Photoelectric conversion element for imaging element, and amine compound

Abstract

Provided are: a photoelectric conversion element for an imaging element with excellent dark current characteristics and responsiveness; and an amine compound that contributes to the production of the photoelectric conversion element with excellent dark current characteristics and responsiveness.　This photoelectric conversion element for an imaging element includes a photoelectric conversion layer and a hole transport layer between a first electrode and a second electrode. The photoelectric conversion layer includes at least two organic materials. The hole transport layer contains a compound represented by formula (1). In formula (1), Ar1 is a specific aromatic hydrocarbon group, Ar2 is a specific aromatic hydrocarbon group or the like, L1 is a specific aromatic hydrocarbon group, L2 is a specific aromatic hydrocarbon group or the like, n1 and n2are each independently an integer of 0-2, L3 is a specific aromatic hydrocarbon group, and A is a group represented by formula (2).

Description

Photoelectric conversion element for image sensors, and amine compounds

[0001] The present invention relates to a photoelectric conversion element for an image sensor and an amine compound.

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

[0003] In recent years, market demand for materials used in photoelectric conversion elements for image sensors has been increasing, with a need for materials that excel in dark current, external quantum efficiency, and response speed. Under these circumstances, the possibilities of various polycyclic compounds are being explored and investigated. As an example of a polycyclic compound, Patent Document 1 discloses a derivative with dibenzo[g,p]chrysene as the parent molecule. Furthermore, Patent Document 2 discloses a derivative with indenophenanthrene as the parent molecule.

[0004] International Publication No. 2022 / 260096, International Publication No. 2022 / 071444

[0005] However, the compounds disclosed in Patent Documents 1 and 2 do not exhibit sufficient dark current characteristics and responsiveness, and there is a need for photoelectric conversion element materials with even better properties in these areas.

[0006] The object of the present invention is to provide a photoelectric conversion element for image sensors that has excellent dark current characteristics and responsiveness, and an amine compound that contributes to the fabrication of a photoelectric conversion element with excellent dark current characteristics and responsiveness.

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

[0008] Aspects of this disclosure relate to the following photoelectric conversion elements for image sensors and amine compounds.

[0009] [1] A photoelectric element for an image sensor, comprising a photoelectric conversion layer and a hole transport layer between a first electrode and a second electrode, wherein the photoelectric conversion layer comprises at least two types of organic materials, and the hole transport layer comprises a compound represented by the following formula (1). In formula (1), Ar １is an aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have a substituent, and is a monocyclic or condensed ring of 3 rings or less, Ar ２ is an aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have a substituent, and is a monocyclic or condensed ring of 4 rings or less, or a heterocyclic aromatic group having 6 to 30 carbon atoms, which may have a substituent, and is a monocyclic or condensed ring of 4 rings or less, L １ is an aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have a substituent, and is a monocyclic or condensed ring of 3 rings or less, L ２ is an aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have a substituent, and is a monocyclic or condensed ring of 4 rings or less, or a heterocyclic aromatic group having 6 to 30 carbon atoms, which may have a substituent, and is a monocyclic or condensed ring of 4 rings or less, n １ and n ２ each independently represents an integer of 0 to 2, L ３ is a single bond or an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have a substituent, and is a monocyclic, linked ring, or condensed ring, and A is a group represented by the following formula (2); In formula (2), Ar ３ is an aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have a substituent, and is a monocyclic, linked ring, or condensed ring, or a heterocyclic aromatic group having 6 to 30 carbon atoms, which may have a substituent, and is composed of carbon, hydrogen, oxygen, and sulfur atoms, and is a monocyclic, linked ring, or condensed ring, R[[ID=十七]] １ ~R ８ each independently represents a hydrogen atom, a deuterium atom, an aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have a substituent, and is a monocyclic, linked ring, or condensed ring, a heterocyclic aromatic group having 6 to 36 carbon atoms, which may have a substituent, and is a monocyclic, linked ring, or condensed ring, or a linear or branched alkyl group having 1 to 18 carbon atoms, provided that R １ ~R ８ any one of the groups is directly bonded to the nitrogen atom adjacent to L ３ or L ３ is directly bonded to the nitrogen atom adjacent to it. [2] Ar １[1] The photoelectric conversion element for an image sensor, wherein the group is a phenyl group, a naphthyl group, anthryl group, a phenanthryl group, or a dimethylfluorenyl group. [3] Ar ２ The photoelectric conversion element for an image sensor according to [1] or [2], wherein the group is a phenyl group, a naphthyl group, anthryl group, a phenanthryl group, a dimethylfluorenyl group, a triphenylenyl group, a dibenzofuranyl group, a dibenzothienyl group, or a carbazolyl group. [4] Ar ３ A photoelectric conversion element for an image sensor according to any one of [1] to [3], wherein the element is a phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, triphenylel group, naphthylphenyl group, phenylnaphthyl group, naphthylnaphthyl group, phenanthrylphenyl group, dimethylfluorenyl group, diphenylfluorenyl group, spirobifluorenyl group, dibenzofuranyl group, dibenzothienyl group, dibenzofuranylphenyl group, or dibenzothienylphenyl group. [5] R １ ~R ８ A photoelectric conversion element for an image sensor according to any one of [1] to [4], wherein each is independently a hydrogen atom, a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, a methyl group, a tert-butyl group, a cyclohexyl group, a 1-adamantyl group, or a 2-adamantyl group. [6] L １ and L ２ However, each is independently a phenylene group, a naphthylene group, or a biphenylene group, n １ and n ２ However, each is independently represented by an integer between 0 and 2, Ar １ and L １ The total number of carbon atoms and Ar ２ and L ２ The total number of carbon atoms is 30 or less, a photoelectric conversion element for an image sensor as described in any of [1] to [5]. [7] L ３ A photoelectric conversion element for an image sensor according to any one of [1] to [6], wherein the element is a single bond, a phenylene group, or a naphthylene group. [8] (L １ )n １ -Ar １ , and (L２ )n ２ -Ar ２ [1] to [7] A photoelectric element for an image sensor according to any one of [1] to [7], wherein the total number of carbon atoms of each is independently 13 to 24. [9] A photoelectric element for an image sensor according to any one of [1] to [8], wherein the glass transition temperature of the compound represented by formula (1) is 140°C or higher.

[10] A photoelectric element for an image sensor according to any one of [1] to [8], wherein the molecular weight of the compound represented by formula (1) is less than 1000.

[11] A photoelectric element for an image sensor according to any one of [1] to

[10] , wherein the photoelectric conversion layer comprises at least three materials.

[12] A photoelectric element for an image sensor according to any one of [1] to

[11] , comprising a photoelectric conversion layer, a hole transport layer, and a buffer layer in this order between a first electrode and a second electrode, wherein the buffer layer comprises an organic material.

[13] A photoelectric element for an image sensor according to any one of [1] to

[12] , wherein the photoelectric conversion layer comprises a fullerene.

