cyano group, a heteroaryl group having 3 to 16 carbon atoms, and a group represented by the formula (4-2). Among them, when R 61 ~R 76 is selected from a heteroaryl group having 3 to 16 carbon atoms, the heteroaryl group may or may not contain a carbazolyl group.

[0065] In addition, from the viewpoint of increasing the glass transition temperature Tg, R 61 ~R 76 is preferably selected from the above (b), 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.

[0066] In formula (4-1), when R 61 ~R 76 forms a ring by bonding of two adjacent groups to each other, the ring can form a part of the condensed polycyclic aromatic hydrocarbon group exemplified as Ar in formula (1). That is, the compound represented by formula (4-1) has a condensed polycyclic aromatic hydrocarbon group, and the condensed polycyclic aromatic hydrocarbon group can be (A21) exemplified as Ar represented by formula (1). When R 61 ~R 76 forms a ring, it can be the condensed polycyclic aromatic hydrocarbon group exemplified by (A-22) to (A-25). In formula (4-1), from the viewpoint of further increasing the Tg of the compound, it is preferred that R 61 ~R 76 forms a ring.

[0067] In the group represented by formula (4-2), L is selected from aromatic hydrocarbon groups having 6 to 16 carbon atoms in the specific examples of L represented by formula (1), and can be phenyl, naphthyl, phenanthryl, anthryl, fluorenyl, dimethylfluorenyl, etc. The aromatic hydrocarbon group having 6 to 16 carbon atoms may have a substituent. Here, as the substituent of the aromatic hydrocarbon group having 6 to 16 carbon atoms, it may be selected from the substituents described as the substituents of EWG such as heteroaryl groups having 3 to 30 carbon atoms containing a nitrogen atom. Of course, the case where L represented by formula (4-2) is a direct bond corresponds to the case where k in formula (1) is 0.

[0068] In the group represented by formula (4-2), the ring structure having X 6 ~X 10 is selected from phenyl substituted with 2 to 3 cyano groups and pyridyl substituted with 2 cyano groups, and has R 77 as a group other than the cyano group, which is the same as the EWG represented by formula (1) and is an electron-withdrawing group. The ring structure having X 6 ~X 10 is more preferably that 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 .

[0069] Each R 77 is independently selected from a hydrogen atom, a nitro group, a halogen atom, a haloalkyl 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 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.

[0070] In addition, the substituents represented by R 61 ~R 77 have at least one substituent or do not have the substituent. In the case of having a substituent, the substituent may be selected from the substituents described as the substituents represented by EWG such as heteroaryl groups having 3 to 30 carbon atoms containing a nitrogen atom.

[0071] <Preferred Specific Examples of Materials for Photoelectric Conversion Elements> Hereinafter, preferred specific examples of the material for a photoelectric conversion element represented by any one of formula (1) are shown, but are not limited thereto.

[0072] [Chemical Formula 10-1] [Chemical Formula 10-2] [Chemical Formula 10-3] [Chemical Formula 10-4] [Chemical Formula 10-5] [Chemical Formula 10-6] [Chemical Formula 10-7] [Chemical Formula 10-8] [Chemical Formula 10-9] [Chemical Formula 10-10] [Chemical Formula 10-11] [Chemical Formula 10-12] [Chemical Formula 10-13] [Chemical Formula 10-14] [Chemical Formula 10-15] [Chemical Formula 10-16] [Chemical Formula 10-17] [Chemical Formula 10-18] [Chemical Formula 10-19] [Chemical Formula 10-20] [Chemical Formula 10-21] [Chemical Formula 10-22] [Chemical Formula 10-23] [Chemical formula 10-24] [Chemical formula 10-25] [Chemical formula 10-26] [Chemical formula 10-27] [Chemical formula 10-28] [Chemical formula 10-29] Among the above (B001) to (B685), specific preferred examples of the compound represented by formula (3) include (B395) to (B397), (B400) to (B425), but are not limited thereto.

[0073] The compounds represented by formula (3) and formula (4-1) can be suitably used, for example, as materials for photoelectric conversion elements.

[0074] <Materials for photoelectric conversion elements, hole blocking materials for photoelectric conversion elements> Hereinafter, the use of the material for a photoelectric conversion element according to one embodiment of the present invention will be described. As described above, by taking into account both the response speed and the external quantum efficiency, the material for a photoelectric conversion element can be suitably used for the photoelectric conversion layer and the hole blocking layer provided in the photoelectric conversion element.

[0075] In addition, since the material for a photoelectric conversion element has a high Tg, it is possible to prevent changes in the film state such as crystallization caused by annealing during the manufacture of the photoelectric conversion element. Thereby, a decrease in the external quantum efficiency and the dark current in the photoelectric conversion element formed of the material for a photoelectric conversion element is prevented. Therefore, the material for a photoelectric conversion element can be suitably used as a material for a photoelectric conversion element and a hole blocking material of an imaging element that require resistance to annealing after formation of the photoelectric conversion layer.

[0076] The material for photoelectric conversion can be used, for example, as a material for the photoelectric conversion layer in an imaging element or a hole blocking material, which is a material for the hole blocking layer in the imaging element.

[0077] One aspect of the present invention relates to a material for a photoelectric conversion element including a skeleton represented by the above formula (1), formula (3), or formula (4-1). The material for a photoelectric conversion element and the hole blocking material included in the layer of the imaging element, which include the skeleton represented by formula (1), formula (3), or formula (4-1), contribute to the production of a material for a photoelectric conversion element for an imaging element having excellent response speed and external quantum efficiency characteristics.

[0078] <Regarding the LUMO level> In order to improve the dark current, external quantum efficiency, and response speed of the material for a photoelectric conversion element, it may be necessary to enable the charges generated in the photoelectric conversion layer to move quickly. For the quick movement of charges, it is preferable that the LUMO levels of the n-type semiconductor material in the photoelectric conversion layer and the material used in the hole blocking layer are close. For example, when fullerene (C60) is used in the photoelectric conversion layer, the LUMO level of the hole blocking layer, based on the quantum calculation value obtained by the density functional theory (DFT) described below, is preferably -2.2 eV or less, more preferably -2.3 eV or less. In addition, the LUMO level of the hole blocking layer is not limited as long as it is -5.0 eV or more, preferably -4.0 eV or more.

[0079] The LUMO levels of the materials for a photoelectric conversion element represented by formula (1) and formula (3) are not particularly limited. From the viewpoint of suitability for the imaging element, the LUMO level is preferably -2.2 eV or less, more preferably -2.3 eV or less.

[0080] In the photoelectric conversion element according to one aspect of the present invention, the above LUMO level of the material for a photoelectric conversion element is a value calculated by quantum chemical calculation. The optimization of the molecular structure and the calculation of the LUMO level can be obtained by the density functional theory (DFT) under the calculation conditions based on the B3LYP functional and the 6-31G(d) basis function using the Gaussian program.

