Material for photoelectric conversion element for imaging element, amine compound, material for organic electronic element, material for photoelectric conversion element, organic thin film, and organic electronic element

Abstract

Provided are a material for a photoelectric conversion element for an imaging element, and the like, that contribute to producing a photoelectric conversion element that has a low dark current and excels in responsiveness.　A compound represented by formula (1) is used. In formula (1), R1-R13 are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a hydroxy group, a thiol group, an allyl group, a 6-30C monocyclic, linked, or condensed aromatic hydrocarbon group that may have a substituent, a 3-36C monocyclic, linked, or condensed heteroaromatic group that may have a substituent, or a group represented by formula (2). However, R5 and R6, and / or R7 and R8, are linked to each other to form a benzene ring, and form a group represented by formula (3).

Description

Material for photoelectric conversion element for imaging device, amine compound, material for organic electronic element, material for photoelectric conversion element, organic thin film, and organic electronic element

[0001] The present invention relates to a material for a photoelectric conversion element for an imaging element, an amine compound, a material for an organic electronic element, a material for a photoelectric conversion element, an organic thin film, and an organic electronic element.

[0002] Photoelectric conversion elements for image pickup devices are used in applications such as mobile phones and cameras, and their development is being actively pursued.

[0003] In recent years, market demand for photoelectric conversion elements for image sensors has been increasing, and materials that are excellent in dark current, external quantum efficiency, and response speed are being sought. Under these circumstances, the possibility of various polycyclic compounds as the mother nucleus of new materials has been continuously explored and studied. As polycyclic compounds, Patent Document 1 discloses derivatives having benzothienobenzothiophene as the mother nucleus. Furthermore, Patent Document 2 discloses various mother nuclei in addition to benzothienobenzothiophene. Patent Document 3 discloses unsubstituted dibenzo[g,p]chrysene.

[0004] International Publication No. 2015 / 163349 International Publication No. 2020 / 022421 Japanese Patent Application Laid-Open No. 2010-258438

[0005] An object of one embodiment of the present invention is to propose a material for a photoelectric conversion element and a photoelectric conversion element using a compound having a new mother nucleus, while the possibility of using various polycyclic compounds as the mother nucleus of a new material is being explored and investigated.

[0006] Another object of the present invention is to provide a photoelectric conversion element material for an imaging device that contributes to the production of a photoelectric conversion element having low dark current and excellent response, a compound that contributes to the production of a photoelectric conversion element having low dark current and excellent response, and an organic electronic device material and a photoelectric conversion element material containing the compound. Meanwhile, Patent Document 3 describes the use of unsubstituted dibenzo[g,p]chrysene as a crystalline layer between a photoelectric conversion layer and a second electrode. However, Patent Document 3 does not mention the molecular structural characteristics of dibenzo[g,p]chrysene or an amorphous film containing dibenzo[g,p]chrysene. In addition, the dibenzo[g,p]chrysene described in Patent Document 3 does not provide any knowledge about improving the performance of a photoelectric conversion element for an imaging device.

[0007] The present inventors have found that the above problems can be solved by using a specific fused ring compound, and have completed the present invention.

[0008] Aspects of the present disclosure relate to the following materials for photoelectric conversion elements for imaging elements, amine compounds, materials for organic electronic elements, materials for photoelectric conversion elements, organic thin films, and organic electronic elements.

[0009] [1] A material for a photoelectric conversion element for an imaging element, comprising a compound represented by the following formula (1): In formula (1), R １ ~R １３ are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a hydroxy group, a thiol group, an allyl group, an optionally substituted monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms, or a group represented by the following formula (2), wherein R ５ and R ６ , R ７ and R ８ At least one of these groups is linked to each other to form a benzene ring, thereby forming a group represented by the following formula (3). In formula (2), R ａ ~R ｂeach independently represents a hydrogen atom, a deuterium atom, a monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, a monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms which may have a substituent, a group in which the aromatic hydrocarbon group and the heteroaromatic group are linked together, or a linear or branched alkyl group having 1 to 18 carbon atoms; R ａ and R ｂ may be bonded to each other to form a ring, and each Y independently represents a monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, a monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms which may have a substituent, or a single bond; n represents 1 or 2, and when Y is a single bond, n is 1, and when Y is not a single bond, n is 1 or 2; and when n is 2, multiple R ａ ~R ｂ may be the same or different; Y is an integer between adjacent R ａ and R ｂ In formula (3), R may be bonded to either or both of them to form a ring. １４ ~R １７ are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a hydroxy group, a thiol group, an allyl group, an optionally substituted monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms, or a group represented by the formula (2). １ ~R １７ At least one of R is a group represented by the formula (2). ５ and R ６ , or R ７ and R ８ When either of them is bonded to each other to form a benzene ring to form a group represented by the formula (3), R １ ~R ４The material for a photoelectric conversion element for an imaging element according to [1], wherein at least one of the following is a group represented by formula (2): [3] The material for a photoelectric conversion element for an imaging element according to [1] or [2], wherein Y is a single bond: [4] An amine compound represented by the following formula (1): In formula (1), R １ ~R １3 are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a hydroxy group, a thiol group, an allyl group, an optionally substituted monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms, or a group represented by the following formula (2), wherein R ５ and R ６ , R ７ and R ８ At least one of these groups is linked to each other to form a benzene ring, thereby forming a group represented by the following formula (3). In formula (2), R ａ ~R ｂ each independently represents a hydrogen atom, a deuterium atom, a monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, a monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms which may have a substituent, a group in which the aromatic hydrocarbon group and the heteroaromatic group are linked together, or a linear or branched alkyl group having 1 to 18 carbon atoms; R ａ and R ｂ may be bonded to each other to form a ring, and each Y independently represents a monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, a monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms which may have a substituent, or a single bond; n represents 1 or 2, and when Y is a single bond, n is 1, and when Y is not a single bond, n is 1 or 2; and when n is 2, multiple R ａ ~R ｂ may be the same or different; Y is an integer between adjacent R ａ and Rｂ In formula (3), R may be bonded to either or both of them to form a ring. １４ ~R １７ are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a hydroxy group, a thiol group, an allyl group, an optionally substituted monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms, or a group represented by the following formula (2), wherein R １ ~R １７ At least one of R is a group represented by the formula (2), ５ and R ６ , or R ７ and R ８ When either of them is bonded to each other to form a benzene ring to form a group represented by the formula (3), R １ ~R ４ At least one of R is a group represented by the formula (2). ａ and R ｂ are each independently a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a chrysenyl group, a fluorenyl group, a benzofluorenyl group, a spirobifluorenyl group, a dibenzofuranyl group, a dibenzothionyl group, a carbazolyl group, a naphthylphenyl group, a phenylnaphthyl group, a naphthylnaphthyl group, a phenanthrylphenyl group, a dibenzofuranylphenyl group, a dibenzothionylphenyl group, or a carbazolylphenyl group. [6] The amine compound according to [4] or [5], wherein n is 1. [7] R １ ~R １７ are each independently a hydrogen atom, a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a dibenzofuranyl group, a dibenzothionyl group, a carbazolyl group, or a group represented by the formula (2), １ ~R １７ At least one of R is a group represented by the formula (2), ５ and R ６ , or R ７and R ８ When either of them is bonded to each other to form a benzene ring to form a group represented by the formula (3), R １ ~R ４ [8] The amine compound according to any one of [4] to [7], wherein at least one of R is a group represented by formula (2). [9] The amine compound according to any one of [4] to [7], wherein Y is a single bond. １ ~R ４

[10] The amine compound according to any one of [4] to [8], wherein any one of the following is a group represented by formula (2):

[10] The amine compound according to any one of [4] to [9], wherein the HOMO value is 5.0 to 6.5 eV.

[11] The amine compound according to any one of [4] to

[10] , wherein the band gap is 2.5 to 4.0 eV.

[12] The amine compound according to any one of [4] to

[11] , wherein the LUMO value is 2.0 to 3.5 eV.

[13] The amine compound according to any one of [4] to

[12] , wherein the glass transition temperature is 140° C. or higher.

[14] The amine compound according to any one of [4] to

[13] , wherein the molecular weight is less than 1,000.

[15] A material for an organic electronic device, comprising the amine compound according to any one of [4] to

[14] .

[16] A material for a photoelectric conversion device, comprising the amine compound according to any one of [4] to

[14] .

[17] A charge transport material for a photoelectric conversion element for an imaging device or a charge blocking material for a photoelectric conversion element for an imaging device, comprising the amine compound according to any one of [4] to

[14] .

[18] A hole transport material for a photoelectric conversion element for an imaging device or an electron blocking material for a photoelectric conversion element for an imaging device, comprising the amine compound according to any one of [4] to

[14] .

[19] An organic thin film comprising the amine compound according to any one of [4] to

[14] .

[20] An organic electronic element comprising the amine compound according to any one of [4] to

[14] .

[0010] According to one embodiment of the present invention, it is possible to provide a material for a photoelectric conversion element for an imaging element that contributes to the production of a photoelectric conversion element having low dark current and excellent response, a compound that contributes to the production of a photoelectric conversion element having low dark current and excellent response, and a material for an organic electronic element and a material for a photoelectric conversion element that include the compound.

[0011] 1 is a schematic cross-sectional view showing an example of a layer structure of a photoelectric conversion element for an imaging element including a material for a photoelectric conversion element for an imaging element according to one aspect of the present invention.

[0012] Hereinafter, a material for a photoelectric conversion element for an imaging element according to one embodiment of the present disclosure will be described in detail.