[14] An amine compound represented by the following formula (3). In formula (3), Ar ４ and Ar ５ Each is independently a monocyclic or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents, or a monocyclic or fused heterocyclic aromatic group having 6 to 30 carbon atoms, which may have substituents, L ４ and L ５ Each is independently a monocyclic or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents, or a monocyclic or fused heterocyclic aromatic group having 6 to 30 carbon atoms, which may have substituents, n ４ and n ５ Each of these is independently represented by an integer between 0 and 2, L ６ R is a monocyclic, linking, or fused aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have single bonds or substituents. ９ ~R １５Each of these independently represents a hydrogen atom, a deuterium atom, a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents, a monocyclic, linked, or fused heterocyclic aromatic group having 3 to 36 carbon atoms, which may have substituents, or a linear or branched alkyl group having 1 to 18 carbon atoms.

[15] Ar ４ and Ar ５ The amine compound according to

[14] , wherein each of these groups may independently be substituted with a methyl group: a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, anthryl group, a phenanthryl group, a triphenylel group, a naphthylphenyl group, a phenylnaphthyl group, a naphthylnaphthyl group, a phenanthrylphenyl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a spirobifluorenyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, a dibenzofuranylphenyl group, a dibenzothienylphenyl group, or a carbazolylphenyl group.

[16] R ９ ~R １５ The amine compound according to

[14] or

[15] , wherein each is independently a hydrogen atom, a phenyl group, or a naphthyl group.

[17] L ６ An amine compound according to any one of

[14] to

[16] , wherein is a single bond, a phenylene group, or a naphthylene group.

[18] An amine compound represented by the following formula (4). In equation (4), B is a base represented by the following equation (5): In formula (5), R １６ ~R ２３ Each independently represents a hydrogen atom, a deuterium atom, a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms (which may have substituents), a monocyclic, linked, or fused heterocyclic aromatic group having 3 to 36 carbon atoms (which may have substituents), or a linear or branched alkyl group having 1 to 18 carbon atoms, provided that R １７ or R １９ One of the groups is directly bonded to the nitrogen atom in formula (4), Ar ６ R represents an aromatic hydrocarbon group having 10 to 25 carbon atoms, consisting of a monocycle, linking ring, or fused ring, which may have substituents.

[19] １６ , R １８ , and R ２０ ~R ２３ The amine compound described in

[18] , wherein is a hydrogen atom.

[20] The amine compound represented by the following formula (6). In formula (6), L ５ , and L ６ Each is independently a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have single bonds or substituents, or a monocyclic, linked, or fused heterocyclic aromatic group having 6 to 30 carbon atoms, which may have substituents, n ５ and n ６ Each of these is independently represented by an integer between 0 and 2, L ４ is a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have single bonds or substituents, where C is a group represented by the following formula (7); In formula (7), R ２４ ~R ３１ Each independently represents a hydrogen atom, a deuterium atom, a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms (which may have substituents), a monocyclic, linked, or fused heterocyclic aromatic group having 3 to 36 carbon atoms (which may have substituents), or a linear or branched alkyl group having 1 to 18 carbon atoms, provided that R ２５ or R ２７ One of the groups is directly bonded to the L4 group in formula (6), and Ar ７ This is a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 25 carbon atoms, which may have substituents, or a monocyclic, linked, or fused heterocyclic aromatic group having 6 to 30 carbon atoms, which may have substituents.

[21] L ４ and L ５ The amine compound described in

[20] , wherein each is independently a single bond or a phenylene group.

[22] The amine compound represented by the following formula (8). In equation (8), D is the group represented by the following equation (9); In formula (9), R ３２ ~R ３９Each independently represents a hydrogen atom, a deuterium atom, a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms (which may have substituents), a monocyclic, linked, or fused heterocyclic aromatic group having 3 to 36 carbon atoms (which may have substituents), or a linear or branched alkyl group having 1 to 18 carbon atoms, provided that R ３２ or R ３４ One of the groups is directly bonded to the nitrogen in formula (8), and Ar ８ This is a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 25 carbon atoms, which may have substituents, or a monocyclic, linked, or fused heterocyclic aromatic group having 6 to 30 carbon atoms, which may have substituents.

[0010] According to one aspect of the present invention, a photoelectric conversion element for an image sensor with excellent dark current characteristics and responsiveness, and an amine compound that contributes to the fabrication of a photoelectric conversion element with excellent dark current characteristics and responsiveness can be provided.

[0011] A schematic cross-sectional view showing an example of an image sensor stacking configuration according to one aspect of the present invention.

[0012] The following describes in detail a photoelectric conversion element for an image sensor according to one aspect of this disclosure.

[0013] Compounds included in the hole transport layer of a photoelectric conversion element for image sensors. Compounds represented by the following formula (1) can be suitably used as compounds included in the hole transport layer of a photoelectric conversion element for image sensors. That is, a photoelectric conversion element for image sensors according to one aspect of this disclosure includes a compound represented by the following formula (1) in its hole transport layer.

[0014] In formula (1), Ar １ Ar is an aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents, and is monocyclic or tricyclic or less fused. ２ L is a monocyclic or quaternary fused aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents, or a heterocyclic aromatic group having 6 to 30 carbon atoms, which may have substituents, and １L is an aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents, and is monocyclic or tricyclic or less fused. ２ This is a monocyclic or quaternary fused aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents, or a heterocyclic aromatic group having 6 to 30 carbon atoms, which may have substituents, n １ and n ２ Each of these is independently represented by an integer between 0 and 2, L ３ A is a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have single bonds or substituents, and A is a group represented by the following formula (2).

[0015]

[0016] In formula (2), Ar ３ R is a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents, or a heterocyclic aromatic group having 6 to 30 carbon atoms, which may have substituents, and is composed of carbon, hydrogen, oxygen, and sulfur atoms. １ ~R ８ Each of these independently represents a hydrogen atom, a deuterium atom, a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms (which may have substituents), a monocyclic, linked, or fused heterocyclic aromatic group having 3 to 36 carbon atoms (which may have substituents), or a linear or branched alkyl group having 1 to 18 carbon atoms. However, R １ ~R ８ Any one of the groups is L ３ , or L ３ It is directly bonded to an adjacent nitrogen atom.

[0017] Having the above-described specific structure, a photoelectric conversion element for an image sensor containing the compound represented by formula (1) can provide a photoelectric conversion element with low dark current and excellent responsiveness. For this reason, the compound represented by formula (1) is suitably used as a hole transport layer for an image sensor.

[0018] Preferred embodiments of the definitions in the above formula (1) are as follows.

[0019] <Ar １ > Ar １ The monocyclic or condensed-ring aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent represented by may preferably be a monocyclic or condensed-ring aromatic hydrocarbon group having 6 to 18 carbon atoms.