[0081] <Regarding the glass transition temperature> The material for a photoelectric conversion element used in the formation of the layer of the imaging element according to one aspect of the present invention is a material for a photoelectric conversion element represented by formula (1) or formula (3). The glass transition temperatures of the materials for a photoelectric conversion element represented by these formula (1) and formula (3) are not particularly limited. From the viewpoint of suitability for the imaging element, that is, the photoelectric conversion element for the imaging element, the glass transition temperature is preferably 140°C or higher, more preferably 150°C or higher. It should be noted that this glass transition temperature is a value obtained by differential scanning calorimetry.

[0082] The differential scanning calorimeter and test conditions are as follows. Under the conditions of differential scanning calorimeter model: Hitachi High-Technologies Corporation DSC702; operating conditions: heating rate: 10 °C / min, temperature range: 40 °C to 380 °C, the glass transition temperature is obtained from the peaks during two scans.

[0083] <Regarding amorphousness> As the material for the photoelectric conversion element of the imaging element according to one embodiment of the present invention or the materials for the photoelectric conversion element represented by Formula (1) and Formula (3), it is preferable that an amorphous layer is formed from the vapor deposition film of this material. If the vapor deposition film is a crystalline layer, the interface with the adjacent layer is uneven, and thus it becomes a cause of element defects.

[0084] The method for confirming whether the vapor deposition film is an amorphous layer is not particularly limited, and it can be confirmed by the following: visually judging the presence or absence of crystallization, or not observing sharp diffraction peaks by XRD measurement of the vapor deposition film, etc.

[0085] <Imaging element> The photoelectric conversion element according to one embodiment of the present invention is preferably an imaging element, which includes a layer containing the material for the photoelectric conversion element according to one embodiment of the present invention.

[0086] The structure of the imaging element is not particularly limited, and for example, the structures of (i) to (vi) shown below can be cited.

[0087] (i) First electrode / Photoelectric conversion layer / Second electrode (ii) First electrode / Hole blocking layer / Photoelectric conversion layer / Second electrode (iii) First electrode / Photoelectric conversion layer / Electron blocking layer / Second electrode (iv) First electrode / Hole blocking layer / Photoelectric conversion layer / Electron blocking layer / Second electrode (v) First electrode / Hole blocking layer / Photoelectric conversion layer / Electron blocking layer / Hole transport layer / Second electrode (vi) First electrode / Electron transport layer / Hole blocking layer / Photoelectric conversion layer / Electron blocking layer / Hole transport layer / Second electrode Hereinafter, taking the structure of (v) above as an example, refer to Figure 1 The imaging element according to one embodiment of the present invention will be described in more detail. Figure 1 It is a schematic cross-sectional view showing an example of the layer structure of an imaging element including a layer containing the material for the photoelectric conversion element according to one embodiment of the present invention.

[0088] The imaging element 100 sequentially includes 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. Among them, some of these layers may be omitted, and conversely, other layers may be added. It should be noted that among the above-mentioned 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.

[0089] Specifically, Figure 1 The imaging element 100 shown can be a photoelectric conversion element for imaging. Light enters the imaging element 100 from below the transparent first electrode 1, and is received by the photoelectric conversion layer 3 as a light-receiving layer. The incident direction of the light is not particularly limited, and the second electrode 6 can also be made transparent to allow light to enter from the second electrode 6.

[0090] In the imaging element 100, due to the internal electric field generated by the concentration difference of the carriers constituting each layer and the work function difference between the first electrode 1 and the second electrode 6, among the charges (holes and electrons) generated by the light reception of the photoelectric conversion layer 3, electrons move to the first electrode 1, and holes move to the second electrode 6. In addition, 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 is used as an electron collection electrode, and the second electrode 6 is used as a hole collection electrode.

[0091] It should be noted that each layer can also be replaced with a layer having other names or functions as needed. As a layer having other names or functions, for example, as other names for the hole transport layer, a hole injection layer, a work function adjustment layer, a hole transport promotion layer, etc. can be cited.

[0092] It should be noted that in Figure 1 the substrate provided below the first electrode 1 is omitted. The substrate here is not particularly limited, and for example, a glass plate, a quartz plate, a plastic plate, etc. can be cited. In addition, in the case of a structure in which light enters from the substrate side, the substrate is transparent with respect to the wavelength of the light. It should be noted that the substrate can also be provided on the second electrode 6 side. Hereinafter, the above-mentioned layers will be described.

[0093] Hereinafter, the above-mentioned layers will be described.

[0094] [Layers containing materials for photoelectric conversion elements] An imaging element as a mode of the photoelectric conversion element may contain the material for the photoelectric conversion element shown in the above formula (1) or (3), or formula (4-1) in one or more layers selected from the photoelectric conversion layer and the layer between the photoelectric conversion layer and the second electrode. In Figure 1In the illustrated structural example, the imaging element 100 contains a material for a photoelectric conversion element in at least one of the hole blocking layer 2 and the photoelectric conversion layer 3. The imaging element according to one aspect of the present invention preferably contains a material for a photoelectric conversion element in the hole blocking layer 2. Thereby, there is an effect of controlling the reverse movement of holes while allowing required charges to move quickly.

[0095] It should be noted that the material for a photoelectric conversion element represented by the above formula (1) or (3), or formula (4-1) may be included in a plurality of layers included in the photoelectric conversion element. When an electron transport layer is provided, the electron transport layer may contain the material for a photoelectric conversion element.

[0096] Hereinafter, the imaging photoelectric conversion element 100 in which the hole blocking layer 2 contains a material for a photoelectric conversion element will be described.

[0097] [First electrode 1] The first electrode 1 is provided on the substrate.

[0098] In the case of an imaging element having a structure in which light passes through the first electrode and is incident on the photoelectric conversion layer 3, the first electrode 1 may be formed of a transparent material that allows light to pass through or substantially pass through.

[0099] The transparent material used for the lower electrode of the first electrode 1 is not particularly limited. For example, indium-tin oxide (ITO; Indium Tin Oxide), indium-zinc oxide (IZO; Indium Zinc Oxide), tin oxide, aluminum-doped tin oxide, magnesium-indium oxide, nickel-tungsten oxide, other metal oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, and metal sulfides such as zinc sulfide can be cited.

[0100] It should be noted that in the case where the imaging element 100 has a structure in which light is incident on the photoelectric conversion layer 3 only from the side of the second electrode 6, the light transmission characteristics of the first electrode 1 are not important. Therefore, as an example of the material used for the first electrode 1 in this case, gold, iridium, molybdenum, palladium, platinum, etc. can be cited.

[0101] [Hole blocking layer 2] The hole blocking layer 2 is provided between the first electrode 1 and the photoelectric conversion layer 3 which will be described later as a light-receiving layer.

[0102] The hole blocking layer 2 has a function of transporting electrons generated in the photoelectric conversion layer 3 to the first electrode 1, and a function of blocking the movement of holes from the photoelectric conversion layer 3 to the first electrode 1 as an electron transport destination. In addition, depending on the use, it sometimes has a function of blocking the injection of holes from the first electrode 1.