[0013] <Photoelectric conversion element material for imaging device> A compound represented by the following formula (1) can be suitably used as a photoelectric conversion element material for imaging devices. That is, a photoelectric conversion element material for imaging devices according to one embodiment of the present disclosure contains a compound represented by the following formula (1).

[0014] R １ ~R １３ are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a hydroxy group, a thiol group, an allyl group, an optionally substituted monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms, or a group represented by the following formula (2), wherein R ５ and R ６ , R ７ and R ８ At least one of these groups is linked to each other to form a benzene ring, thereby forming a group represented by the following formula (3).

[0015]

[0016]

[0017] In formula (2), R ａ ~R ｂ each independently represents a hydrogen atom, a deuterium atom, a monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, a monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms which may have a substituent, a group in which the aromatic hydrocarbon group and the heteroaromatic group are linked together, or a linear or branched alkyl group having 1 to 18 carbon atoms; R ａ and R ｂmay be bonded to each other to form a ring, and each Y independently represents a monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, a monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms which may have a substituent, or a single bond; n represents 1 or 2, and when Y is a single bond, n is 1, and when Y is not a single bond, n is 1 or 2; and when n is 2, multiple R ａ ~R ｂ may be the same or different; Y is an integer between adjacent R ａ and R ｂ may be bonded to either or both of the following to form a ring.

[0018] In formula (3), R １４ ~R １７ are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a hydroxy group, a thiol group, an allyl group, an optionally substituted monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms, or a group represented by the formula (2). １ ~R １７ At least one of the above is a group represented by formula (2).

[0019] By having the specific structure, a photoelectric conversion element material for an imaging device containing the compound represented by formula (1) can provide a photoelectric conversion element with low dark current and excellent response. Therefore, the compound represented by formula (1) is suitably used as a photoelectric conversion element material for an imaging device.

[0020] Preferred embodiments of the definition in the above formula (1) are as follows:

[0021] <R １ ~R １３ > (aromatic hydrocarbon group) R １ ~R １３Examples of the optionally substituted monocyclic, linked, or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms as (a-1) include a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a chrysenyl group, a benzochrysenyl group, a dibenzochrysenyl group, a fluorenyl group, a benzofluorenyl group, a spirobifluorenyl group, a naphthylphenyl group, a phenylnaphthyl group, a naphthylnaphthyl group, and a phenanthrylphenyl group. Furthermore, the monocyclic, linked, or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms is preferably a monocyclic, linked, or fused ring aromatic hydrocarbon group having 6 to 18 carbon atoms.

[0022] In addition, R １ ~R １３ When the aromatic hydrocarbon group as represented by formula (I) has a substituent, the substituents are preferably each independently a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, a phosphine oxide group which may have a substituent, a silyl group which may have a substituent, a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms, an alkyl group, an alkoxy group, an aromatic hydrocarbon group, a heteroaromatic group, or a trifluoromethylsulfonyloxy group. Of these, an alkyl group, an aromatic hydrocarbon group, or a heteroaromatic group is more preferred.

[0023] The phosphine oxide group as the substituent includes an unsubstituted phosphine oxide group and a phosphine oxide group having a substituent, and is preferably a phosphine oxide group having a substituent.

[0024] The phosphine oxide group having a substituent, which is the above-mentioned substituent, is preferably a phosphine oxide group having a monocyclic, linked, or fused ring aromatic hydrocarbon group or a fused ring heteroaromatic group having 6 to 18 carbon atoms. Specific examples include groups substituted with two aryl groups, such as diphenylphosphine oxide.

[0025] The silyl group as the substituent includes an unsubstituted silyl group and a silyl group having a substituent, and a silyl group having a substituent is preferred.

[0026] The silyl group having a substituent, which is the above-mentioned substituent, is preferably a silyl group having a monocyclic, linked, or fused ring aromatic hydrocarbon group or a fused ring heteroaromatic group having 6 to 18 carbon atoms. Specific examples include groups substituted with three aryl groups, such as a triphenylsilyl group.

[0027] Examples of the boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms as the substituent include a dihydroxyboryl group (-B(OH) ２ ), 4,4,5,5-tetramethyl-[1,3,2]-dioxaborolanyl group, 5,5-dimethyl-[1,3,2]-dioxaborinane group, and the like.

[0028] The alkyl group as the substituent is preferably a linear or branched alkyl group having 1 to 18 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an n-hexyl group, a cyclohexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group.

[0029] The alkoxy group as the substituent is preferably a linear or branched alkoxy group having 1 to 18 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, an n-hexyloxy group, a cyclohexyloxy group, an octyloxy group, a decyloxy group, a dodecyloxy group, and an octadecyloxy group.

[0030] Examples of the aromatic hydrocarbon group as the substituent include a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, a fluorenyl group, a fluoranthenyl group, an anthryl group, a phenanthryl group, a benzofluorenyl group, a triphenylenyl group, a spirobifluorenyl group, a diphenylfluorenyl group, a dibenzo[g]chrysenyl group, and a dibenzo[g,p]chrysenyl group.

[0031] Examples of the heteroaromatic group as the substituent include a pyrrolyl group, a thienyl group, a furyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a pyridyl group, a phenylpyridyl group, a pyridylphenyl group, a pyrimidyl group, a pyrazyl group, a 1,3,5-triazyl group, a 1,3,5-triazylphenyl group, a 1,3,5-triazylbiphenylyl group, a 4,6-diphenyl-1,3,5-triazyl group, an indolyl group, a benzothienyl group, a benzofuranyl group, a benzoimid ... Examples thereof include an adazolyl group, an indazolyl group, a benzothiazolyl group, a benzisothiazolyl group, a 2,1,3-benzothiadiazolyl group, a benzoxazolyl group, a benzisoxazolyl group, a 2,1,3-benzoxadiazolyl group, a quinolyl group, an isoquinolyl group, a quinoxalyl group, a quinazolyl group, a carbazolyl group, a 9-phenylcarbazolyl group, a 9-(4-biphenylyl)carbazolyl group, a dibenzothienyl group, a dibenzofuranyl group, a phenoxazinyl group, a phenothiazinyl group, a phenazine group, and a thianthrenyl group.

[0032] (heteroaromatic group) R １ ~R １３ Examples of the optionally substituted monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms as (a-2) (hereinafter also referred to as "group represented by (a-2)") include monocyclic, linked or fused ring heteroaromatic groups having 3 to 36 carbon atoms and containing at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom and a sulfur atom on the aromatic ring.

[0033] Examples of the heteroaromatic group include a dibenzofuranyl group, a dibenzothionyl group, a carbazolyl group, a dibenzofuranylphenyl group, a dibenzothionylphenyl group, a carbazolylphenyl group, a pyrrolyl group, a thienyl group, a furyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a pyridyl group, a phenylpyridyl group, a pyridylphenyl group, a pyrimidyl group, a pyrazyl group, a 1,3,5-triazyl group, a 1,3,5-triazylphenyl group, a 1,3,5-triazylbiphenylyl group, and a 4,6-diphenyl-1,3,5-triazyl group. , an indolyl group, a benzothienyl group, a benzofuranyl group, a benzimidazolyl group, an indazolyl group, a benzothiazolyl group, a benzisothiazolyl group, a 2,1,3-benzothiadiazolyl group, a benzoxazolyl group, a benzisoxazolyl group, a 2,1,3-benzoxadiazolyl group, a quinolyl group, an isoquinolyl group, a quinoxalyl group, a quinazolyl group, a carbazolyl group, a 9-phenylcarbazolyl group, a 9-(4-biphenylyl)carbazolyl group, a dibenzothienyl group, a dibenzofuranyl group, a phenoxazinyl group, a phenothiazinyl group, a phenazine group, a thianthrenyl group, and the like.

[0034] In addition, R １ ~R １３ When the heteroaromatic group as (I) has a substituent, the substituent is preferably each independently a cyano group, a fluorine atom, a trifluoromethyl group, an alkyl group, an alkoxy group, an aromatic hydrocarbon group, a heteroaromatic group, or a trifluoromethylsulfonyloxy group. Among these, an alkyl group, an aromatic hydrocarbon group, or a heteroaromatic group is more preferred.

[0035] The alkyl group as the substituent is preferably a linear or branched alkyl group having 1 to 18 carbon atoms. １ ~R １３ When the aromatic hydrocarbon group as the alkyl group has a substituent, examples of the substituent include the same alkyl groups as those exemplified above.

[0036] The alkoxy group as the substituent is preferably a linear or branched alkoxy group having 1 to 18 carbon atoms. １ ~R １３ When the aromatic hydrocarbon group as the group has a substituent, examples of the substituent include the same as those of the alkoxy group exemplified above.

[0037] The aromatic hydrocarbon group as the substituent is the same as the above-mentioned R １ ~R １３ When the aromatic hydrocarbon group as the aromatic hydrocarbon group has a substituent, examples of the substituent include the same as those of the aromatic hydrocarbon group exemplified above.

[0038] The heteroaromatic group as the substituent is the R １ ~R １３ When the aromatic hydrocarbon group as the heteroaromatic group has a substituent, examples of the substituent include the same substituents as those given as examples of the heteroaromatic group.

[0039] (Group represented by formula (2)) R １ ~R １３ In the group represented by the above formula (2), R ａ and R ｂ Examples of the optionally substituted monocyclic, linked, or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms as (a-1) include the same as the group shown above.

[0040] R １ ~R １３ In the group represented by the above formula (2), R ａ and R ｂ Examples of the monocyclic, linked, or fused ring heteroaromatic group having 3 to 36 carbon atoms, which may have a substituent, include the same as the group represented by (a-2) above.