[0020] Examples of the above aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a dimethylfluorenyl group, and the like.

[0021] When the aromatic hydrocarbon group has a substituent, the substituents are 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, or an aromatic hydrocarbon group. Among these, an alkyl group and an aromatic hydrocarbon group are more preferable.

[0022] Examples of the phosphine oxide group as the above substituent include an unsubstituted phosphine oxide group and a phosphine oxide group having a substituent. A phosphine oxide group having a substituent is preferable.

[0023] Examples of the phosphine oxide group having a substituent as the above substituent preferably include a phosphine oxide group having a monocyclic, linked, or condensed-ring aromatic hydrocarbon group having 6 to 18 carbon atoms, or a condensed-ring heteroaromatic group. Specifically, for example, a group substituted with two aryl groups such as diphenylphosphine oxide and the like can be mentioned.

[0024] Examples of the silyl group as the above substituent include an unsubstituted silyl group and a silyl group having a substituent. A silyl group having a substituent is preferable.

[0025] Preferred silyl groups having the above substituents are monocyclic, linked, or fused aromatic hydrocarbon groups having 6 to 18 carbon atoms, or fused heterocyclic aromatic groups. Specifically, examples include groups substituted with three aryl groups, such as a triphenylsilyl group.

[0026] Examples of the above substituents, which may have saturated hydrocarbon groups having 2 to 10 carbon atoms, include dihydroxyboryl group (-B(OH) ２ Examples include the 4,4,5,5-tetramethyl-[1,3,2]-dioxavoloranyl group and the 5,5-dimethyl-[1,3,2]-dioxaborinane group.

[0027] The alkyl group that is a substituent is preferably a linear or branched alkyl group having 1 to 18 carbon atoms. Examples of such alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, n-hexyl group, cyclohexyl group, octyl group, decyl group, dodecyl group, octadecyl group, and the like.

[0028] The alkoxy group that is a substituent is preferably a linear or branched alkoxy group having 1 to 18 carbon atoms. Examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, tert-butoxy, pentyloxy, n-hexyloxy, cyclohexyloxy, octyloxy, decyloxy, dodecyloxy, and octadecyloxy groups.

[0029] Examples of the above-mentioned substituent aromatic hydrocarbon groups include phenyl groups, biphenylyl groups, and naphthyl groups.

[0030] Ar １ Specifically, it is preferable that the group is a phenyl group, a naphthyl group, anthryl group, a phenanthryl group, or a dimethylfluorenyl group.

[0031] <Ar ２ > Ar ２The monocyclic or condensed ring aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent represented by is preferably a monocyclic or condensed ring aromatic hydrocarbon group having 6 to 18 carbon atoms. Ar ２ The heterocyclic aromatic group having 6 to 30 carbon atoms which may have a substituent represented by is preferably a heterocyclic aromatic group having 6 to 18 carbon atoms and having a monocyclic or condensed ring of 4 or less rings.

[0032] (Aromatic hydrocarbon group) Examples of the above aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a fluorenyl group, a triphenylenyl group, a pyrenyl group, a benzofluorenyl group, and the like.

[0033] (Heterocyclic aromatic group) Examples of the above heterocyclic aromatic group include a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, a benzonaphthofuranyl group, a benzonaphthothienyl group, a benzocarbazolyl group, and the like.

[0034] Ar ２ Specifically, it is preferably a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a dimethylfluorenyl group, a triphenylenyl group, a dibenzofuranyl group, a dibenzothienyl group, or a carbazolyl group.

[0035] <L １ > The monocyclic or condensed ring aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent represented by is preferably a monocyclic or condensed ring aromatic hydrocarbon group having 6 to 18 carbon atoms and having a monocyclic or condensed ring of 3 or less rings. １

[0036] Examples of the above aromatic hydrocarbon group include a phenylene group, a naphthylene group, a biphenylene group, a phenanthrene-diyl group, and the like.

[0037] <L ２ > L ２ ​A monocyclic or quaternary fused aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents represented by , is preferably a monocyclic or quaternary fused aromatic hydrocarbon group having 6 to 18 carbon atoms. ２ A heterocyclic aromatic group having 6 to 30 carbon atoms, which may have substituents represented by , is preferably a heterocyclic aromatic group having 6 to 18 carbon atoms, which may be a monocyclic or fused ring of 4 or fewer rings.

[0038] (Aromatic hydrocarbon group) Examples of the above aromatic hydrocarbon group include phenylene group, naphthylene group, biphenylene group, etc.

[0039] (Heterocyclic aromatic groups) Examples of the above heterocyclic aromatic groups include thiophene-diyl group, furan-diyl group, benzofuran-diyl group, benzothiophene-diyl group, dibenzofuran-diyl group, dibenzothiophene-diyl group, carbazole-diyl group, pyridine-diyl group, etc.

[0040] L １ and L ２ Specifically, these are preferably a phenylene group, a naphthylene group, or a biphenylene group, each independently.

[0041] <L ３ > L ３ Examples of monocyclic, linking, or fused aromatic hydrocarbon groups having 6 to 20 carbon atoms, which may have substituents represented by , include phenylene groups, naphthylene groups, and biphenylene groups.

[0042] L ３ Specifically, it is preferable that this is a single bond, a phenylene group, or a naphthylene group.

[0043] <Ar ３ > Ar ３ The aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents represented by Ar, is preferably a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 18 carbon atoms. ３A heterocyclic aromatic group having 6 to 30 carbon atoms, composed of carbon, hydrogen, oxygen, and sulfur atoms, which may have substituents represented by , is preferably a heterocyclic aromatic group having 6 to 18 carbon atoms, which may be a monocyclic, linked, or fused ring.

[0044] (Aromatic hydrocarbon groups) Examples of the above aromatic hydrocarbon groups include phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, triphenylel group, naphthylphenyl group, phenylnaphthyl group, naphthylnaphthyl group, phenanthrylphenyl group, dimethylfluorenyl group, diphenylfluorenyl group, spirobifluorenyl group, dinaphthylphenyl group, naphthylbiphenyl group, and the like.

[0045] (Heterocyclic aromatic groups) Examples of the above heterocyclic aromatic groups include dibenzofuranyl group, dibenzothienyl group, carbazolyl group, dibenzofuranylphenyl group, dibenzothienylphenyl group, carbazolylphenyl group, phenyldibenzofuranyl group, and phenyldibenzothienyl group.

[0046] Ar ３ Specifically, it is preferable that the group is a phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, triphenylel group, naphthylphenyl group, phenylnaphthyl group, naphthylnaphthyl group, phenanthrylphenyl group, dimethylfluorenyl group, diphenylfluorenyl group, spirobifluorenyl group, dibenzofuranyl group, dibenzothienyl group, dibenzofuranylphenyl group, or dibenzothienylphenyl group.