[0103] The hole blocking layer 2 may further contain a conventionally known hole blocking material (electron transport material) in addition to the materials for the photoelectric conversion element represented by the above formulas (1) and (3), or formula (4-1). Examples of the conventionally known hole blocking material (electron transport material) include manganese bis(8-hydroxyquinoline), aluminum tris(8-hydroxyquinoline), aluminum tris(2-methyl-8-hydroxyquinoline), BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis(2-methyl-8-hydroxyquinoline)-4-(phenylphenol)aluminum), 4,6-bis(3,5-di(pyridin-4-yl)phenyl)-2-methylpyrimidine, N,N'-diphenyl-1,4,5,8-naphthalenetetracarboxylic diimide, and N,N'-bis(4-pyridyl)-1,4,5,8-naphthalenetetracarboxylic diimide, etc.

[0104] The hole blocking layer 2 may be a single-layer structure containing one or more than two materials, or a multilayer stacked structure containing the same composition or different compositions.

[0105] [Photoelectric conversion layer 3] A photoelectric conversion layer 3 serving as a light-receiving layer is provided between the hole blocking layer 2 and the electron blocking layer 4 described later. As the material for the photoelectric conversion layer 3, materials having a photoelectric conversion function can be cited.

[0106] The photoelectric conversion layer 3 may be a single-layer structure containing one or more than two materials, or a multilayer stacked structure containing the same composition or different compositions. Among them, in order to improve the photoelectric conversion efficiency, the photoelectric conversion layer 3 preferably contains a layer containing at least two materials (organic components).

[0107] Examples of the material used in the photoelectric conversion layer 3 having a single-layer structure containing one material include (i) coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, etc.

[0108] Examples of the material used in the photoelectric conversion layer 3 having a single-layer structure containing two materials include the combination of the above (i) coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives and (ii) fullerene and its derivatives. The photoelectric conversion layer 3 containing these materials can be formed by evaporation in a state of pre-mixed powder, or can be formed by co-evaporation in any proportion.

[0109] As the materials used in the single-layer structure including three materials, i.e., the photoelectric conversion layer 3, the combinations of the above-mentioned (i) coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, (ii) fullerene and its derivatives, and (iii) hole transport materials can be cited. The production of the photoelectric conversion layer 3 containing these materials can be formed by evaporation coating in a state of pre-mixing powders, or can be formed by co-evaporation coating at an arbitrary ratio.

[0110] (i) As specific examples of coumarin derivatives, coumarin 6 and coumarin 30 can be cited. As specific examples of quinacridone derivatives, N,N-dimethylquinacridone can be cited. As specific examples of phthalocyanine derivatives, boron subphthalocyanine chloride and boron subnaphthalocyanine chloride (Sub NC) can be cited.

[0111] As specific examples of (ii) fullerene and its derivatives,

[60] fullerene,

[70] fullerene, and [6,6]-phenyl-C61-butyric acid methyl ester (

[60] PCBM) can be cited.

[0112] (iii) The hole transport material can be a known hole transport material. As the hole transport material, for example, 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, naphthalenedithiophene compounds, naphthothiophenothiophene compounds, benzodifuran compounds, benzodithiophene compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, chrysenedithiophene compounds, benzothiophenobenzothiophene compounds, indolocarbazole compounds, etc. can be cited. Among them, fluorene compounds, naphthalenedithiophene compounds, naphthothiophenothiophene compounds, benzodifuran compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, chrysenedithiophene compounds, benzothiophenobenzothiophene compounds, indolocarbazole compounds, etc. are preferred, and fluorene compounds, chrysenedithiophene compounds, benzothiophenobenzothiophene compounds, indolocarbazole compounds are more preferred.

[0113] As specific examples of the hole transport material, 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]benzothiophene, naphtho[1,2-b:5,6-b']bis[1]benzothiophene, chryseno[1,2-b:8,7-b']dithiophene, [1]benzothieno[3,2-b][1]benzothiophene, the compounds (ic-1), (ic-2), and (ic-3) shown below, etc. can be cited.

[0114] [Chemical Formula 11] In addition, the material for the photoelectric conversion element is not limited to being contained only in the photoelectric conversion layer. For example, the material for the photoelectric conversion element can be contained in a layer (hole blocking layer 2 or electron blocking layer 4) adjacent to the photoelectric conversion layer 3.

[0115] [Electron blocking layer 4] An electron blocking layer 4 is provided between the photoelectric conversion layer 3 and the hole transport layer 5.

[0116] The electron blocking layer 4 has the function of transporting the holes generated in the photoelectric conversion layer 3 from the photoelectric conversion layer 3 to the second electrode 6, and the function of blocking the electrons generated in the photoelectric conversion layer 3 from moving toward the second electrode 6 side. In addition, depending on the use, it sometimes also has the function of blocking the electron injection from the second electrode 6.

[0117] The electron blocking layer 4 can be a single-layer structure containing one or two or more materials, or a laminated structure containing multiple layers of the same composition or different compositions. For example, it can be a two-layer structure containing the following layers: a layer adjacent to the photoelectric conversion layer 3 containing a material specifically for electron blocking property, and a layer adjacent to the hole transport layer 5 containing a material specifically for hole transport property.

[0118] The electron blocking layer 4 preferably contains a known hole transport material. As the known hole transport material, the same materials as those used in the above photoelectric conversion layer 3 can be cited.

[0119] [Hole transport layer 5] A hole transport layer 5 is provided between the electron blocking layer 4 and the second electrode 6 described later. The hole transport layer 5 is provided to facilitate the hole transport from the electron blocking layer 4 to the second electrode 6. The facilitation of hole transport is brought about by changing the internal electric field through the interaction between the hole transport material and the surrounding materials. In addition, when the second electrode 6 is formed by a sputtering method, the hole transport layer 5 has the effect of reducing the damage to the organic layer (such as the electron blocking layer 4) during sputtering.

[0120] The hole transport layer 5 can be a known material, for example, it can be naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN), etc.

[0121] The hole transport layer 5 can be a single-layer structure containing one or more than two materials. For example, it can have the above materials and the conventionally known hole transport materials. Examples of the conventionally known hole transport materials include the same materials as those used in the above-mentioned photo-electric conversion layer 3.

[0122] [Second Electrode 6] The second electrode 6 is provided on the electron blocking layer 4.

[0123] As the material of the second electrode 6, examples include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al2O3) mixture, indium, lithium / aluminum mixture, gold, rare earth metals, etc.

[0124] [Formation Methods of Each Layer] For the layers other than the first electrode 1 and the first electrode 6 described above, they can be formed by the following methods. For example, the materials of each layer (together with materials such as binder resin and solvents as required) are made into thin films by known methods such as vacuum evaporation method, spin coating method, casting method, LB (Langmuir-Blodgett method), etc.

[0125] There is no particular limitation on the film thickness of each layer formed in this way, and it can be appropriately selected according to the situation. Usually, it is in the range of 5 nm or more and 5 μ m or less.

[0126] The first electrode 1 as the lower electrode and the second electrode 6 as the upper electrode can be formed by making the electrode materials into thin films by using methods such as evaporation and sputtering. Patterns can be formed by using a mask with a desired shape during evaporation and sputtering, or patterns with a desired shape can be formed by photolithography after forming a thin film by evaporation, sputtering, etc.