[0041] R １ ~R １３ In the group represented by the above formula (2), R ａ and R ｂExamples of the linear or branched alkyl group having 1 to 18 carbon atoms as the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an n-hexyl group, a cyclohexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group.

[0042] R １ ~R １３ In the group represented by the above formula (2), examples of the monocyclic, linked, or fused-ring aromatic hydrocarbon group having 6 to 30 carbon atoms and optionally having a substituent as Y include the same as the group represented by the above formula (a-1).

[0043] R １ ~R １３ In the group represented by the above formula (2), examples of the monocyclic, linked, or fused ring heteroaromatic group having 3 to 36 carbon atoms and optionally having a substituent as Y include the same as the group represented by the above formula (a-2).

[0044] (Group represented by formula (3)) In the group represented by formula (3), R １４ ~R １７ Examples of the optionally substituted monocyclic, linked, or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms as (a-1) include the same as the group described above.

[0045] In the group represented by the above formula (3), R １４ ~R １７ Examples of the optionally substituted monocyclic, linked, or fused ring heteroaromatic group having 3 to 36 carbon atoms as (a-1) include the same as the group represented by (a-2) above.

[0046] <Preferred embodiment of fused ring compound> In the fused ring compound represented by formula (1), R ５ and R ６ , or R ７ and R ８ When either of them is bonded to each other to form a benzene ring to form a group represented by the formula (3), R １ ~R ４It is preferable that at least one of the above is a group represented by the formula (2).

[0047] In the fused ring compound represented by formula (1), Y is preferably a single bond.

[0048] In the fused ring compound represented by formula (1), R ａ and R ｂ are each independently a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a chrysenyl group, a fluorenyl group, a benzofluorenyl group, a spirobifluorenyl group, a dibenzofuranyl group, a dibenzothionyl group, a carbazolyl group, a naphthylphenyl group, a phenylnaphthyl group, a naphthylnaphthyl group, a phenanthrylphenyl group, a dibenzofuranylphenyl group, a dibenzothionylphenyl group, or a carbazolylphenyl group.

[0049] In the fused ring compound represented by formula (1), n ​​is preferably 1.

[0050] In the fused ring compound represented by formula (1), R １ ~R １７ are each independently a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a dibenzofuranyl group, a dibenzothionyl group, a carbazolyl group, or a group represented by the above formula (2), provided that R １ ~R １７ At least one of the groups represented by formula (2) is a group represented by formula (2), and R ５ and R ６ , or R ７ and R ８ When either of them is bonded to each other to form a benzene ring to form a group represented by the formula (3), R １ ~R ４ It is preferable that at least one of the above is a group represented by the formula (2).

[0051] In the fused ring compound represented by formula (1), R １ ~R ４ It is preferable that any one of the above is a group represented by the formula (2).

[0052] <Physical Properties of Fused Ring Compound> Preferred physical properties of the fused ring compound represented by formula (1) are described below.

[0053] (HOMO Value) The HOMO value of the fused ring compound represented by formula (1) is not particularly limited, but from the viewpoint of compatibility with photoelectric conversion elements for image sensors, it is preferably 5.0 to 6.5 eV. Note that this HOMO value is a value obtained by measuring a vapor-deposited film using an atmospheric photoelectron yield spectrometer.

[0054] (Band Gap) The band gap of the fused ring compound represented by formula (1) is not particularly limited, but from the viewpoint of compatibility with photoelectric conversion elements for image sensors, it is preferably 2.5 to 4.0 eV. Note that this band gap is a value obtained from the wavelength edge of the absorption spectrum of the vapor-deposited film.

[0055] (LUMO Value) The LUMO value of the fused ring compound represented by formula (1) is not particularly limited, but from the viewpoint of compatibility with photoelectric conversion elements for image sensors, it is preferably 2.0 to 3.5 eV. Note that this LUMO value is a value obtained from the above-mentioned HOMO value and band gap.

[0056] (Glass Transition Temperature) The glass transition temperature of the fused ring compound represented by formula (1) is not particularly limited, but from the viewpoint of compatibility with photoelectric conversion elements for imaging devices, it is preferably 140° C. or higher. Note that this glass transition temperature is a value obtained by differential scanning calorimetry.

[0057] (Molecular Weight) The molecular weight of the fused ring compound represented by formula (1) is not particularly limited, but from the viewpoint of achieving both a high glass transition temperature and heat resistance stability during sublimation, it is preferably less than 1,000, and more preferably 680 or more and less than 1,000.

[0058] <Specific Examples of Fused Ring Compounds> Preferred examples of the fused ring compounds represented by formula (1) are shown below, but the fused ring compounds are not limited to these compounds.

[0059] Among the skeletons (A) to (G), (L) to (O), and (T) to (AH) shown in Tables 1 and 2, compounds in which the substituent A is a group n selected from the groups shown in Tables 3 and 4 are defined as (X-n). Among the skeletons (H) to (K), (P) to (S), and (AI) to (AP) shown in Tables 1 and 2, compounds in which the substituent A is a group n selected from the groups shown in Tables 3 and 4 and the substituent R is a group m selected from the groups shown in Tables 5 and 6 are defined as (X-nm). Here, X represents any symbol from A to AP, n represents any integer from 1 to 59, and m represents any lowercase alphabetic character from a to ax. For example, the compound (N-15) has a skeleton (N), and the substituent A of the skeleton is a di([1,1':4',1''-terphenyl]-4-yl)amino group. The compound (H-2f) has a skeleton (H), and the substituent A of the skeleton is a bisbiphenylylamino group, and the substituent R is a phenyl group.

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066] <Amine Compound> An amine compound according to one embodiment of the present disclosure is represented by the following formula (1).

[0067] In formula (1), R １ ~R １３ are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a hydroxy group, a thiol group, an allyl group, an optionally substituted monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms, or a group represented by the following formula (2), wherein R ５ and R６ , R ７ and R ８ At least one of these groups is linked to each other to form a benzene ring, thereby forming a group represented by the following formula (3).

[0068]

[0069]

[0070] In formula (2), R ａ ~R ｂ each independently represents a hydrogen atom, a deuterium atom, a monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, a monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms which may have a substituent, a group in which the aromatic hydrocarbon group and the heteroaromatic group are linked together, or a linear or branched alkyl group having 1 to 18 carbon atoms; R ａ and R ｂ may be bonded to each other to form a ring, and each Y independently represents a monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, a monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms which may have a substituent, or a single bond; n represents 1 or 2, and when Y is a single bond, n is 1, and when Y is not a single bond, n is 1 or 2; and when n is 2, multiple R ａ ~R ｂ may be the same or different; Y is an integer between adjacent R ａ and R ｂ In formula (3), R may be bonded to either or both of them to form a ring. １４ ~R １７ are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a hydroxy group, a thiol group, an allyl group, an optionally substituted monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms, or a group represented by the following formula (2), wherein R １ ~R １７At least one of R is a group represented by the formula (2), ５ and R ６ , or R ７ and R ８ When either of them is bonded to each other to form a benzene ring to form a group represented by the formula (3), R １ ~R ４ At least one of the above is a group represented by formula (2).

[0071] By virtue of having the specific structure, a material containing the amine compound represented by formula (1) can provide a photoelectric conversion element having a low dark current and excellent response. Therefore, the amine compound represented by formula (1) is suitably used as a material for organic electronic elements and photoelectric conversion elements.

[0072] The amine compound represented by formula (1) is ５ and R ６ , or R ７ and R ８ When either of them is bonded to each other to form a benzene ring to form a group represented by the formula (3), R １ ~R ４ The compound is the same as the fused ring compound represented by the formula (1) described above in the section "Material for photoelectric conversion element for imaging element" except that at least one of R １ ~R １７ Specific and preferred embodiments of the substituent in the above are the same as those of R in the fused ring compound represented by the above formula (1) explained in <<Material for photoelectric conversion element for imaging element>>. １ ~R １７ This is similar to the explanation for

[0073] <Preferred Amine Compound> In the amine compound represented by formula (1), R ａ and R ｂare each independently a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a chrysenyl group, a fluorenyl group, a benzofluorenyl group, a spirobifluorenyl group, a dibenzofuranyl group, a dibenzothionyl group, a carbazolyl group, a naphthylphenyl group, a phenylnaphthyl group, a naphthylnaphthyl group, a phenanthrylphenyl group, a dibenzofuranylphenyl group, a dibenzothionylphenyl group, or a carbazolylphenyl group.

[0074] In the amine compound represented by formula (1), n ​​is preferably 1.

[0075] In the amine compound represented by formula (1), R １ ~R １７ are each independently a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a dibenzofuranyl group, a dibenzothionyl group, a carbazolyl group, or a group represented by the formula (2), １ ~R １７ At least one of R is a group represented by the formula (2), ５ and R ６ , or R ７ and R ８ When either of them is bonded to each other to form a benzene ring to form a group represented by the formula (3), R １ ~R ４ It is preferable that at least one of the above is a group represented by the formula (2).

[0076] In the amine compound represented by formula (1), Y is preferably a single bond.

[0077] In the amine compound represented by formula (1), R １ ~R ４ It is preferable that any one of the above is a group represented by the formula (2).

[0078] <Physical Properties of Amine Compound> The preferred HOMO value, band gap, LUMO value, glass transition temperature, and molecular weight of the amine compound represented by formula (1) are the same as the preferred HOMO value, band gap, LUMO value, glass transition temperature, and molecular weight of the fused ring compound represented by formula (1) in the above-mentioned <<Material for Photoelectric Conversion Element for Image Sensor>>.