[0047] <R １ ~R ８ > (Aromatic hydrocarbon group) R １ ~R ８ A monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents represented by , is preferably a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 18 carbon atoms.

[0048] Examples of the above aromatic hydrocarbon groups include phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, chrysenyl group, triphenylenyl group, benzochrysenyl group, dibenzochrysenyl group, fluorenyl group, benzofluorenyl group, naphthylphenyl group, phenylnaphthyl group, naphthylnaphthyl group, phenanthrylphenyl group, phenylphenanthryl group, triphenylenylphenyl group, and phenyltriphenylenyl group.

[0049] (Heterocyclic aromatic group) R １ ~R ８ A heterocyclic aromatic group having 3 to 36 carbon atoms, which may have substituents represented by , is preferably a heterocyclic aromatic group having 3 to 36 carbon atoms, which contains at least one atom selected from the group consisting of oxygen, nitrogen, and sulfur atoms on the aromatic ring.

[0050] Examples of the above heterocyclic aromatic groups include dibenzofuranyl group, dibenzothienyl group, carbazolyl group, pyrrolyl group, thienyl group, furyl group, imidazolyl group, pyrazolyl group, thiazolyl group, isothiazolyl group, oxazolyl group, isoxazolyl group, pyridyl group, pyrimidyl group, pyrazyl group, indolyl group, benzothienyl group, benzofuranyl group, benzimidazolyl group, indazolyl group, benzothiazolyl group, benzoisothiazolyl group, 2,1,3-benzothiadiazolyl group, benzoxazolyl group, benzoisoxazolyl group, 2,1,3-benzoxadiazolyl group, quinolyl group, isoquinolyl group, quinoxalyl group, quinazolyl group, dibenzothienyl group, dibenzofuranyl group, phenoxazinyl group, phenothiazinyl group, phenazine group, thianthrenyl group, and the like.

[0051] (Alkyl group) R １ ~R ８Examples of linear or branched alkyl groups having 1 to 18 carbon atoms, represented by , include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, n-hexyl group, cyclohexyl group, octyl group, decyl group, dodecyl group, octadecyl group, 1-adamantyl group, 2-adamantyl group, and the like.

[0052] <Substituents> As mentioned above, Ar ２ and Ar ３ The above aromatic hydrocarbon group and the above heterocyclic aromatic group, L １ and L ３ The above aromatic hydrocarbon group represented by L ２ The above aromatic hydrocarbon group and the above heterocyclic aromatic group, R １ ~R ８ Either the aromatic hydrocarbon group represented by or the heterocyclic aromatic group may have substituents. The form of the substituent and specific examples are as described above. １ In this case, examples of substituents similar to those described above can be found when the aromatic hydrocarbon group has substituents.

[0053] <Preferred embodiment of the compound represented by formula (1)>

[0054] R １ ~R ８ Specifically, it is preferable that each of these groups independently be a hydrogen atom, a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, a methyl group, a tert-butyl group, a cyclohexyl group, a 1-adamantyl group, or a 2-adamantyl group.

[0055] In the compound represented by the above formula (1), L １ and L ２ However, each is independently a phenylene group, a naphthylene group, or a biphenylene group, n １ and n ２ However, each is independently represented by an integer between 0 and 2, Ar １ and L １ The total number of carbon atoms and Ar ２ and L ２Preferably, the total number of carbon atoms is 30 or less.

[0056] (L １ )n １ -Ar １ , and (L ２ )n ２ -Ar ２ The total number of carbon atoms in each element is preferably 13 to 24, independently of the others.

[0057] <Physical properties of the compound represented by formula (1)> The preferred physical properties of the compound represented by formula (1) are described below.

[0058] (HOMO value) The HOMO value of the compound represented by formula (1) is not particularly limited, but from the viewpoint of compatibility with the image sensor, it is preferably 5.0 to 6.5 eV. This HOMO value is obtained from measurements of the vapor-deposited film using an atmospheric photoelectron yield spectrometer.

[0059] (Band Gap) The band gap of the compound represented by formula (1) is not particularly limited, but from the viewpoint of compatibility with the image sensor, it is preferably 2.5 to 4.0 eV. This band gap is a value obtained from the wavelength edge of the absorption spectrum of the deposited film.

[0060] (LUMO value) The LUMO value of the compound represented by formula (1) is not particularly limited, but from the viewpoint of compatibility with the image sensor, it is preferably 2.0 to 3.5 eV. This LUMO value is obtained from the above HOMO value and band gap.

[0061] (Glass transition temperature) The glass transition temperature of the compound represented by formula (1) is not particularly limited, but from the viewpoint of compatibility with the image sensor, it is preferably 140°C or higher. This glass transition temperature is a value obtained from differential scanning calorimetry.

[0062] (Molecular weight) The molecular weight of the compound represented by formula (1) is not particularly limited, but from the viewpoint of achieving both a high glass transition temperature and heat stability during sublimation, it is preferably less than 1000, and more preferably 680 or more and less than 1000.

[0063] <Specific Examples of Compounds> Below are examples of preferred compounds represented by formula (1), but the compounds are not limited to these.

[0064] A compound is defined as (X-mn) in which substituent A is a group m selected from the groups shown in Tables 2 to 4, and substituent B is a group n selected from the groups shown in Tables 5 to 6, within the (A) to (P) skeletons shown in Table 1. Here, X represents any symbol from A to P, m represents any integer from 1 to 67, and n represents any lowercase letter from a to bg. For example, (B-29aa) has the skeleton of (B), and substituent A on the skeleton is a bis(4-(naphthalene-2-yl)phenyl)amino group, and substituent B is a triphenylene-1-yl group.

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071] <Method for producing the compound represented by formula (1)> The amine compound represented by formula (1) is, for example, an aryl halide having a carbazole derivative skeleton and Ar as a substituent. １ and Ar ２ It is produced by reacting an aromatic secondary amine having the properties of a palladium acetate catalyst or the like with the amine.

[0072] <Uses of the compound represented by formula (1)> The compound represented by formula (1) can be used as a material for photoelectric conversion elements. Examples of photoelectric conversion element materials that can be used with the compound represented by formula (1) include materials for image sensor photoelectric conversion elements. For example, charge transport materials or charge blocking materials for image sensor photoelectric conversion elements are preferred as materials that can be used with the compound represented by formula (1). For example, hole transport materials for image sensor photoelectric conversion elements are preferred as charge transport materials that can be used with the compound represented by formula (1). For example, electron blocking materials for image sensor photoelectric conversion elements are preferred as charge blocking materials that can be used with the compound represented by formula (1).

[0073] The following describes, as an example, a photoelectric conversion element for an image sensor according to this embodiment.

[0074] <<Photoelectric Conversion Element for Image Sensor>> The photoelectric conversion element for image sensor of this embodiment includes a photoelectric conversion layer and a hole transport layer between a first electrode and a second electrode. The photoelectric conversion layer includes at least two types of organic materials. The hole transport layer includes the compound represented by formula (1) described above.