[0127] The film thickness of the first electrode 1 and the second electrode 6 is preferably 1μ less than m, more preferably 10 nm or more and 200 nm or less.

[0128] An imaging element including the photoelectric conversion element according to one embodiment of the present invention can be applied to, for example, imaging elements of digital cameras, digital video cameras, and imaging elements incorporated in mobile phones and the like.

[0129] [Summary] The photoelectric conversion element according to Embodiment 1 of the present invention includes a layer containing a material for a photoelectric conversion element. The material for the photoelectric conversion element is represented by the following formula (1): [Chemical formula 12] In the formula (1), EWG represents an electron-withdrawing group; Ar represents a condensed polycyclic 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 of 1 to 8; k represents an integer of 0 to 2; p represents an integer of 1 to 8; When k is 0, p is 1. When there are two or more of the EWGs, the EWGs are the same or different electron-withdrawing groups. Each of the Ar, L, and EWG may have at least one substituent or may not have the substituent.

[0130] In the photoelectric conversion element according to Embodiment 2 of the present invention, in Embodiment 1, the EWG is preferably selected from a cyano group, a fluorine atom, a fluoroalkyl group, and a heteroaryl group having 3 to 30 carbon atoms containing a nitrogen atom.

[0131] In the photoelectric conversion element according to Embodiment 3 of the present invention, in Embodiment 1 or 2 above, the heteroaryl group having 3 to 30 carbon atoms containing a nitrogen atom is preferably substituted with a group selected from a cyano group, a fluorine atom, and a fluoroalkyl group.

[0132] In the photoelectric conversion element according to Embodiment 4 of the present invention, in any one of Embodiments 1 to 3 above, k is preferably an integer of 0 or 1.

[0133] In the photoelectric conversion element according to Embodiment 5 of the present invention, in any one of Embodiments 1 to 4 above, preferably, k is 1, and the EWG is at least one group selected from a cyano group, a fluorine group, and a fluoroalkyl group.

[0134] In the photoelectric conversion element according to Mode 6 of the present invention, in any one of Modes 1 to 5 described above, Ar preferably represents a condensed polycyclic aromatic hydrocarbon group containing 4 or more six-membered rings.

[0135] In the photoelectric conversion element according to Mode 7 of the present invention, in any one of Modes 1 to 6 described above, Ar is preferably selected from: condensed polycyclic aromatic hydrocarbon groups selected from triphenylenyl, fluoranthenyl, and spirofluorene groups, and condensed polycyclic aromatic hydrocarbon groups containing triphenylenyl, fluoranthenyl, and spirofluorene groups.

[0136] In the photoelectric conversion element according to Mode 8 of the present invention, in any one of Modes 1 to 7 described above, Ar preferably represents a condensed polycyclic aromatic hydrocarbon group having 20 to 40 carbon atoms with or without the substituent.

[0137] In the photoelectric conversion element according to Mode 9 of the present invention, in any one of Modes 1 to 8 described above, Ar is preferably represented by the following formulas (2-1), (2-2), and (2-3): [Chemical Formula 13] In the above formulas (2-1), (2-2), and (2-3), R 1 ~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, R 1 ~R 38 form a ring by bonding of a part of them through two adjacent groups, wherein, the R 1 ~R 35 each independently has at least one substituent or does not have the substituent.

[0138] In the photoelectric conversion element according to Mode 10 of the present invention, in any one of Modes 1 to 9 described above, the quantum calculation value of the LUMO energy level of the material for the photoelectric conversion element calculated by using the density functional theory (DFT) with the B3LYP functional and the 6-31G(d) basis function is preferably -2.2 eV or less.

[0139] In the photoelectric conversion element according to Mode 11 of the present invention, in any one of Modes 1 to 10 described above, the glass transition temperature of the material for the photoelectric conversion element is preferably 140 °C or higher.

[0140] In Mode 12 of the present invention, the layer containing the material for the photoelectric conversion element according to any one of Modes 1 to 11 is preferably a hole blocking layer.

[0141] The photoelectric conversion element according to any one of Modes 1 to 13 of the present invention is preferably an imaging element.

[0142] The material for the photoelectric conversion element according to Mode 14 of the present invention is the material for the photoelectric conversion element represented by the above formula (1), and can be a material for the photoelectric conversion element for forming the layer included in the photoelectric conversion element according to any one of Modes 1 to 13.

[0143] The material for the photoelectric conversion element according to Mode 15 of the present invention can be a material for the photoelectric conversion element for an imaging element.

[0144] The material for the photoelectric conversion element according to Mode 16 of the present invention, the material for the photoelectric conversion element described in Mode 14 above, can be a hole blocking material.

[0145] The photoelectric conversion element according to Mode 17 of the present invention preferably has a layer containing fullerene between the hole blocking layer included in the photoelectric conversion element according to Mode 12 and the electrode.

[0146] The photoelectric conversion element according to Mode 18 of the present invention has a layer containing a material for the photoelectric conversion element. The material for the photoelectric conversion element is a compound represented by the following formula (3): [Chemical Formula 14] In the above formula (3), X 1 ~X 5 represents a nitrogen atom or CR 55 ; X 1 ~X 5 Among them, the number of the nitrogen atoms is an integer from 0 to 3; R 40 ~R 55 are each independently selected from a hydrogen atom, a cyano group, a nitro group, a halogen atom, a haloalkyl 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 R 40 ~R 55 part of them form a ring by bonding of two adjacent groups to each other; R 55 At least one of them is selected from a cyano group, a halogen atom or a haloalkyl group; In the case of X 1 ~X 5 All are CR 55 In this case, two or more of the said R 55 are selected from a cyano group, a halogen atom and a haloalkyl group; The said R 40 ~R 55 Each independently further has at least one substituent or does not have the said substituent.

[0147] For the compound according to Mode 19 of the present invention, in the above Mode 18, the said R 55 Each independently is preferably selected from a hydrogen atom, a cyano group, a halogen atom, a haloalkyl group, an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 1 to 20 carbon atoms.

[0148] For the compound according to Mode 20 of the present invention, in the above Scheme 18 or 19, any one of the said R 55 is preferably a cyano group.

[0149] For the compound according to Mode 21 of the present invention, in any one of the above Modes 18 to 20, preferably, the said halogen atom is a fluorine atom, any one of the said aromatic hydrocarbon group having 6 to 30 carbon atoms and the heteroaryl group having 3 to 30 carbon atoms is substituted or unsubstituted by a group selected from a cyano group, a fluorine group and a fluoroalkyl group.

[0150] For the compound according to Mode 22 of the present invention, in any one of the above Modes 18 to 21, the quantum calculation value of the LUMO energy level of the material for a photoelectric conversion element calculated by density functional theory (DFT) using the B3LYP functional and the 6-31G(d) basis function is preferably -2.2 eV or less.

[0151] For the compound according to Mode 23 of the present invention, in any one of the above Modes 18 to 22, the glass transition temperature of the material for a photoelectric conversion element is preferably 140 °C or higher.

[0152] The material for a photoelectric conversion element according to Mode 24 of the present invention preferably contains the compound according to any one of the above Modes 18 to 23.