[0079] <Preferred Specific Examples of Amine Compounds> Preferred amine compounds represented by formula (1) are the same as the preferred fused ring compounds represented by formula (1) in the above-mentioned <<Materials for Photoelectric Conversion Elements for Imaging Elements>>.

[0080] <Uses of Amine Compound> The amine compound represented by formula (1) can be used as a material for an organic electronic device or a material for a photoelectric conversion device. That is, the material for an organic electronic device or a material for a photoelectric conversion device of this embodiment includes the amine compound represented by formula (1). Examples of materials for photoelectric conversion devices include materials for photoelectric conversion devices used in image sensors. Examples of materials for photoelectric conversion devices used in image sensors include charge transport materials for photoelectric conversion devices used in image sensors or charge blocking materials for photoelectric conversion devices used in image sensors. Examples of charge transport materials for photoelectric conversion devices used in image sensors include hole transport materials for photoelectric conversion devices used in image sensors. Examples of charge blocking materials for photoelectric conversion devices used in image sensors include electron blocking materials for photoelectric conversion devices used in image sensors. Examples of organic electronic devices include organic electroluminescence devices and organic photoelectric conversion devices. Examples of materials for organic electronic devices include materials for organic electroluminescence devices and materials for organic photoelectric conversion devices. The material for an organic electronic device containing the amine compound represented by formula (1) is preferably used as an organic thin film.

[0081] Hereinafter, a photoelectric conversion element for an image sensor according to this embodiment will be described as an example.

[0082] <<Photoelectric Conversion Element for Image Sensor>> The photoelectric conversion element for image sensor of this embodiment contains the charge transport material for photoelectric conversion element for image sensor described above. The configuration of the photoelectric conversion element for image sensor is not particularly limited, but examples thereof include the following configurations (i) to (v).

[0083] (i) first electrode / photoelectric conversion layer / second electrode (ii) first electrode / electron transport layer (hole blocking layer) / photoelectric conversion layer / second electrode (iii) first electrode / photoelectric conversion layer / hole transport layer (electron blocking layer) / second electrode (iv) first electrode / electron transport layer (hole blocking layer) / photoelectric conversion layer / hole transport layer (electron blocking layer) / second electrode (v) first electrode / electron transport layer (hole blocking layer) / photoelectric conversion layer / hole transport layer (electron blocking layer) / buffer layer / second electrode

[0084] The buffer layer may be replaced with a layer having a different name or function, as necessary. Examples of layers having a different name or function include a hole injection layer and a work function adjustment layer. The photoelectric conversion element for an imaging device may contain a charge transport material for a photoelectric conversion element for an imaging device or a charge blocking material for a photoelectric conversion element for an imaging device in at least one layer selected from the group consisting of an electron transport layer (hole blocking layer), a photoelectric conversion layer, a hole transport layer (electron blocking layer), and a buffer layer. The photoelectric conversion element for an imaging device preferably contains a charge transport material for a photoelectric conversion element for an imaging device or a charge blocking material for a photoelectric conversion element for an imaging device in the photoelectric conversion layer and / or hole transport layer (electron blocking layer), and more preferably contains a charge transport material for a photoelectric conversion element for an imaging device or a charge blocking material for a photoelectric conversion element for an imaging device in the hole transport layer (electron blocking layer). The charge transport material for a photoelectric conversion element for an imaging device or the charge blocking material for a photoelectric conversion element for an imaging device may be contained in a plurality of layers included in the photoelectric conversion element for an imaging device.

[0085] Hereinafter, the photoelectric conversion element for an image sensor according to this embodiment will be described in more detail using the configuration (v) above as an example, with reference to Fig. 1. Fig. 1 is a schematic cross-sectional view showing an example of the layered configuration of a photoelectric conversion element for an image sensor including a hole transport material for a photoelectric conversion element for an image sensor or an electron blocking material for a photoelectric conversion element for an image sensor according to this embodiment.

[0086] 1 includes, in this order, a substrate 1, a first electrode 2, an electron transport layer (hole blocking layer) 3, a photoelectric conversion layer 4, a hole transport layer (electron blocking layer) 5, a buffer layer 6, and a second electrode 7. Note that in the photoelectric conversion element for an image sensor of this embodiment, some of these layers may be omitted, and other layers may be added.

[0087] In the photoelectric conversion element 100 for an imaging device, light is incident from below the transparent first electrode 2. Furthermore, a voltage is applied to the photoelectric conversion element 100 for an imaging device so that, of the charges (holes and electrons) generated in the photoelectric conversion layer 4, the electrons move to the first electrode 2 and the holes move to the second electrode 7. That is, in the photoelectric conversion element 100 for an imaging device, the first electrode 2 serves as an electron collecting electrode and the second electrode 7 serves as a hole collecting electrode.

[0088] [Layer Containing Charge Transport Material for Photoelectric Conversion Element for Image Sensor] The photoelectric conversion element 100 for image sensors contains a material for photoelectric conversion elements for image sensors in at least one layer selected from the group consisting of the electron transport layer (hole blocking layer) 3, the photoelectric conversion layer 4, the hole transport layer (electron blocking layer) 5, and the buffer layer 6. The photoelectric conversion element 100 for image sensors preferably contains a charge transport material for photoelectric conversion elements for image sensors or a charge blocking material for photoelectric conversion elements for image sensors in the photoelectric conversion layer 4 and / or the hole transport layer (electron blocking layer) 5, and more preferably contains a charge transport material for photoelectric conversion elements for image sensors or a charge blocking material for photoelectric conversion elements for image sensors in the hole transport layer (electron blocking layer) 5. The charge transport material for photoelectric conversion elements for image sensors or the charge blocking material for photoelectric conversion elements for image sensors may be contained in multiple layers of the photoelectric conversion element 100 for image sensors.

[0089] Hereinafter, a photoelectric conversion element 100 for an imaging device in which the hole transport layer (electron blocking layer) 5 contains a hole transport material for a photoelectric conversion element for an imaging device or an electron blocking material for a photoelectric conversion element for an imaging device will be described.

[0090] [Substrate 1] The substrate is not particularly limited, and examples thereof include a glass plate, a quartz plate, a plastic plate, etc. In a configuration in which light is incident from the substrate 1 side, it is preferable that the substrate 1 has high transmittance to the wavelength of light (for example, a transmittance of 80% or more, preferably a transmittance of 90% or more).

[0091] [First electrode 2] A first electrode 2 is provided on the substrate 1. In the case of a photoelectric conversion element for an imaging device configured so that light passes through the first electrode 2 and enters the photoelectric conversion layer, it is preferable that the first electrode 2 has high transmittance (for example, a transmittance of 80% or more, preferably a transmittance of 90% or more) to the wavelength of the incident light.

[0092] There are no particular limitations on the transparent material used for the first electrode 2. From the viewpoint of excellent light transmittance, the material constituting the first electrode 2 may be, for example, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide, aluminum-doped tin oxide, magnesium-indium oxide, nickel-tungsten oxide, other metal oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, metal sulfides such as zinc sulfide, or the like.

[0093] In the case of a photoelectric conversion element for an imaging device configured so that light enters the photoelectric conversion layer only from the second electrode 7 side, the transmission characteristics of the first electrode 2 are not important. Therefore, examples of materials that can be used for the first electrode 2 in this case include gold, iridium, molybdenum, palladium, platinum, etc.

[0094] [Electron Transport Layer (Hole Blocking Layer) 3 ] The electron transport layer (hole blocking layer) 3 is provided between the first electrode 2 and the photoelectric conversion layer 4 .

[0095] The electron transport layer (hole blocking layer) 3 has the role of transporting electrons generated in the photoelectric conversion layer 4 to the first electrode 2 and the role of blocking holes generated in the photoelectric conversion layer 4 from moving to the first electrode 2.

[0096] The electron transport layer (hole blocking layer) 3 may have a single layer structure made of one or more materials, or may have a laminate structure made of multiple layers of the same or different compositions. The electron transport layer (hole blocking layer) 3 may have, for example, a two-layer structure including a layer made of a material specialized for hole blocking properties and adjacent to the photoelectric conversion layer 4, and a layer made of a material specialized for electron transport properties and adjacent to the first electrode 2.

[0097] The electron transport layer (hole blocking layer) 3 may be a layer containing a conventionally known electron transport material, such as bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis(2-methyl-8-quinolinolato)-4-(phenylphenolato)aluminum), 4,6-bis(3,5-di(pyridin-4-yl)phenyl)-2-methylpyrimidine, N,N'-diphenyl-1,4,5,8-naphthalenetetracarboxylic acid diimide, and N,N'-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxylic acid diimide.

[0098] [Photoelectric conversion layer 4] The photoelectric conversion layer 4 is provided between the electron transport layer (hole blocking layer) 3 and a hole transport layer (electron blocking layer) 5 described later. The photoelectric conversion layer 4 contains a material having a photoelectric conversion function.