[0075] The layer configuration of the photoelectric conversion element for the image sensor is not particularly limited, but examples include the configurations shown below (A) to (D). (A) A photoelectric conversion layer and a hole transport layer are provided between the first electrode and the second electrode in this order. (B) A photoelectric conversion layer, a hole transport layer, and a buffer layer are provided between the first electrode and the second electrode in this order. (C) An electron transport layer, a photoelectric conversion layer, and a hole transport layer are provided between the first electrode and the second electrode in this order. (D) An electron transport layer, a photoelectric conversion layer, a hole transport layer, and a buffer layer are provided between the first electrode and the second electrode in this order. In this configuration, light can be incident on the photoelectric conversion element from either the first electrode or the second electrode.

[0076] The configuration of the photoelectric conversion element for the image sensor is not particularly limited, but for example, the following configurations (i) to (iv) can be cited: (i) First electrode / photoelectric conversion layer / hole transport layer (electron blocking layer) / second electrode (ii) First electrode / photoelectric conversion layer / hole transport layer (electron blocking layer) / buffer layer / second electrode (iii) First electrode / electron transport layer (hole blocking layer) / 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) / buffer layer / second electrode

[0077] The buffer layer may be replaced with another layer with a different name or function, if necessary. Examples of other layers with different names or functions include hole injection layers and work function adjustment layers.

[0078] The photoelectric conversion element for the image sensor according to this embodiment will be described in more detail below, with reference to Figure 1, using the configuration of (iv) above as an example. Figure 1 is a schematic cross-sectional view showing an example of a stacked configuration of the photoelectric conversion element for the image sensor according to this embodiment. Of the embodiments of each layer described below, the same embodiments as those of the configurations of (i), (ii), and (iii) above apply to each layer described below.

[0079] The photoelectric conversion element 100 for the image sensor shown in Figure 1 comprises, 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. In this embodiment, some of these layers may be omitted, or other layers may be added.

[0080] In the photoelectric conversion element 100 for the image sensor, light is incident from below the transparent first electrode 2. Furthermore, a voltage is applied to the photoelectric conversion element 100 for the image sensor such that electrons move to the first electrode 2 and holes move to the second electrode 7 from the charge (holes and electrons) generated in the photoelectric conversion layer 4. In other words, the photoelectric conversion element 100 for the image sensor uses the first electrode 2 as an electron collection electrode and the second electrode 7 as a hole collection electrode.

[0081] The compound represented by formula (1) may be included in multiple layers other than the hole transport layer of the photoelectric conversion element 100 for the image sensor.

[0082] The following describes a photoelectric conversion element 100 for an image sensor in which the hole transport layer (electron blocking layer) 5 contains a compound represented by formula (1).

[0083] [Substrate 1] There are no particular limitations on the substrate; for example, glass plates, quartz plates, plastic plates, etc. In a configuration where light is incident from the substrate 1 side, it is preferable that the substrate 1 has high transmittance with respect to the wavelength of light (for example, transmittance of 80% or more, preferably transmittance of 90% or more).

[0084] [First Electrode 2] A first electrode 2 is provided on the substrate 1. In the case of a photoelectric conversion element for an image sensor in which light passes through the first electrode 2 and is incident on the photoelectric conversion layer, it is preferable that the first electrode 2 has high transmittance with respect to the wavelength of the incident light (for example, transmittance of 80% or more, preferably transmittance of 90% or more).

[0085] The transparent material used for the first electrode 2 is not particularly limited. From the viewpoint of excellent light transmittance, the material constituting the lower 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, etc.

[0086] Furthermore, in the case of a photoelectric conversion element for an image sensor in which light is incident on 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 used for the first electrode 2 in this case include thorium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, silver, gold, magnesium / silver mixture, aluminum, magnesium / aluminum mixture, magnesium / indium mixture, and aluminum / aluminum oxide (Al ２ O ３) may be mixtures, indium, lithium / aluminum mixtures, iridium, molybdenum, palladium, platinum, and rare earth metals, etc.

[0087] [Electron transport layer (hole blocking layer) 3] An electron transport layer (hole blocking layer) 3 is provided between the first electrode 2 and the photoelectric conversion layer 4.

[0088] 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.

[0089] The electron transport layer (hole blocking layer) 3 may be a single-layer structure made of one or more materials, or a laminated structure made of multiple layers of the same or different compositions. The electron transport layer (hole blocking layer) 3 may be a two-layer structure including, for example, a layer adjacent to the photoelectric conversion layer 4 made of a material specialized for hole blocking, and a layer adjacent to the lower electrode 2 made of a material specialized for electron transport.

[0090] The electron transport layer (hole blocking layer) 3 may be a layer containing a conventionally known electron transport material. Examples of conventionally known electron transport materials include bis(8-hydroxyquinolinate)manganese, tris(8-hydroxyquinolinate)aluminum, tris(2-methyl-8-hydroxyquinolinate)aluminum, BCP(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen(4,7-diphenyl-1,10-phenanthroline), BAlq(bis(2-methyl-8-quinolinolate)-4-(phenylphenolate)aluminum), 4,6-bis(3,5-di(pyridine-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.

[0091] [Photoelectric Conversion Layer 4] A photoelectric conversion layer 4 is provided between the electron transport layer (hole blocking layer) 3 and the hole transport layer (electron blocking layer) 5, which will be described later. The photoelectric conversion layer 4 contains a material that has a photoelectric conversion function.

[0092] From the viewpoint of increasing photoelectric conversion efficiency, the photoelectric conversion layer 4 preferably contains at least two types of organic materials and at least three types of materials. The photoelectric conversion layer 4 may be a single-layer structure or a laminated structure consisting of multiple layers of the same or different compositions.

[0093] Materials used in the photoelectric conversion layer 4 include n-type semiconductors and p-type semiconductors. N-type semiconductors are acceptor-type organic semiconductors, and compounds that readily accept electrons and have high electron transport properties are used. P-type semiconductors are donor-type organic semiconductors, and compounds that readily donate electrons and have high hole transport properties are used. When multiple materials are used in the photoelectric conversion layer 4, possible combinations include, for example, an n-type semiconductor and a p-type semiconductor, an n-type semiconductor and a compound with lower acceptor properties than the n-type semiconductor, or a p-type semiconductor and a compound with lower donor properties than the p-type semiconductor. Each material may be used individually, or two or more materials may be used. The photoelectric conversion layer 4 may also contain a dye compound that is excellent at 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. In terms of increasing photoelectric conversion efficiency, it is desirable that the photoelectric conversion layer 4 contains a dye compound in addition to the n-type semiconductor and p-type semiconductor.

[0094] Examples of compounds included 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, the photoelectric conversion layer 4 preferably contains fullerene and two compounds selected from the group consisting of phthalocyanine and its derivatives and hole transport materials, and more preferably contains fullerene, phthalocyanine derivatives, and hole transport materials.