[0153] The material for a photoelectric conversion element according to Mode 25 of the present invention is preferably a hole blocking material in the above Mode 24.

[0154] The material for a photoelectric conversion element according to Mode 26 of the present invention preferably has a layer containing the material for a photoelectric conversion element according to Mode 24 or 25 described above.

[0155] The photoelectric conversion element according to Mode 27 of the present invention can be an imaging element in the above Mode 26.

[0156] The compound according to Mode 28 of the present invention is a compound represented by the following formula (4-1): [Chemical Formula 15] In the formula (4-1), R 61 ~R 76 are each independently selected from a hydrogen atom, a cyano group, a nitro group, a halogen atom, a haloalkyl 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 the formula (4-2), or form a ring by bonding two adjacent groups to each other; R 61 ~R 74 any one of them is a group represented by the formula (4-2); L represents a direct bond or an aromatic hydrocarbon group having 6 to 16 carbon atoms; X 6 ~X 10 represent a nitrogen atom, C(CN), or CR 77 ; X 9 ~X 10 in, X 9 is C(CN), or X 10 is a nitrogen atom or C(CN); X 6 ~X 10 in, the number of the nitrogen atoms is 0 or 1. When the number of the nitrogen atoms is 0, the number of the C(CN) is any one of 2 to 3. When the number of the nitrogen atoms is 1, the number of the C(CN) is 2; R 77 are each independently selected from a hydrogen atom, a nitro group, a halogen atom, a haloalkyl 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; the R 61~R 77 and the L has at least one substituent or does not have the substituent.

[0157] For the compound according to Mode 29 of the present invention, in the above Mode 28, the R 77 are each independently preferably selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 1 to 20 carbon atoms.

[0158] For the compound according to Mode 30 of the present invention, in the above Mode 28 or 29, the R 61 ~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 the formula (4-2), or form an aromatic hydrocarbon ring by bonding two adjacent groups to each other.

[0159] For the compound according to Mode 31 of the present invention, in any one of the above Modes 28 to 30, preferably, X 10 is a nitrogen atom or C(CN), X 7 and X 8 is C(CN) or CR 77 , X 6 and X 9 is CR 77 .

[0160] For the compound according to Mode 32 of the present invention, in any one of the above Modes 28 to 31, the quantum calculation value of the LUMO energy level calculated by the density functional theory (DFT) using the B3LYP functional and the 6-31G(d) basis function is preferably -2.2 eV or less.

[0161] For the compound according to Mode 33 of the present invention, in any one of the above Modes 28 to 32, the glass transition temperature is preferably 140 °C or higher.

[0162] The material for a photoelectric conversion element according to Mode 34 of the present invention preferably contains the compound according to any one of the above Modes 28 to 33.

[0163] The material for a photoelectric conversion element according to Mode 35 of the present invention is preferably a hole blocking material in the above Mode 34.

[0164] The photoelectric conversion element according to Mode 36 of the present invention preferably includes a layer containing the material for a photoelectric conversion element according to the above Mode 34.

[0165] The photoelectric conversion element according to Mode 37 of the present invention can be an imaging element in the above Mode 36.

[0166] The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope shown in the claims. Embodiments obtained by appropriately combining technical means separately disclosed in different embodiments are also included in the technical scope of the present invention.

[0167] Example Hereinafter, the present invention will be described in further detail based on examples, but these examples do not make any limiting interpretation of the present invention.

[0168] Synthesis Example - 1 [Chemical Formula 16] Under an argon stream, (4,4,5,5 - tetramethyl - 2 - (dibenzo[g,p]chrysen - 3 - yl) - 1,3,2 - dioxaborolane (2.2 g), 4 - bromophthalonitrile (950 mg), and tetrakis(triphenylphosphine)palladium (168 mg) were suspended in 48 ml of THF, and 2 equivalents of an aqueous solution of tripotassium phosphate (7.3 ml) was added, followed by refluxing for 17 hours. After cooling the reaction solution to room temperature, water was added and the resulting solid was filtered to obtain 2.1 g of a yellow solid. The obtained yellow solid was recrystallized from 120 ml of toluene to obtain the target compound (B408) (1.7 g, yield 78%).

[0169] The obtained compound (B408) was identified by 1H - NMR.

[0170] 1H - NMR (CDCl3) δ (ppm): 8.88 (d, J = 1.9 Hz, 1H), 8.83 (d, J = 9.3 Hz, 1H), 8.77 - 8.71 (m, 5H), 8.65 (d, J = 8.2 Hz, 1H), 8.26 (d, J = 1.4 Hz, 1H), 8.16 (dd, J = 8.5, 2.0 Hz, 1H), 7.96 (d, J = 8.3 Hz, 1H), 7.82 (dd, J = 8.7, 1.7 Hz, 1H), 7.77 - 7.65 (m, 6H). Synthesis Example - 2 [Chemical Formula 17] Under an argon stream, (4,4,5,5-tetramethyl-2-(dibenzo[g,p]chrysen-3-yl)-1,3,2-dioxaborolane (2.0 g), 4-chloropyridine-2,6-dicarbonitrile (790 mg), palladium acetate (30 mg), and dicyclohexyl(2’,4’,6’-triisopropyl-(1,1’-biphenyl)-2-yl)phosphine (126 mg) were suspended in 44 ml of THF. 2 equivalents of aqueous potassium phosphate tribasic solution (6.6 ml) was added, and the mixture was refluxed for 6 hours. After the reaction solution was cooled to room temperature, water was added and the resulting solid was filtered to obtain 2.1 g of a yellow solid. The obtained yellow solid was washed with hexane and methanol to obtain the target compound (B395) (2.0 g, yield 100%).

[0171] The obtained compound (B395) was identified by 1H-NMR.

[0172] 1H-NMR (CDCl3) δ (ppm): 8.94 (d, J = 1.9 Hz, 1H), 8.86 (d, J = 8.7 Hz, 1H), 8.78 - 8.71 (m, 5H), 8.61 (d, J = 7.8 Hz, 1H), 8.29 (S, 2H), 8.84 (dd, J = 8.8, 2.5 Hz, 1H), 7.80 - 7.67 (m, 6H). Synthesis Example - 3 [Chemical Formula 18] Under an argon stream, 3,6-dichloro-benzo[g]indeno[1,2,3-qr]chrysene (1.7 g), 4-cyanophenylboronic acid (1.2 g), palladium acetate (27 mg), and dicyclohexyl(2’,4’,6’-triisopropyl-(1,1’-biphenyl)-2-yl)phosphine (114 mg) were suspended in 46 ml of THF. Aqueous potassium phosphate tribasic solution (6.0 ml) of 2 equivalents was added, and the mixture was refluxed for 17 hours. After the reaction solution was cooled to room temperature, water was added and the resulting solid was filtered to obtain 2.2 g of a yellow solid. The obtained yellow solid was recrystallized with 120 ml of toluene to obtain the target compound (B499) (2.0 g, yield 89%).

[0173] The obtained compound (B499) was identified by 1H-NMR.