[0099] The photoelectric conversion layer 4 may be made of either an organic or inorganic material, as long as it is capable of generating signal charges corresponding to the amount of received light. When the photoelectric conversion layer 4 is made of an organic material, it may have a single-layer structure made of one or more materials, or a laminate structure made of multiple layers of the same or different compositions. Materials used for the photoelectric conversion layer 4 include n-type and p-type semiconductors. N-type semiconductors are organic semiconductors with acceptor properties, and compounds that readily accept electrons and have high electron transport properties are used. P-type semiconductors are organic semiconductors with donor properties, and compounds that readily donate electrons and have high hole transport properties are used. When multiple materials are used for the photoelectric conversion layer 4, combinations include, for example, n-type and p-type semiconductors, n-type and compounds with lower acceptor properties than the n-type semiconductor, and p-type and compounds with lower donor properties than the p-type semiconductor. Each material may be used alone, or two or more materials may be used. The photoelectric conversion layer 4 may also contain a dye compound that excels in absorbing specific light. The dye compound may be a compound with lower acceptor properties than the n-type semiconductor, or a compound with lower donor properties than the p-type semiconductor. To improve photoelectric conversion efficiency, the photoelectric conversion layer 4 desirably contains a dye compound in addition to the n-type and p-type semiconductors. Examples of compounds contained in the photoelectric conversion layer 4 include coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, fullerene and its derivatives, azole derivatives such as imidazole, thiazole, thiadiazole, oxazole, oxadiazole, and triazole, naphthalenetetracarboxylic acid diimide, and hole transport materials. Among these, phthalocyanine and its derivatives, and fullerene and its derivatives are preferred. The photoelectric conversion layer 4 made of these materials may be formed, for example, by vapor deposition using a mixed powder of powders of the respective materials, or by co-evaporation of the respective materials in any ratio.

[0100] Specific examples of coumarin derivatives include coumarin 6 and coumarin 30. Specific examples of quinacridone derivatives include N,N-dimethylquinacridone. Specific examples of phthalocyanine derivatives include boron subphthalocyanine chloride, boron subnaphthalocyanine chloride (SubNC), F6-SubPC-OC6F5, and Cl6-SubPC-OC6. Specific examples of fullerenes and their derivatives include

[60] fullerene,

[70] fullerene, and [6,6]-phenyl-C61-methyl butyrate (

[60] PCBM). The hole transport material may be a known hole transport material. Examples of hole transport materials include aromatic tertiary amine compounds, naphthalene compounds, anthracene compounds, tetracene compounds, pentacene compounds, phenanthrene compounds, pyrene compounds, perylene compounds, fluorene compounds, carbazole compounds, indole compounds, pyrrole compounds, picene compounds, thiophene compounds, benzotrifuran compounds, benzotrithiophene compounds, naphthodithiophene compounds, naphthothienothiophene compounds, benzodifuran compounds, benzodithiophene compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, chrysenodithiophene compounds, benzothienobenzothiophene compounds, and indolocarbazole compounds. Among these, fluorene compounds, naphthodithiophene compounds, naphthothienothiophene compounds, benzodifuran compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, chrysenodithiophene compounds, benzothienobenzothiophene compounds, indolocarbazole compounds, and the like are preferred, and fluorene compounds, chrysenodithiophene compounds, benzothienobenzothiophene compounds, and indolocarbazole compounds are more preferred.

[0101] Specific examples of hole transport materials include 9,9'-(9,9'-spirobi[9H-fluorene]-2,7'-diyl)bis[9H-carbazole], 2,7-diphenyl[1]benzothieno[3,2-b][1]benzothiophene (DiPh-BTBT), benzo[1,2-b:3,4-b':5,6-b'']trifuran compounds, benzo[1,2-b:3,4-b':5,6-b'']trithiophene compounds, naphtho[1,2-b:5,6-b']dithiophene, naphtho[2,3-b]naphtho[2',3' :4,5]thieno[2,3-d]thiophene, benzo[1,2-b:4,5-b']difuran, benzo[1,2-b:4,5-b']dithiophene, benzo[1,2-b:4,5-b']bis[1]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, compounds represented by the following formula (ic-1), and compounds represented by the following formula (ic-2) are listed.

[0102]

[0103] The material having the photoelectric conversion function described above may be contained only in the photoelectric conversion layer 4, or may also be contained in layers other than the photoelectric conversion layer 4. For example, layers adjacent to the photoelectric conversion layer 4 (electron transport layer (hole blocking layer) 3, hole transport layer (electron blocking layer) 5) may contain a material having the photoelectric conversion function.

[0104] [Hole Transport Layer (Electron Blocking Layer) 5] The hole transport layer (electron blocking layer) 5 is provided between the photoelectric conversion layer 4 and a buffer layer 6 described later.

[0105] The hole transport layer (electron blocking layer) 5 has a role of transporting holes generated in the photoelectric conversion layer 4 toward the second electrode 7, and a role of blocking electrons generated in the photoelectric conversion layer 4 from moving toward the second electrode 7. The hole transport layer (electron blocking layer) 5 preferably contains the above-mentioned charge transport material for a photoelectric conversion element for an imaging element or the charge blocking material for a photoelectric conversion element for an imaging element.

[0106] The hole transport layer (electron blocking layer) 5 may have a single layer structure made of one or more materials, or may have a laminate structure made of multiple layers of the same or different compositions. The hole transport layer (electron blocking layer) 5 may have, for example, a two-layer structure including a layer made of a material specialized for electron blocking properties and adjacent to the photoelectric conversion layer 4, and a layer made of a material specialized for hole transport properties and adjacent to the buffer layer 6.

[0107] The hole transport layer (electron blocking layer) 5 may further contain a conventionally known hole transport material in addition to the above-mentioned material for a photoelectric conversion element for an imaging device. Preferred compounds and specific examples of the conventionally known hole transport material include the same compounds as those described in the section on the photoelectric conversion layer 4.

[0108] [Buffer Layer 6] A buffer layer 6 is provided between the hole transport layer (electron blocking layer) 5 and the second electrode 7 described later. When the second electrode 7 is formed by sputtering, the buffer layer 6 serves to reduce damage to the organic layer (e.g., the hole transport layer (electron blocking layer) 5) during sputtering. The buffer layer 6 also serves to efficiently accept holes from the hole transport layer (electron blocking layer) 5 by adjusting the work function of the buffer layer 6, and is also called a hole injection layer or a work function adjustment layer.

[0109] The material constituting the buffer layer 6 may be a known material, such as naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN), or the like.

[0110] [Second Electrode 7] A second electrode 7 is provided on the buffer layer 6. The material of the second electrode 7 is not particularly limited, and examples thereof include sodium, a sodium-potassium alloy, magnesium, lithium, a magnesium / copper mixture, silver, a magnesium / silver mixture, aluminum, a magnesium / aluminum mixture, a magnesium / indium mixture, and aluminum / aluminum oxide (Al ２ O ３) mixtures, indium, lithium / aluminum mixtures, rare earth metals, etc.

[0111] [Method of Forming Each Layer] Each layer other than the first electrode 2 and the second electrode 7 can be formed by thinning the material of each layer (and, if necessary, materials such as a binder resin, a solvent, etc.) by a known method such as vacuum deposition, spin coating, casting, or the LB (Langmuir-Blodgett) method. The thickness of each layer other than the first electrode 2 and the second electrode 7 is not particularly limited and can be selected appropriately depending on the situation. The thickness of each layer other than the first electrode 2 and the second electrode 7 is usually in the range of 5 nm to 5 μm.

[0112] The first electrode 2 and the second electrode 7 can be formed by thinning an electrode material by a method such as vapor deposition or sputtering. When the first electrode 2 and the second electrode 7 have a pattern, the pattern can be formed, for example, through a mask of a desired shape. Alternatively, after forming a thin film by vapor deposition, sputtering, or the like, a pattern of a desired shape can be formed by photolithography.

[0113] The film thickness of the first electrode 2 and the second electrode 7 may be 1 μm or less, and is preferably 10 nm or more and 200 nm or less.

[0114] The materials constituting the first electrode 2 and the second electrode 7 may be interchanged as necessary (also called an inverted structure). In such a structure, light passes through the second electrode 7 and enters the photoelectric conversion layer 4, forming a photoelectric conversion element for an imaging device.

[0115] In the above embodiments, the photoelectric conversion element for an imaging device preferably includes an electrode, a photoelectric conversion layer, and a hole transport layer, the photoelectric conversion layer preferably containing fullerene, and the hole transport layer preferably containing the material for a photoelectric conversion element for an imaging device described above. More specifically, the photoelectric conversion element for an imaging device preferably includes a first electrode, a photoelectric conversion layer, a hole transport layer, and a second electrode, in this order. The photoelectric conversion element for an imaging device may include an electron transport layer between the first electrode and the photoelectric conversion layer. The photoelectric conversion element for an imaging device may also include a buffer layer between the hole transport layer and the second electrode. In the photoelectric conversion element for an imaging device, the photoelectric conversion layer preferably contains fullerene.

[0116] An imaging element including a photoelectric conversion element according to this embodiment can be applied to, for example, imaging elements in digital cameras, digital video cameras, etc., and imaging elements built into mobile phones, etc. Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments.

[0117] The present invention will be described in more detail below based on examples, but the present invention should not be construed as being limited to these examples.

[0118] [Synthesis Example 1] Synthesis of 2-(4-chloro-2-(pyrrolidin-1-yldiazenyl)phenyl)[1,1-binaphthalene]

[0119] Under an argon atmosphere, a 300 mL two-necked flask was charged with [1,1-binaphthalen]-2-yl triflate (6.04 g, 15.0 mmol), 4-chloro-[2-(pyrrolidin-1-yldiazenyl)phenyl]boronic acid (4.56 g, 18.0 mmol), palladium acetate (67.4 mg, 0.300 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyldicyclohexyl (246 mg, 0.600 mmol), 4M aqueous potassium phosphate trihydrate (7.50 mL, 30 mmol), and 1,4-dioxane (150 mL) and stirred at 100°C for 6 hours. The mixture was cooled to room temperature, transferred to a separatory funnel, and extracted with ethyl acetate. After washing with brine, the mixture was dried over magnesium sulfate and evaporated under reduced pressure to give a black oil. Silica gel chromatography (Rf value = 0.56, hexane / toluene = 1 / 1) was used to obtain 4.2 g (9.13 mmol, yield 61%) of a white solid of (2-(4-chloro-2-(1-naphthalenyl)-2-(pyrrolidin-1-yldiazenyl)phenyl)[1,1-binaphthalene]. This was used in the next step without further purification.