[0095] The photoelectric conversion layer 4 made of these materials may be formed by depositing the powders in a mixed state, or by co-depositing them in any proportion. The photoelectric conversion layer 4 made of these materials may be formed, for example, by depositing a mixed powder obtained by mixing the powders of each material, or by co-depositing each material in any proportion.

[0096] 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 any 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, naphthiothiophene compounds, benzodithiophene compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, crisenodithiophene compounds, benzothienobenzothiophene compounds, and indolocarbazole compounds. Among these, fluorene compounds, naphthodithiophene compounds, naphthothienothiophene compounds, benzodifuran compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, crisenodithiophene compounds, benzothienobenzothiophene compounds, and indolocarbazole compounds are preferred, with fluorene compounds, crisenodithiophene compounds, benzothienobenzothiophene compounds, and indolocarbazole compounds being more preferred.

[0097] 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, 2Ph-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' Examples include [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, criseno[1,2-b:8,7-b']dithiophene, [1]benzothieno[3,2-b][1]benzothiophene, compounds represented by the following formula (ic-1), compounds represented by the following formulas (ic-2) and (ic-3), etc.

[0098]

[0099] The material having the photoelectric conversion function described above may be contained only in the photoelectric conversion layer 4, or it may 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 the material having the photoelectric conversion function.

[0100] [Hole transport layer (electron blocking layer) 5] A hole transport layer (electron blocking layer) 5 is provided between the photoelectric conversion layer 4 and the buffer layer 6, which will be described later.

[0101] The hole transport layer (electron blocking layer) 5 has the role of transporting holes generated in the photoelectric conversion layer 4 to the second electrode 7, and the role of blocking electrons generated in the photoelectric conversion layer 4 from moving to the second electrode 7. The hole transport layer (electron blocking layer) 5 contains a compound represented by formula (1).

[0102] The hole transport layer (electron blocking layer) 5 may be a single layer structure consisting only of the compound represented by formula (1), a single layer structure consisting of two or more materials, or a laminated structure consisting of multiple layers of the same or different compositions. For example, the hole transport layer (electron blocking layer) 5 may be a two-layer structure including a layer adjacent to the photoelectric conversion layer 4 made of a material specialized for electron blocking, and a layer adjacent to the buffer layer 6 made of a material specialized for hole transport.

[0103] The hole transport layer (electron blocking layer) 5 may further contain conventionally known hole transport materials in addition to the compound represented by formula (1). Preferred conventionally known hole transport materials and specific examples are the same as those described in the section on photoelectric conversion layer 4.

[0104] [Buffer Layer 6] A buffer layer 6 is provided between the hole transport layer (electron blocking layer) 5 and the upper electrode 7, which will be described later. The buffer layer 6 plays a role in reducing damage to the organic layer (for example, the hole transport layer (electron blocking layer) 5) during sputtering when the second electrode 7 is formed by sputtering. In addition, by adjusting the work function of the buffer layer 6, it also plays a role in efficiently receiving holes from the hole transport layer (electron blocking layer) 5 and receiving electrons from the second electrode 7, and is also called a hole injection layer or work function adjustment layer.

[0105] The material constituting the buffer layer 6 may be a known organic material, such as naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA) or its derivatives, or aromatic compounds having a cyano group such as 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN). Among these, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN) is preferred.

[0106] [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 can be, for example, sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, silver, gold, magnesium / silver mixture, aluminum, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ２ O ３ ) may be a mixture, indium, lithium / aluminum mixture, rare earth metals, etc. In the case of a photoelectric conversion element for an image sensor in which light is incident on the photoelectric conversion layer from the second electrode 7 side, the material constituting the second electrode 7 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, etc.

[0107] [Method for forming each layer] Each layer other than the first electrode 2 and the second electrode 7 can be formed by thinning the material of the respective layer (and optionally, a binder resin or other material, solvent, etc.) using known methods 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 appropriately selected 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.

[0108] The first electrode 2 and the second electrode 7 can be formed by thinning the electrode material using methods such as vapor deposition and sputtering. If the first electrode 2 and the second electrode 7 have patterns, the patterns can be formed, for example, through a mask of a desired shape. Alternatively, after forming a thin film by vapor deposition, sputtering, etc., a pattern of a desired shape may be formed using photolithography.

[0109] The film thickness of the first electrode 2 and the second electrode 7 may be 1 μm or less, and is preferably 10 nm to 200 nm.

[0110] The first electrode 2 and the second electrode 7 may be made of different materials as needed (this is also called an inverse structure). In this structure, the light passes through the second electrode 7 and enters the photoelectric conversion layer 4, resulting in a photoelectric conversion element for an image sensor.

[0111] In the above embodiments, the photoelectric conversion element for the image sensor preferably comprises a photoelectric conversion layer and a hole transport layer in this order between a first electrode and a second electrode, wherein the photoelectric conversion layer contains a fullerene and the hole transport layer contains a compound represented by the above formula (1).

[0112] The image sensor equipped with the photoelectric conversion element according to this embodiment can be applied, for example, to image sensors in digital cameras, digital video cameras, and image sensors built into mobile phones, etc. Although preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments.

[0113] ≪Amine Compounds≫ An amine compound according to one aspect of the present disclosure is represented by the following formula (3).

[0114] In formula (3), Ar ４ and Ar ５ Each is independently a monocyclic or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents, or a monocyclic or fused heterocyclic aromatic group having 6 to 30 carbon atoms, which may have substituents, L ４ and L ５ Each is independently a monocyclic or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents, or a monocyclic or fused heterocyclic aromatic group having 6 to 30 carbon atoms, which may have substituents, n ４ and n ５ Each of these is independently represented by an integer between 0 and 2, L ６R is a monocyclic, linking, or fused aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have single bonds or substituents. ９ ~R １５ Each of these independently represents a hydrogen atom, a deuterium atom, a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms (which may have substituents), a monocyclic, linked, or fused heterocyclic aromatic group having 3 to 36 carbon atoms (which may have substituents), or a linear or branched alkyl group having 1 to 18 carbon atoms.

[0115] Having the above-described specific structure, the material containing the amine compound represented by formula (3) can provide a photoelectric conversion element with low dark current and excellent responsiveness. For this reason, the amine compound represented by formula (3) is suitably used as a material for photoelectric conversion elements for image sensors.

[0116] The preferred embodiment of the definition in formula (3) above is as follows:

[0117] <Ar ４ and Ar ５ > Ar ４ and Ar ５ The aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents represented by Ar, is preferably a monocyclic or fused ring aromatic hydrocarbon group having 6 to 18 carbon atoms. ４ and Ar ５ A heterocyclic aromatic group having 6 to 30 carbon atoms, which may have substituents represented by , is preferably a heterocyclic aromatic group having 6 to 18 carbon atoms, which may be a monocyclic or fused ring.