[0174] 1H-NMR (CDCl3) δ (ppm): 9.12 (s, 1H), 9.05 (d, J = 8.4 Hz, 1H), 8.93 (d, J = 5.1 Hz, 1H), 8.91 (dd, J = 5.3, 1.9 Hz, 2H), 8.89 (d, J = 8.6 Hz, 1H), 8.12 - 8.10 (m, 1H), 8.05 (d, J = 7.0 Hz, 1H), 8.00 - 7.91 (m, 7H), 7.87 - 7.82 (m, 5H), 7.50 - 7.48 (m, 2H). Synthesis Example - 4 [Chemical Formula 19] Under an argon stream, 3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-benzo[g]indeno[1,2,3-qr]anthracene (6.7 g), 4-bromophthalonitrile (4.6 g), and tetrakis(triphenylphosphine)palladium (380 mg) were suspended in 440 ml of THF. 2 equivalents of aqueous potassium phosphate solution (33 ml) was added, and the mixture was refluxed for 4 hours. After cooling the reaction solution to room temperature, water was added and the resulting solid was filtered to obtain 7.8 g of a yellow solid. The obtained yellow solid was washed with chlorobenzene to obtain the target compound (B509) (5.5 g, yield 83%).

[0175] The obtained compound (B499) was identified by 1H-NMR.

[0176] 1H-NMR (DMSO) δ (ppm): 9.74 (s, 2H), 9.54 (d, J = 7.3 Hz, 2H), 9.33 (d, J = 9.0 Hz, 1H), 9.11 (d, J = 9.0 Hz, 1H), 8.95 (dd, J = 4.8 Hz, 1.6 Hz, 2H), 8.87 (d, J = 8.9 Hz, 1H), 8.70 (dd, J = 8.6 Hz, 2.0 Hz, 1H), 8.65 (dd, J = 8.3 Hz, 1.8 Hz, 1H), 8.45 (d, J = 6.5 Hz, 1H), 8.40 (dd, J = 8.0 Hz, 1.7 Hz, 2H), 8.36 - 8.30 (m, 2H), 8.16 (d, J = 6.6 Hz, 1H), 7.98 (t, J = 7.8 Hz, 1H), 7.55 (t, J = 4.0 Hz, 2H). Synthesis Example - 5 [Chemical Formula 20] Under an argon stream, (4,4,5,5-tetramethyl-2-(dibenzo[g,p]chrysen-3-yl)-1,3,2-dioxaborolane (2.2 g), 4-bromophthalonitrile (910 mg), and tetrakis(triphenylphosphine)palladium (150 mg) were suspended in 44 ml of THF, and 2 equivalents of an aqueous potassium phosphate solution (6.6 ml) was added. The mixture was refluxed for 5 hours. After the reaction solution was cooled to room temperature, water was added, and the resulting solid was collected by filtration to obtain 2.0 g of a yellow solid. The obtained yellow solid was recrystallized from toluene to obtain the target compound (B426) (1.5 g, yield 75%).

[0177] The obtained compound (B426) was identified by 1H-NMR.

[0178] 1H-NMR (CDCl3) δ (ppm): 8.86 (d, J = 2.1 Hz, 1H), 8.81 (d, J = 8.7 Hz, 1H), 8.72 - 8.67 (m, 5H), 8.65 (d, J = 8.4 Hz, 1H), 8.11 (d, J = 1.7 Hz, 1H), 7.94 (dd, J = 8.3, 1.6 Hz, 1H), 7.81 (d, J = 8.3 Hz, 1H), 7.77 (dd, J = 8.3, 2.2 Hz, 1H), 7.73 - 7.64 (m, 6H). Synthesis Example - 6 [Chemical Formula 21] Under an argon stream, (4,4,5,5-tetramethyl-2-(spiro(benzo[c]fluorene-7,9'-fluorene)-5-yl)-1,3,2-dioxaborolane (1.0 g), 4-chloropyridine-2,6-dicarbonitrile (315 mg), palladium acetate (13 mg), and dicyclohexyl(2',4',6'-triisopropyl-(1,1'-biphenyl)-2-yl)phosphine (58 mg) were suspended in 20 ml of THF, and 2 equivalents of an aqueous potassium phosphate solution (3.0 ml) was added. The mixture was refluxed for 4 hours. After the reaction solution was cooled to room temperature, water was added, and the resulting solid was collected by filtration to obtain 0.95 g of a yellow solid. The obtained yellow solid was purified by silica gel column chromatography to obtain the target compound (B622) (0.7 g, yield 70%).

[0179] The obtained compound (B622) was identified by 1H-NMR.

[0180] 1H-NMR (DMSO) δ (ppm): 8.98 (s, 2H), 8.60 (d, J = 8.3 Hz, 1H), 7.94 (t, J = 5.9 Hz, 2H), 7.70 (t, J = 7.5 Hz, 1H), 7.51 (t, J = 7.6 Hz, 1H), 7.40 - 7.11 (m, 8H), 7.03 (t, J = 7.7 Hz, 1H), 6.71 (d, J = 7.3 Hz, 1H), 6.67 (d, J = 6.7, 1H), 6.57 (d, J = 7.3 Hz, 1H). Synthesis Example - 7 [Chemical formula 22] Under an argon stream, 2,7-dibromo-9,9'-spirobifluorene (1.5 g), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phthalonitrile (844 mg), and tetrakis(triphenylphosphine)palladium (110 mg) were suspended in 30 ml of THF, and 2 equivalents of aqueous potassium phosphate solution (4.7 ml) was added, followed by refluxing for 5 hours. After cooling the reaction solution to room temperature, water was added and the resulting solid was filtered to obtain 1.81 g of a yellow solid. The obtained yellow solid was recrystallized from 180 ml of chlorobenzene to obtain the target compound (B577) (1.1 g, yield 61%).

[0181] The obtained compound (B577) was identified by 1H-NMR.

[0182] 1H-NMR (DMSO) δ (ppm): 8.35 (s, 2H), 8.32 (d, J = 7.8 Hz, 2H), 8.08 - 8.02 (m, 6H), 7.98 (dd, J = 7.8 Hz, 1.6 Hz, 2H), 7.44 (t, J = 7.6 Hz, 2H), 7.15 (t, J = 7.6 Hz, 2H), 7.09 (s, 2H), 7.70 (d, J = 7.2 Hz, 2H). Synthesis Example - 8 [Chemical formula 23] Under an argon stream, 2-(4-(2-bromotriphenylene-7-yl)phenyl)-6-(4-cyanophenyl)-4-phenylpyridine (1.0 g), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phthalonitrile (610 mg), palladium acetate (7.2 mg), and dicyclohexyl(2’,4’,6’-triisopropyl-(1,1’-biphenyl)-2-yl)phosphine (30 mg) were suspended in 16 ml of THF. 2 equivalents of aqueous tripotassium phosphate solution (2.4 ml) was added, and the mixture was refluxed for 4 hours. After the reaction solution was cooled to room temperature, water was added and the resulting solid was collected by filtration to obtain 1.3 g of a solid. The obtained solid was purified by silica gel column chromatography to obtain the target compound (B104) (0.81 g, yield 73%).

[0183] The obtained compound (B104) was identified by 1H-NMR.