[0120] [Synthesis Example 2] Synthesis of 2-chloronaphtho[1,2-g]chrysene

[0121] Under an argon atmosphere, (2-(4-chloro-2-(1-naphthalenyl)-2-(pyrrolidin-1-yldiazenyl)phenyl)[1,1-binaphthalene] (4.09 g, 8.85 mmol) and chlorobenzene (44 mL) were placed in a 100 mL two-necked flask, and the solution was cooled to 0°C with stirring. Iron tribromide (3.40 g, 11.5 mmol) was added, and the mixture was stirred at room temperature for 1 hour. Pure water and methanol were added to the reaction solution to precipitate a solid. Recrystallization was carried out using a mixed solvent of toluene and ethanol to obtain 0.80 g (2.20 mmol, 20% yield) of a white solid, 2-chloronaphtho[1,2-g]chrysene. The compound was identified as follows: １ This was measured by H-NMR. １ H-NMR (DMSO-d ６) δ (ppm): 8.99 (d, J = 1.6 Hz, 1H), 8.96 (d, J = 8.8 Hz, 2H), 8.91 (d, J = 9.2 Hz, 1H), 8.25 (dd, J = 8.8 Hz, 2.0 Hz, 2H), 8.12 (dd, J = 8.8Hz, 2.0Hz, 2H), 7.92 (dd, J = 8.4Hz, 3.6Hz, 2H), 7.81 (dd, J =8.8Hz, 2.0Hz, 1H), 7.55-7.62 (m, 2H), 7.30 (t, J = 7.6Hz, 2H)

[0122] [Synthesis Example 1] Synthesis of 2-[bis(4-biphenylyl)amino]naphtho[1,2-g]chrysene (compound (B-2))

[0123] Under an argon atmosphere, 2-chloronaphtho[1,2-g]chrysene (0.80 g, 2.2 mmol), bisbiphenylylamine (0.78 g, 2.4 mmol), palladium acetate (9.9 mg, 44 μmmol), tri-t-butylphosphine (25% xylene solution) (71 mg, 88 μmmol), sodium tert-butoxide (0.32 g, 3.3 mmol), and xylene (22 mL) were added to a 50 mL two-neck flask and stirred at 140°C for 4 hours. After cooling to room temperature, purified water and methanol were added, and the crystallized solid was recovered. The solid was then treated with activated carbon in chlorobenzene at 140°C and stirred. The solution obtained by hot filtration was concentrated and recrystallized from a mixed solvent of chlorobenzene and butanol to obtain 0.93 g of compound (B-2) (1.4 mmol, yield 63%). The sublimation temperature of the compound (B-2) was 330°C, and it was confirmed that the sublimed compound (B-2) was in a glassy state. １ This was measured by H-NMR. １ H-NMR (DMSO-d ６) δ (ppm): 8.87 (d, J = 9.6 Hz, 1H), 8.83 (d, J = 9.6 Hz, 1H), 8.51 (s, 1H), 8 .49 (d, J=6.4Hz, 2H), 8.21 (d, J=8.8Hz, 1H), 8.10 (d, J=8.8Hz, 1H), 8.0 9 (d, J = 7.6Hz, 1H), 8.04 (d, 7.6Hz, 1H), 7.93 (d, J = 8.4Hz, 1H), 7.89 (d , J=7.89, 1H), 7.67-7.71 (m, 8H), 7.44-7.56 (m, 7H), 7.26-7.36 (m, 8H)

[0124] Synthesis Example 3: Synthesis of 1-((5-chloro-2-(1-(phenanthrene-9-yl)naphthalen-2-yl)phenyl)diazenyl)pyrrolidine

[0125] Under an argon atmosphere, 1-(9-phenanthrenyl)2-naphthalenyl triflate (3.16 g, 6.98 mmol), 4-chloro-[2-(pyrrolidin-1-yldiazenyl)phenyl]boronic acid (1.95 g, 7.68 mmol), palladium acetate (94.1 mg, 0.419 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyldicyclohexyl (344 mg, 0.838 mmol), 2M aqueous potassium phosphate trihydrate (6.98 mL, 14.0 mmol), and 1,4-dioxane (34.9 mL) were placed in a 300 mL two-neck flask and stirred at 100°C for 6 hours. The mixture was cooled to room temperature, transferred to a separatory funnel, and extracted with ethyl acetate. After washing with brine, the mixture was dried over magnesium sulfate and evaporated under reduced pressure to give a black oil. Recrystallization using a mixed solvent of ethanol and heptane gave 4.2 g (9.13 mmol, yield 61%) of a white solid of 1-((5-chloro-2-(1-(phenanthren-9-yl)naphthalen-2-yl)phenyl)diazenyl)pyrrolidine.

[0126] [Synthesis Example 4] Synthesis of 16-chlorotribenzo[c,g,p]chrysene

[0127] Under an argon atmosphere, 1-((5-chloro-2-(1-(phenanthren-9-yl)naphthalen-2-yl)phenyl)diazenyl)pyrrolidine (1.77 g, 3.46 mmol) and chlorobenzene (34.6 mL) were placed in a 100 mL two-necked flask, and the solution was cooled to 0°C with stirring. Iron tribromide (1.33 g, 4.49 mmol) was added, and the mixture was stirred at room temperature for 1 hour. Purified water was added to the reaction solution, and the mixture was separated into chloroform and purified water. The resulting organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. The resulting oil was diluted with toluene, and activated carbon (0.20 g) was added. The mixture was heated and stirred at 100°C for 15 minutes, and then suction filtered. The resulting liquid was concentrated and recrystallized from a mixed solvent of toluene and butanol to obtain 0.80 g (1.94 mmol, 56% yield) of a light brown powder of 16-chlorotribenzo[c,g,p]chrysene. １ This was measured by H-NMR. １ H-NMR (DMSO-d ６ ) δ (ppm): 9.07 (d, J = 9.2Hz, 1H), 8.94 (d, J = 9.2Hz, 1H), 8.91 (m, 1H), 8.76 (d , J=8.0Hz, 1H), 8.72 (d, 2Hz, 1H), 8.67-8.70 (m, 1H), 8.26 (d, J=8.8Hz, 1H), 8 .11 (d, J=7.2Hz, 1H), 8.06 (d, J=8.06, 1H), 7.79-7.87 (m, 4H), 7.64 (t, J=7. 2Hz, 1H), 7.56 (t, J=7.2Hz, 1H), 7.35 (t, J=7.2Hz, 1H), 7.29 (t, J=7.2Hz, 1H)

[0128] [Synthesis Example 2] Synthesis of 16-[bis(4-biphenylyl)amino]tribenzo[c,g,p]chrysene (compound (N-2))

[0129] Under an argon atmosphere, 16-chlorotribenzo[c,g,p]chrysene (0.78 g, 1.89 mmol), bisbiphenylylamine (0.668 g, 2.08 mmol), palladium acetate (8.48 mg, 37.8 μmmol), tri-t-butylphosphine (25% xylene solution) (61.1 mg, 75.6 μmmol), sodium tert-butoxide (0.236 g, 2.46 mmol), and xylene (19 mL) were placed in a 50 mL two-neck flask and stirred at 140°C for 4 hours. After cooling to room temperature, purified water and methanol were added, and the crystallized solid was collected. The solid was then treated with activated carbon and stirred in chlorobenzene at 140°C. The solution obtained by hot filtration was concentrated and recrystallized from a mixed solvent of chlorobenzene and butanol to obtain 0.90 g of compound (N-2) (1.30 mmol, yield 69%). The sublimation temperature of compound (N-2) was 340°C, and it was confirmed that the sublimed compound (N-2) was in a glassy state. The compound was identified as follows: １ This was measured by H-NMR. １ H-NMR (DMSO-d ６ ) δ (ppm): 8.94 (d, 9.6Hz, 1H), 8.87 (d, 9.6Hz, 1H), 8.79 (d, 7.6Hz, 1H), 8.68 (d, J=7.6Hz, 1H), 8.29 (d, J = 7.6Hz, 1H), 8.22 (s, 1H), 8.21 (d, J = .6Hz, 1H), 8.07 (d, J = 8.8Hz, 1H), 8 .04 (d, J=8.8Hz, 1H), 8.88 (d, J=8.0Hz, 1H), 7.69-7.74 (m, 8H), 7.65 (t, J =7.6Hz, 1H), 7.60 (t, J = 7.6Hz, 1H), 7.46-7.54 (m, 6H), 7.23-7.41 (m, 9H)

[0130] [Synthesis Example 3] Synthesis of 16-[N,N-bis(naphthalen-2-yl)amino]tribenzo[c,g,p]chrysene (compound (N-17))