[0118] (Aromatic hydrocarbon groups) Examples of the above aromatic hydrocarbon groups include phenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, crisenyl group, benzocrisenyl group, dibenzocrisenyl group, fluorenyl group, benzofluorenyl group, spirobifluorenyl group, naphthylphenyl group, phenylnaphthyl group, naphthylnaphthyl group, phenanthrylphenyl group, and the like.

[0119] (Heterocyclic aromatic groups) Examples of the above heterocyclic aromatic groups include dibenzofuranyl group, dibenzothionyl group, carbazolyl group, dibenzofuranylphenyl group, dibenzothionylphenyl group, carbazolylphenyl group, pyrrolyl group, thienyl group, furyl group, imidazolyl group, pyrazolyl group, thiazolyl group, isothiazolyl group, oxazolyl group, isoxazolyl group, pyridyl group, phenylpyridyl group, pyridylphenyl group, pyrimidyl group, pyrazyl group, 1,3,5-triazyl group, 1,3,5-triazylphenyl group, 1,3,5-triazylbiphenyl group, and 4,6-diphenyl-1,3,5-triazyl group. Examples include indolyl group, benzothienyl group, benzofuranyl group, benzimidazolyl group, indazolyl group, benzothiazolyl group, benzoisothiazolyl group, 2,1,3-benzothiadiazolyl group, benzoxazolyl group, benzoisoxazolyl group, 2,1,3-benzoxadiazolyl group, quinolyl group, isoquinolyl group, quinoxalyl group, quinazolyl group, carbazolyl group, 9-phenylcarbazolyl group, 9-(4-biphenylyl)carbazolyl group, dibenzothienyl group, dibenzofuranyl group, phenoxazinyl group, phenothiazinyl group, phenazine group, thianthrenyl group, etc.

[0120] Ar ４ and Ar ５ Specifically, it is preferable that each of these groups is independently substituted with a methyl group, and may be a phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, triphenylel group, naphthylphenyl group, phenylnaphthyl group, naphthylnaphthyl group, phenanthrylphenyl group, dimethylfluorenyl group, diphenylfluorenyl group, spirobifluorenyl group, dibenzofuranyl group, dibenzothienyl group, carbazolyl group, dibenzofuranylphenyl group, dibenzothienylphenyl group, or carbazolylphenyl group.

[0121] <L ４ and L ５ > L ４ and L ５The aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents represented by , is preferably a monocyclic or fused ring aromatic hydrocarbon group having 6 to 18 carbon atoms. ４ and L ５ A heterocyclic aromatic group having 6 to 30 carbon atoms, which may have substituents represented by , is preferably a heterocyclic aromatic group having 6 to 18 carbon atoms, which may be a monocyclic or fused ring.

[0122] (Aromatic hydrocarbon group) Examples of the above aromatic hydrocarbon group include phenylene group, naphthylene group, biphenylene group, etc.

[0123] (Heterocyclic aromatic groups) Examples of the above heterocyclic aromatic groups include thiophene-diyl group, furan-diyl group, benzofuran-diyl group, benzothiophene-diyl group, dibenzofuran-diyl group, dibenzothiophene-diyl group, carbazole-diyl group, pyridine-diyl group, etc.

[0124] <L ６ > L ６ Examples of monocyclic, linking, or fused aromatic hydrocarbon groups having 6 to 20 carbon atoms, which may have substituents represented by , include phenylene groups, naphthylene groups, and biphenylene groups.

[0125] L ６ Specifically, it is preferable that this is a single bond, a phenylene group, or a naphthylene group.

[0126] <R ９ ~R １５ > (Aromatic hydrocarbon group) R ９ ~R １５ A monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents represented by , is preferably a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 18 carbon atoms.

[0127] Examples of the above aromatic hydrocarbon groups include phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, chrysenyl group, triphenylenyl group, benzochrysenyl group, dibenzochrysenyl group, fluorenyl group, benzofluorenyl group, naphthylphenyl group, phenylnaphthyl group, naphthylnaphthyl group, phenanthrylphenyl group, phenylphenanthryl group, triphenylenylphenyl group, and phenyltriphenylenyl group.

[0128] (Heterocyclic aromatic group) R ９ ~R １５ A heterocyclic aromatic group having 3 to 36 carbon atoms, which may have substituents represented by , is preferably a heterocyclic aromatic group having 3 to 36 carbon atoms, which contains at least one atom selected from the group consisting of oxygen, nitrogen, and sulfur atoms on the aromatic ring.

[0129] Examples of the above heterocyclic aromatic groups include dibenzofuranyl group, dibenzothienyl group, carbazolyl group, pyrrolyl group, thienyl group, furyl group, imidazolyl group, pyrazolyl group, thiazolyl group, isothiazolyl group, oxazolyl group, isoxazolyl group, pyridyl group, pyrimidyl group, pyrazyl group, indolyl group, benzothienyl group, benzofuranyl group, benzimidazolyl group, indazolyl group, benzothiazolyl group, benzoisothiazolyl group, 2,1,3-benzothiadiazolyl group, benzoxazolyl group, benzoisoxazolyl group, 2,1,3-benzoxadiazolyl group, quinolyl group, isoquinolyl group, quinoxalyl group, quinazolyl group, dibenzothienyl group, dibenzofuranyl group, phenoxazinyl group, phenothiazinyl group, phenazine group, thianthrenyl group, and the like.

[0130] (Alkyl group) R ９ ~R １５Examples of linear or branched alkyl groups having 1 to 18 carbon atoms, represented by , include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, n-hexyl group, cyclohexyl group, octyl group, decyl group, dodecyl group, octadecyl group, 1-adamantyl group, 2-adamantyl group, and the like.

[0131] <Substituents> As mentioned above, Ar ４ and Ar ５ The above aromatic hydrocarbon group and the above heterocyclic aromatic group, L ４ and L ５ The above aromatic hydrocarbon group and the above heterocyclic aromatic group, L ６ The above aromatic hydrocarbon group represented by R ９ ~R １５ Either the aromatic hydrocarbon group represented by the above or the heterocyclic aromatic group may have substituents. The form of the substituent and specific examples are given in the above-mentioned "Compounds contained in the hole transport layer of a photoelectric conversion element for an image sensor", Ar １ Examples of substituents similar to those described above can be found when the aromatic hydrocarbon group represented by has substituents.

[0132] R ９ ~R １５ Specifically, these are preferably a hydrogen atom, a phenyl group, or a naphthyl group, each independently.

[0133] ≪Amine Compounds≫ An amine compound according to one aspect of this disclosure is represented by the following formula (4).