[0184] 1H-NMR (DMSO) δ (ppm): 8.96 (s, 1H), 8.86 - 8.77 (m, 4H), 8.37 (dd, J = 8.4 Hz, 3.4 Hz, 4H), 8.24 (d, J = 1.8 Hz, 1H), 8.16 (dd, J = 8.1 Hz, 1.8 Hz, 1H), 8.05 - 7.95 (m, 6H), 7.88 (d, J = 8.1 Hz, 1H), 7.83 (d, J = 8.7 Hz, 1H), 7.78 - 7.75 (m, 4H), 7.59 - 7.50 (m, 4H). <Glass transition temperature · LUMO energy level> For the compounds (B408), (B395), (B499), (B509), (B426), (B622), (B577), (B104) of Synthesis Examples 1 - 8, Comparative Compound 1 described in Reference 1, and Comparative Compound 2 described in Reference 2, the glass transition temperature was measured using a differential scanning calorimeter (DSC702 manufactured by Hitachi High-Technologies) with an aluminum pan at a scanning rate of 10 °C / min. Additionally, for the LUMO energy level, using the Gaussian16 software, density functional theory (DFT) with calculation conditions based on the B3LYP functional and 6-31G(d) basis functions was used to optimize the molecular structure and calculate the LUMO energy level. The results of the obtained glass transition temperature and LUMO energy level (Calc.LUMO) are summarized in Table 1.

[0185] [Chemical formula 24] [Table 1] <Element Example-1 (referenceFigure 1 )> As Figure 1 shown, a photoelectric conversion element having a laminated structure including 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 was fabricated into an imaging element 100, and the dark current, external quantum efficiency, and responsiveness of the imaging element were evaluated.

[0186] (Preparation of the first electrode 1) As a substrate having a first electrode on its surface, a glass substrate with an indium tin oxide (ITO) film (film thickness: 110 nm) that is 2 mm wide and patterned into stripes was prepared as a transparent electrode with ITO. Then, after cleaning the substrate with isopropyl alcohol, surface treatment was performed by ozone ultraviolet cleaning.

[0187] (Preparation for vacuum evaporation) On the substrate that had undergone surface treatment after cleaning, each layer was formed by vacuum evaporation using the vacuum evaporation method.

[0188] First, the above-mentioned glass substrate was introduced into the vacuum evaporation chamber, and the pressure was reduced to 7.0×10 -5 Pa. Then, fabrication was performed according to the film formation conditions for each layer in the following order.

[0189] (Fabrication of the hole blocking layer 2) The sublimation-purified compound (B408) was formed into a film at a rate of 0.03 nm / second for 10 nm to fabricate the hole blocking layer 2.

[0190] (Fabrication of the photoelectric conversion layer (light-receiving layer) 3) N,N-dimethylquinacridone and C60 were formed into a film at a ratio of 4:1 (mass ratio) for 120 nm to fabricate the photoelectric conversion layer 3. The film formation rate was 0.15 nm / second.

[0191] (Fabrication of the electron blocking layer 4) The compound (ic-3) was formed into a film at a rate of 0.10 nm / second for 10 nm to fabricate the electron blocking layer 4. It should be noted that (ic-3) was synthesized by the method described in JP-A-2018-193371.

[0192] (Fabrication of the hole transport layer 5) The compound 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN) was formed into a film at a rate of 0.10 nm / second for 10 nm to fabricate the hole transport layer 5.

[0193] (Fabrication of the second electrode 6) Finally, a metal mask is disposed in a manner orthogonal to the ITO stripes on the substrate, and a second electrode 6 serving as the upper electrode is formed. Specifically, silver is formed at a rate of 0.1 nm / second for 80 nm to fabricate the second electrode 6 serving as the upper electrode.

[0194] Thereby, a photoelectric conversion element 100 for imaging as shown in Figure 1 with an area of 4 mm 2 is fabricated. It should be noted that each film thickness is measured using a stylus type film thickness gauge (DEKTAK, manufactured by Bruker).

[0195] Furthermore, the element is sealed in a nitrogen atmosphere glove box with an oxygen and moisture concentration of 1 ppm or less. The sealing is performed using a bisphenol F type epoxy resin (manufactured by Nagase ChemteX) for the glass sealing cover and the film-forming substrate (element).

[0196] The dark current (dark current), external quantum efficiency, and response time are evaluated when a voltage of 2.6 V is applied to the imaging element fabricated as described above in the dark. The measurement of the dark current is evaluated using a source measure unit (Source Measure Unit) 2636B manufactured by Keithley. The measurement of the external quantum efficiency is performed using a solar cell spectral sensitivity measurement device (manufactured by Soma Optical Co., Ltd.). The wavelength of the irradiated light is measured at 560 nm and the intensity is 50 μ W / cm 2 The response time is measured by irradiating a light pulse and measuring the time until the current value returns to the value before irradiation.

[0197] It should be noted that the dark current, external quantum efficiency, and response time are relative values with the result of element comparative example - 1 as the reference value (1.0). It shows that the lower the value of the dark current, the more excellent the performance; the higher the value of the external quantum efficiency, the more excellent the performance; and the shorter the response time, the more excellent the performance. The obtained measurement results are shown in Table 1.

[0198] Element examples 2 - 7, element comparative examples - 1 - 2 In element example - 1, compound (B395), compound (B499), compound (B509), compound (B426), compound (B577), compound (B104), or comparative compound 1 is used in turn to replace compound (B408). Except for this, a photoelectric conversion element for imaging is fabricated and evaluated using the same method as in element example - 1. The obtained measurement results are shown in Table 1.

[0199] [Table 2] Based on the results in Table 1, by forming a layer using the compound shown in Formula (1) or Formula (3) or Formula (4-1) as a material for an imaging element and a photoelectric conversion element, excellent results in terms of dark current, external quantum efficiency, and responsiveness are shown as compared with the case of forming a layer using a comparative example compound.

[0200] Industrial Applicability An imaging element including the photoelectric conversion element according to one embodiment of the present invention can be applied to, for example, an imaging element of a digital camera, a digital video camera, an imaging element built in a mobile phone, etc., and an image input device of a driving assistance system.

[0201] Explanation of Reference Numerals 1 First electrode 2 Hole blocking layer 3 Photoelectric conversion layer (light-receiving layer) 4 Electron blocking layer 5 Hole transport layer 6 Second electrode 10 Organic layer 100 Imaging element (photoelectric conversion element).

Claims

1. A photoelectric conversion element, characterized in that, having a layer containing a material for a photoelectric conversion element, the material for a photoelectric conversion element being represented by the following formula (1): ， in the formula (1), Ar represents a condensed polycyclic 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 of 1 to 8; k represents an integer of 0 to 2; p represents an integer of 1 to 8; when k is 0, p is 1, when there are two or more of the EWGs, the EWGs are the same or different electron-withdrawing groups, the Ar, L, and EWG each have at least one substituent or do not have the substituent.

2. The photoelectric conversion element according to claim 1, wherein, the EWG is selected from a cyano group, a fluorine atom, a fluoroalkyl group, and a heteroaryl group having 3 to 30 carbon atoms containing a nitrogen atom.