[0131] Under an argon atmosphere, 16-chlorotribenzo[c,g,p]chrysene (2.04 g, 4.94 mmol), N,N-bis(2-naphthalenyl)amine (1.40 g, 5.19 mmol), palladium acetate (22.2 mg, 98.8 μmmol), tri-t-butylphosphine (25% xylene solution) (240 mg, 296 μmmol), sodium tert-butoxide (617 g, 6.42 mmol), and xylene (50 mL) were placed in a 100 mL two-neck flask and stirred at 140°C for 6 hours. After cooling to room temperature, purified water and hexane were added, and the crystallized solid was collected. The solid was then treated with activated carbon and stirred in toluene at 100°C. The solution obtained by hot filtration was concentrated and subjected to column chromatography using silica gel with a mixed solvent of toluene and hexane to obtain 1.50 g of compound (N-17) (4.94 mmol, yield 47%). The sublimation temperature of compound (N-17) was 330°C, and it was confirmed that the sublimed compound (N-17) was in a glassy state. The compound was identified as follows: １ This was measured by H-NMR. １ H-NMR (DMSO-d ６ ) δ (ppm): 8.94 (d, J = 9.2 Hz, 1H), 8.85 (d, J = 9.2 Hz, 1H), 8.72 (d, J = 7.6 Hz, 1H), 8.63 (d, J = 8.0Hz, 1H), 8.29-8.12(m, 3H), 8.11-8.00(m, 2H), 7.97(d, J=9.2Hz, 2H), 7.94-7.89(m, 2 H), 7.85 (d, J = 8.0 Hz, 1H), 7.81-7.72 (m, 2H), 7.67 (d, J = 2.4Hz, 2H), 7.58 (t, J = 7.6Hz, 1H) ), 7.54-7.39 (m, 9H), 7.32 (t, J = 7.6Hz, 1H), 7.22 (t, J = 7.8Hz, 1H), 6.92 (t, J = 7.8Hz, 1H)

[0132] [Synthesis Example 4] Synthesis of 16-[N-phenyl-N-(9-phenyl-2-carbazolyl)amino]tribenzo[c,g,p]chrysene (compound (N-33))

[0133] Under an argon atmosphere, 16-chlorotribenzo[c,g,p]chrysene (2.20 g, 5.33 mmol), N-(biphenyl-4-yl)-9-phenylcarbazol-2-amine (2.23 g, 5.43 mmol), palladium acetate (23.9 mg, 0.11 mmol), tri-t-butylphosphine (25% xylene solution) (0.172 mg, 0.21 μmmol), sodium tert-butoxide (0.666 g, 6.93 mmol), and xylene (53 mL) were placed in a 100 mL two-neck flask and stirred at 140°C for 4 hours. After cooling to room temperature, purified water and methanol were added to the mixture, and the crystallized solid was collected. The solid was then treated with activated carbon and stirred in toluene at 100°C. The solution obtained by hot filtration was concentrated and recrystallized from a mixed solvent of toluene and butanol to obtain 3.79 g of compound (N-33) (4.82 mmol, yield 90%). The sublimation temperature of compound (N-33) was 350°C, and it was confirmed that the sublimed compound (N-33) was in a glassy state. The compound was identified as follows: １ This was measured by H-NMR. １ H-NMR (DMSO-d ６ ) δ (ppm): 8.66 (d, J = 9.2Hz, 2H), 8.59 (d, J = 8.0Hz, 1H), 8.49 (d, J = 7.6Hz, 1H), 8.42 (d, J = 1.6Hz, 1H), 8.24 (d, J = 8.0Hz, 1H), 8. 18(d, J=8.8Hz, 1H), 8.09(t, J=7.2Hz, 2H), 8.03(t, J=7.6Hz, 2H), 7.93(d, J=7.2Hz, 1H), 7.65-7.59(m, 2H), 7.59-7.09(m, 24H)

[0134] [Synthesis Example 5] Synthesis of 16-[N-(4-(dibenzofuran-4-yl)phenyl)-N-(triphenylen-2-yl)amino]tribenzo[c,g,p]chrysene (compound (N-42))

[0135] Under an argon atmosphere, 16-chlorotribenzo[c,g,p]chrysene (1.20 g, 2.91 mmol), N-(4-(dibenzofuran-4-yl)phenyl)-N-(triphenylen-2-yl)amine (1.44 g, 2.96 mmol), palladium acetate (13.0 mg, 58.1 μmmol), tri-t-butylphosphine (25% xylene solution) (94.1 mg, 116 μmmol), sodium tert-butoxide (0.363 g, 3.78 mmol), and xylene (29 mL) were placed in a 50 mL two-neck flask and stirred at 140°C for 6 hours. After cooling to room temperature, purified water and hexane were added to the mixture, and the crystallized solid was collected. The solid was then treated with activated carbon and stirred in toluene at 100°C. The solution obtained by hot filtration was concentrated and recrystallized from a mixed solvent of toluene and hexane to obtain 1.50 g of compound (N-42) (4.94 mmol, yield 47%). The sublimation temperature of compound (N-42) was 330°C, and it was confirmed that the sublimed compound (N-42) was in a glassy state. The compound was identified as follows: １ This was measured by H-NMR. １ H-NMR (DMSO-d ６ ) δ (ppm): 8.78 (d, J = 9.2 Hz, 1H), 8.73 (d, J = 9.2 Hz, 1H), 8.70-8.65 (m, 2H), 8.65- 8.58 (m, 4H), 8.56 (d, J = 7.6Hz, 1H), 8.48 (d, J = 7.6Hz, 1H), 8.4 (d, J = 8.0Hz, 1H), 8 .32(d, J=8.0Hz, 1H), 8.21(d, J=8.4Hz, 1H), 8.11-7.91(m, 7H), 7.72-7.55(m, 7H) ), 7.55-7.43 (m, 7H), 7.43-7.33 (m, 2H), 7.29-7.12 (m, 4H), 7.04 (t, J = 7.6Hz, 1H)

[0136] [Synthesis Example 6] Synthesis of 16-[4-(N,N-bis(4-biphenylyl)amino)phenyl]tribenzo[c,g,p]chrysene (compound (N-46))

[0137] Under an argon atmosphere, 16-chlorotribenzo[c,g,p]chrysene (1.88 g, 4.55 mmol), 4-(N,N-bis(4-biphenylyl)amino)phenylboronic acid (2.62 g, 5.01 mmol), XPhos Pd G4 (39.2 mg, 45.5 μmmol), 4 M aqueous potassium phosphate tribasic solution (1.71 mL, 6.83 mmol), and 1,4-dioxane (50 mL) were added to a 100 mL two-neck flask and stirred at 70 °C for 5 hours. After cooling to room temperature, purified water and hexane were added, and the crystallized solid was recovered. The solid was then treated with activated carbon in toluene at 100 °C and stirred. The solution obtained by hot filtration was concentrated and recrystallized from toluene to obtain 3.40 g of compound (N-46) (4.39 mmol, 97% yield). The sublimation temperature of compound (N-46) was 330°C, and it was confirmed that the sublimed compound (N-46) was in a glassy state. １ This was measured by H-NMR. １ H-NMR (DMSO-d ６ ) δ (ppm): 9.09 (d, J = 7.2 Hz, 1H), 9.02-8.96 (m, 2H), 8.94-8.87 (m, 1H), 8.87-8.81 ( m, 1H), 8.76 (d, J = 8.0Hz, 1H), 8.26 (d, J = 8.8Hz, 1H), 8.14-8.05 (m, 3H), 7.88 (d, J = 8 .4Hz, 1H), 7.86-7.79(m, 4H), 7.69-7.60(m, 9H), 7.55(t, J=7.6Hz, 1H), 7.46(t, J= 7.6Hz, 4H), 7.40-7.31(m, 3H), 7.28(td, J=7.6Hz, 1.6Hz, 1H), 7.20(t, J=8.4Hz, 6H)

[0138] (Comparative Example 1) Compound (X1) represented by the following formula was used as Comparative Example 1. Compound (X1) was synthesized according to the method disclosed in JP-A-2019-034939.

[0139] (Glass transition temperature) Measurement was performed using a DSC7020 manufactured by Hitachi High-Tech Science Corp. The results are shown in Table 7.

[0140] (HOMO Value, Band Gap, LUMO Value) The HOMO value of the vapor-deposited film of the above compound (100 nm thick film formed on a quartz substrate at a rate of 0.10 nm / sec) and the band gap were calculated from the wavelength edge of the absorption spectrum. In addition, the LUMO value was calculated from the HOMO value and the band gap. The HOMO value of the vapor-deposited film was measured using an atmospheric photoelectron spectrometer (AC-3) manufactured by Riken Keiki Co., Ltd., and the absorption spectrum was measured using an ultraviolet-visible-near-infrared spectrophotometer (V-750) manufactured by JASCO Corporation. The results are shown in Table 7.

[0141]

[0142] (Element Example 1: Preparation of Photoelectric Conversion Element for Image Sensor Using Compound (B-2)) As shown in FIG. 1 , a photoelectric conversion element 100 for an image sensor having a layered structure consisting of a substrate 1 / first electrode 2 / electron transport layer (hole blocking layer) 3 / photoelectric conversion layer 4 / hole transport layer (electron blocking layer) 5 / buffer layer 6 / second electrode 7 was prepared, and its characteristics were evaluated.

[0143] (Preparation of Substrate 1 and First Electrode 2) A glass substrate with an indium-tin oxide (ITO) transparent electrode, on which a 2 mm wide stripe-patterned ITO film (thickness: 110 nm) was formed, was prepared as a substrate having a first electrode on its surface. The substrate was then washed with isopropyl alcohol and then subjected to surface treatment by ozone ultraviolet cleaning.