3. The photoelectric conversion element according to claim 2, wherein, the heteroaryl group having 3 to 30 carbon atoms containing a nitrogen atom has a substituent, and at least one of the substituents is a group selected from a cyano group, a fluorine atom, and a fluoroalkyl group.

4. The photoelectric conversion element according to claim 1, wherein, the k is an integer of 0 or 1.

5. The photoelectric conversion element according to claim 1, wherein, the k is 1, and the EWG is at least one group selected from a cyano group, a fluoro group, and a fluoroalkyl group.

6. The photoelectric conversion element according to claim 1, wherein, the Ar is a condensed polycyclic aromatic hydrocarbon group containing 4 or more 6-membered rings.

7. The photoelectric conversion element according to claim 1, wherein, the Ar is selected from the following groups: condensed polycyclic aromatic hydrocarbon groups selected from triphenylene, fluoranthenyl, and spirofluorene groups, and condensed polycyclic aromatic hydrocarbon groups containing triphenylene, fluoranthenyl, and spirofluorene groups.

8. The photoelectric conversion element according to claim 1, wherein, the Ar represents a condensed polycyclic aromatic hydrocarbon group having 20 to 40 carbon atoms having or not having the substituent.

9. The photoelectric conversion element according to claim 1, wherein, the Ar is represented by the following formulas (2-1), (2-2), and (2-3), ， in the formulas (2-1), (2-2), and (2-3), R 1 ~R 38 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, R 1 ~R 38 A ring is formed by bonding of a part of ~~ within the two groups adjacent to each other. Among them, the R 1 ~R 35 each independently has at least one substituent or does not have the substituent.

10. The photoelectric conversion element according to claim 1, wherein, the quantum calculation value of the LUMO energy level of the material for a photoelectric conversion element calculated by density functional theory (DFT) using the B3LYP functional and the 6-31G(d) basis function is -2.2 eV or less.

11. The photoelectric conversion element according to claim 1, wherein, the glass transition temperature of the material for a photoelectric conversion element is 140°C or higher.

12. The photoelectric conversion element according to claim 1, wherein, the layer containing the material for a photoelectric conversion element is a hole blocking layer.

13. The photoelectric conversion element according to claim 1, wherein, the photoelectric conversion element is an imaging element.

14. A material for a photoelectric conversion element, characterized in that, For forming the layer included in the photoelectric conversion element according to any one of claims 1 to 13, the material for a photoelectric conversion element is the material for a photoelectric conversion element represented by the formula (1).

15. The material for a photoelectric conversion element according to claim 14, wherein, the material for a photoelectric conversion element is a material for a photoelectric conversion element for an imaging element.

16. The material for an optoelectronic conversion element according to claim 14, wherein, the material for a photoelectric conversion element is a hole blocking material.

17. The photoelectric conversion element according to claim 12, wherein, a layer containing fullerene is provided between the hole blocking layer and the electrode.

18. A compound, characterized in that, represented by the following formula (3): ， in the formula (3), X 1 ~X 5 represents a nitrogen atom or CR 55 ; X 1 ~X 5 wherein the number of the nitrogen atoms is an integer of 0 to 3; R 40 ~R 55 each independently selected from a hydrogen atom, a cyano group, a nitro group, a halogen atom, a haloalkyl 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 R 40 ~R 55 A part of them forms a ring by bonding two adjacent groups to each other; R 55 at least one of which is selected from a cyano group, a halogen atom, or a haloalkyl group; At X 1 ~X 5 are all CR 55 In the case where, the two or more of the R 55 are selected from a cyano group, a halogen atom, and a haloalkyl group; The R 40 to R 55 each independently further has at least one substituent or does not have the substituent.

19. The compound according to claim 18, wherein, The R 55 are each independently selected from a hydrogen atom, a cyano group, a halogen atom, a haloalkyl group, an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl group having 1 to 20 carbon atoms.

20. The compound according to claim 18, wherein Any one of the R 55 is a cyano group.

21. The compound according to claim 18, wherein, the halogen atom is a fluorine atom, the aromatic hydrocarbon group having 6 to 30 carbon atoms is substituted with a group selected from a cyano group, a fluoro group, and a fluoroalkyl group.

22. The compound according to claim 18, wherein the quantum calculation value of the LUMO energy level calculated by density functional theory (DFT) using the B3LYP functional and the 6-31G(d) basis function is -2.2 eV or less.

23. The compound according to claim 18, wherein, the glass transition temperature of the compound is 140°C or higher.

24. A material for a photoelectric conversion element, characterized in that, including the compound according to any one of claims 18 to 23.

25. The material for an optoelectronic conversion element according to claim 24, wherein, the material for a photoelectric conversion element is a hole blocking material.

26. A photoelectric conversion element, characterized in that, It has a layer containing the material for a photoelectric conversion element described in claim 24.

27. The photoelectric conversion element according to claim 26, wherein, The photoelectric conversion element is an imaging element.

28. A compound, characterized in that, It is represented by the following formula (4-1): ， In the formula (4-1), R 61 ~R 76 Each independently selected from a hydrogen atom, a cyano group, a nitro group, a halogen atom, a haloalkyl 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 a ring is formed by bonding two adjacent groups to each other; R 61 ~R 76 Any one of them is a group represented by the formula (4-2); L represents a direct bond or an aromatic hydrocarbon group having 6 to 16 carbon atoms; X 6 ~X 10 represents a nitrogen atom, C(CN), or CR 77 ; X 9 and X 10 in, X 9 is C(CN), or X 10 is a nitrogen atom or C(CN); X 6 ~X 10 Among them, the number of the nitrogen atoms is 0 or 1. When the number of the nitrogen atoms is 0, the number of C(CN) is any one of 2 to 3. When the number of the nitrogen atoms is 1, the number of C(CN) is 2; R 77 each independently selected from a hydrogen atom, a nitro group, a halogen atom, a haloalkyl 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; The R 61 to R 77 and the L have at least one substituent or do not have the substituent.

29. The compound according to claim 28, wherein, The R 77 are 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.

30. The compound according to claim 28, wherein The R 61 to R 76 is 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 the formula (4-2), or forms an aromatic hydrocarbon ring by bonding of two adjacent groups to each other.

31. The compound according to claim 28, wherein, X 10 is a nitrogen atom or C(CN), X 7 and X 8 is C(CN) or CR 77 ,X 6 and X 9 is CR 77 。 32. The compound according to claim 28, wherein, The quantum calculation value of the LUMO energy level calculated by density functional theory (DFT) using the B3LYP functional and the 6-31G(d) basis function is -2.2 eV or less.

33. The compound according to claim 28, wherein The glass transition temperature of the compound is 140°C or higher.

34. A material for a photoelectric conversion element, characterized in that, It contains the compound described in any one of claims 28 to 33.

35. The material for a photoelectric conversion element according to claim 34, wherein, The material for the photoelectric conversion element is a hole blocking material.

36. A photoelectric conversion element, characterized in that, It has a layer containing the material for a photoelectric conversion element described in claim 34.

37. The photoelectric conversion element according to claim 36, wherein, The photoelectric conversion element is an imaging element.

Images