[0144] (Vacuum deposition) Each layer was laminated on the surface-treated substrate after cleaning by vacuum deposition. Specifically, a glass substrate with an ITO transparent electrode was placed in a vacuum deposition chamber, and a 7.0 × 10 －５The pressure was reduced to 100 Pa. Then, each layer was fabricated in the following order. (1) Fabrication of Electron Transport Layer (Hole Blocking Layer) 3) Sublimation-purified 4,6-bis(3,5-di(pyridin-4-yl)phenyl)-2-methylpyrimidine was deposited at a rate of 0.10 nm / sec to form a 10 nm film, thereby fabricating the electron transport layer (hole blocking layer) 3. (2) Fabrication of Photoelectric Conversion Layer 4 2Ph-BTBT, F6-SubPc-OC6F5, and fullerene (C60) were co-evaporated at a deposition rate ratio of 4:4:2 to form a 200 nm film. The film formation rate was 0.15 nm / sec. (3) Fabrication of Hole Transport Layer (Electron Blocking Layer) 5 Sublimation-purified compound (B-2) was deposited at a rate of 0.10 nm / sec to form a 10 nm film, thereby fabricating the hole transport layer 5. (4) Preparation of Buffer Layer 6 Sublimation-purified 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN) was deposited at a rate of 0.10 nm / sec to form a 10 nm thick buffer layer 6.

[0145] (5) (Fabrication of Second Electrode 7) A metal mask was placed perpendicular to the ITO stripes on the substrate, and the second electrode 7 was formed. The second electrode was formed by depositing silver to a thickness of 80 nm. The silver deposition rate was 0.1 nm / sec.

[0146] By the above method, an area of ​​4 mm ２ An imaging photoelectric conversion element having the above structure was fabricated. The thickness of each layer was measured using a stylus film thickness meter (DEKTAK, manufactured by Bruker). The fabricated element was sealed in a nitrogen atmosphere glove box with oxygen and moisture concentrations of 1 ppm or less. Sealing was performed using a glass sealing cap and bisphenol F-type epoxy resin (manufactured by Nagase ChemteX Corporation).

[0147] (Element Example-2) to (Element Example-5) Photoelectric conversion elements for imaging devices of Element Example-2 to -5 were prepared in the same manner as in Element Example-1, except that in preparing the hole transport layer 104 of Element Example-1, compound (N-2), (N-17), (N-33), or (N-46) was used instead of compound (B-2).

[0148] (Element Comparative Example-1) A photoelectric conversion element for an imaging element of Element Comparative Example-1 was prepared in the same manner as in Element Example-1, except that compound (X1) was used instead of compound (B-2) in the preparation of the hole transport layer 104 of Element Example-1.

[0149] (Measurement of dark current, external quantum efficiency, and response time) A voltage of 2.5 V (absolute value) was applied to the photoelectric conversion element for an image sensor fabricated as described above so that electrons were transported to the first electrode 2 side and holes were transported to the second electrode 7 side. The current in a dark place (dark current), external quantum efficiency, and response time were evaluated. The dark current was evaluated using a Keithley Source Measure Unit 2636B. The external quantum efficiency was measured using a solar cell spectral response measurement device (Soma Optical Co., Ltd.) with irradiated light of a wavelength of 560 nm and an intensity of 50 μW / cm. ２ The response time was measured by irradiating a light pulse and measuring the time it took for the current value to return to the value before irradiation.

[0150] The results are shown in Table 8. The results shown in Table 8 are relative values ​​with the result of Comparative Element 1 set as the reference value (1.00). The lower the dark current value, the better the performance, the higher the external quantum efficiency value, and the shorter the response time, the better the performance.

[0151] The compounds used in the examples are listed below.

[0152]

[0153] As shown in Table 8, the elements of the examples using the specific materials for photoelectric conversion elements for image pickup elements had suppressed dark current and were superior in response compared to the elements of the comparative examples.

[0154] REFERENCE SIGNS LIST 1 Substrate 2 First electrode 3 Electron transport layer (hole blocking layer) 4 Photoelectric conversion layer 5 Hole transport layer (electron blocking layer) 6 Buffer layer 7 Second electrode 100 Photoelectric conversion element for imaging device

Claims

1. A material for a photoelectric conversion element for an imaging element, comprising a compound represented by the following formula (1): In formula (1), R １ ~R １３ are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a hydroxy group, a thiol group, an allyl group, an optionally substituted monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms, or a group represented by the following formula (2), wherein R ５ and R ６ , R ７ and R ８ At least one of these groups is linked to each other to form a benzene ring, thereby forming a group represented by the following formula (3). In formula (2), R ａ ~R ｂ each independently represents a hydrogen atom, a deuterium atom, a monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, a monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms which may have a substituent, a group in which the aromatic hydrocarbon group and the heteroaromatic group are linked together, or a linear or branched alkyl group having 1 to 18 carbon atoms; R ａ and R ｂ may be bonded to each other to form a ring, and each Y independently represents a monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, a monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms which may have a substituent, or a single bond; n represents 1 or 2, and when Y is a single bond, n is 1, and when Y is not a single bond, n is 1 or 2; and when n is 2, multiple R ａ ~R ｂ may be the same or different; Y is an integer between adjacent R ａ and R ｂ In formula (3), R may be bonded to either or both of them to form a ring. １４ ~R １７ are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a hydroxy group, a thiol group, an allyl group, an optionally substituted monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms, or a group represented by the formula (2). １ ~R １７ At least one of the above is a group represented by formula (2).

2. R ５ and R ６ , or R ７ and R ８ When either of them is bonded to each other to form a benzene ring to form a group represented by the formula (3), R １ ~R ４ The material for a photoelectric conversion element for an imaging element according to claim 1 , wherein at least one of the following is a group represented by formula (2):

3. The material for a photoelectric conversion element for an imaging element according to claim 1, wherein Y is a single bond.

4. An amine compound represented by the following formula (1): In formula (1), R １ ~R １3 are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a hydroxy group, a thiol group, an allyl group, an optionally substituted monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms, or a group represented by the following formula (2), wherein R ５ and R ６ , R ７ and R ８ At least one of these groups is linked to each other to form a benzene ring, thereby forming a group represented by the following formula (3). In formula (2), R ａ ~R ｂ each independently represents a hydrogen atom, a deuterium atom, a monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, a monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms which may have a substituent, a group in which the aromatic hydrocarbon group and the heteroaromatic group are linked together, or a linear or branched alkyl group having 1 to 18 carbon atoms; R ａ and R ｂ may be bonded to each other to form a ring, and each Y independently represents a monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, a monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms which may have a substituent, or a single bond; n represents 1 or 2, and when Y is a single bond, n is 1, and when Y is not a single bond, n is 1 or 2; and when n is 2, multiple R ａ ~R ｂ may be the same or different; Y is an integer between adjacent R ａ and R ｂ In formula (3), R may be bonded to either or both of them to form a ring. １４ ~R １７ are each independently a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a hydroxy group, a thiol group, an allyl group, an optionally substituted monocyclic, linked or fused ring aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted monocyclic, linked or fused ring heteroaromatic group having 3 to 36 carbon atoms, or a group represented by the following formula (2), wherein R １ ~R １７ At least one of R is a group represented by the formula (2), ５ and R ６ , or R ７ and R ８ When either of them is bonded to each other to form a benzene ring to form a group represented by the formula (3), R １ ~R ４ At least one of the above is a group represented by formula (2).

5. R ａ and R ｂ are each independently a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a chrysenyl group, a fluorenyl group, a benzofluorenyl group, a spirobifluorenyl group, a dibenzofuranyl group, a dibenzothionyl group, a carbazolyl group, a naphthylphenyl group, a phenylnaphthyl group, a naphthylnaphthyl group, a phenanthrylphenyl group, a dibenzofuranylphenyl group, a dibenzothionylphenyl group, or a carbazolylphenyl group.

6. The amine compound of claim 4, wherein n is 1.

7. R １ ~R １７ are each independently a hydrogen atom, a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a dibenzofuranyl group, a dibenzothionyl group, a carbazolyl group, or a group represented by the formula (2), １ ~R １７ At least one of R is a group represented by the formula (2), ５ and R ６ , or R ７ and R ８ When either of them is bonded to each other to form a benzene ring to form a group represented by the formula (3), R １ ~R ４ The amine compound according to claim 4, wherein at least one of the following is a group represented by formula (2):

8. The amine compound according to claim 4, wherein Y is a single bond.

9. R １ ~R ４ The amine compound according to claim 4, wherein any one of the following is a group represented by formula (2):

10. The amine compound according to any one of claims 4 to 9, which has a HOMO value of 5.0 to 6.5 eV.

11. The amine compound according to any one of claims 4 to 9, which has a band gap of 2.5 to 4.0 eV.

12. The amine compound according to any one of claims 4 to 9, which has a LUMO value of 2.0 to 3.5 eV.

13. The amine compound according to any one of claims 4 to 9, which has a glass transition temperature of 140°C or higher.

14. The amine compound according to any one of claims 4 to 9, having a molecular weight of less than 1,000.

15. A material for organic electronic devices, comprising the amine compound according to any one of claims 4 to 9.

16. A material for a photoelectric conversion device, comprising the amine compound according to any one of claims 4 to 9.

17. A charge transport material for a photoelectric conversion element for an imaging device or a charge blocking material for a photoelectric conversion element for an imaging device, comprising the amine compound according to any one of claims 4 to 9.

18. A hole transport material for a photoelectric conversion element for an imaging device or an electron blocking material for a photoelectric conversion element for an imaging device, comprising the amine compound according to any one of claims 4 to 9.

19. An organic thin film comprising the amine compound according to any one of claims 4 to 9.

20. An organic electronic device comprising the amine compound according to any one of claims 4 to 9.

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