[0134] In equation (4), B is a base represented by the following equation (5):

[0135] In formula (5), R １６ ~R ２３Each independently represents a hydrogen atom, a deuterium atom, a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms (which may have substituents), a monocyclic, linked, or fused heterocyclic aromatic group having 3 to 36 carbon atoms (which may have substituents), or a linear or branched alkyl group having 1 to 18 carbon atoms, provided that R １７ or R １９ One of the groups is directly bonded to the nitrogen atom in formula (4), Ar ６ This represents an aromatic hydrocarbon group having 10 to 25 carbon atoms, consisting of a monocycle, linking ring, or fused ring, which may have substituents.

[0136] Having the above-described specific structure, the material containing the amine compound represented by formula (4) can provide a photoelectric conversion element with low dark current and excellent responsiveness. For this reason, the amine compound represented by formula (4) is suitably used as a material for photoelectric conversion elements for image sensors.

[0137] The preferred embodiment of the definition in formula (4) above is as follows:

[0138] <R １６ ~R ２３ > (Aromatic hydrocarbon group) R １６ ~R ２３ A monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents represented by , is preferably a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 18 carbon atoms.

[0139] Examples of the above aromatic hydrocarbon groups include phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, chrysenyl group, triphenylenyl group, benzochrysenyl group, dibenzochrysenyl group, fluorenyl group, benzofluorenyl group, naphthylphenyl group, phenylnaphthyl group, naphthylnaphthyl group, phenanthrylphenyl group, phenylphenanthryl group, triphenylenylphenyl group, and phenyltriphenylenyl group.

[0140] (Heterocyclic aromatic group) R １６ ~R ２３A heterocyclic aromatic group having 3 to 36 carbon atoms, which may have substituents represented by , is preferably a heterocyclic aromatic group having 3 to 36 carbon atoms, which contains at least one atom selected from the group consisting of oxygen, nitrogen, and sulfur atoms on the aromatic ring.

[0141] Examples of the above heterocyclic aromatic groups include dibenzofuranyl group, dibenzothienyl group, carbazolyl group, pyrrolyl group, thienyl group, furyl group, imidazolyl group, pyrazolyl group, thiazolyl group, isothiazolyl group, oxazolyl group, isoxazolyl group, pyridyl group, pyrimidyl group, pyrazyl group, indolyl group, benzothienyl group, benzofuranyl group, benzimidazolyl group, indazolyl group, benzothiazolyl group, benzoisothiazolyl group, 2,1,3-benzothiadiazolyl group, benzoxazolyl group, benzoisoxazolyl group, 2,1,3-benzoxadiazolyl group, quinolyl group, isoquinolyl group, quinoxalyl group, quinazolyl group, dibenzothienyl group, dibenzofuranyl group, phenoxazinyl group, phenothiazinyl group, phenazine group, thianthrenyl group, and the like.

[0142] (Alkyl group) R １６ ~R ２３ Examples of linear or branched alkyl groups having 1 to 18 carbon atoms, represented by , include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, n-hexyl group, cyclohexyl group, octyl group, decyl group, dodecyl group, octadecyl group, 1-adamantyl group, 2-adamantyl group, and the like.

[0143] <Ar ６ > Ar ６ A monocyclic, linked, or fused aromatic hydrocarbon group having 10 to 25 carbon atoms, which may have substituents represented by , is preferably a monocyclic, linked, or fused aromatic hydrocarbon group having 10 to 18 carbon atoms.

[0144] (Aromatic hydrocarbon groups) Examples of the above aromatic hydrocarbon groups include phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, triphenylel group, naphthylphenyl group, phenylnaphthyl group, naphthylnaphthyl group, phenanthrylphenyl group, dimethylfluorenyl group, diphenylfluorenyl group, spirobifluorenyl group, and the like.

[0145] Ar ６ Specifically, it is preferable that the group is a phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, triphenylel group, naphthylphenyl group, phenylnaphthyl group, naphthylnaphthyl group, phenanthrylphenyl group, dimethylfluorenyl group, diphenylfluorenyl group, or spirobifluorenyl group.

[0146] <Substituents> As mentioned above, R １６ ~R ２３ The above aromatic hydrocarbon group and the above heterocyclic aromatic group, Ar ６ The above aromatic hydrocarbon group represented by may have substituents. The form of the substituent and specific examples are given in the above-mentioned "Compounds contained in the hole transport layer of a photoelectric conversion element for an image sensor", Ar １ Examples of substituents similar to those described above can be found when the aromatic hydrocarbon group represented by has substituents.

[0147] In the amine compound represented by the above formula (4), R １６ , R １８ , and R ２０ ~R ２３ Preferably, it is a hydrogen atom.

[0148] ≪Amine Compounds≫ An amine compound according to one aspect of the present disclosure is represented by the following formula (6). Formula (in 6), L ５ , and L ６ Each is independently a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have single bonds or substituents, or a monocyclic, linked, or fused heterocyclic aromatic group having 6 to 30 carbon atoms, which may have substituents, n ５ and n６ Each of these is independently represented by an integer between 0 and 2, L ４ is a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have single bonds or substituents, where C is a group represented by the following formula (7); In formula (7), R ２４ ~R ３１ Each independently represents a hydrogen atom, a deuterium atom, a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms (which may have substituents), a monocyclic, linked, or fused heterocyclic aromatic group having 3 to 36 carbon atoms (which may have substituents), or a linear or branched alkyl group having 1 to 18 carbon atoms, provided that R ２５ or R ２７ One of the groups is directly bonded to the L4 group in formula (6), and Ar ７ This is a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 25 carbon atoms, which may have substituents, or a monocyclic, linked, or fused heterocyclic aromatic group having 6 to 30 carbon atoms, which may have substituents.

[0149] Having the above-described specific structure, the material containing the amine compound represented by formula (6) can provide a photoelectric conversion element with low dark current and excellent responsiveness. For this reason, the amine compound represented by formula (6) is suitably used as a material for photoelectric conversion elements for image sensors.

[0150] The preferred embodiment of the definition in formula (6) above is as follows:

[0151] <L ５ and L ６ > L ５ and L ６ A monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents represented by , is preferably a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 18 carbon atoms. ５ and L ６A heterocyclic aromatic group having 6 to 30 carbon atoms, which may have substituents represented by , is preferably a heterocyclic aromatic group having 6 to 18 carbon atoms, which may be a monocyclic, linking, or fused ring.

[0152] (Aromatic hydrocarbon group) Examples of the above aromatic hydrocarbon group include phenylene group, naphthylene group, biphenylene group, etc.

[0153] (Heterocyclic aromatic groups) Examples of the above heterocyclic aromatic groups include thiophene-diyl group, furan-diyl group, benzofuran-diyl group, benzothiophene-diyl group, dibenzofuran-diyl group, dibenzothiophene-diyl group, carbazole-diyl group, pyridine-diyl group, etc.

[0154] <L ４ > L ４ Examples of aromatic hydrocarbon groups represented by this formula include phenylene groups, naphthylene groups, and biphenylene groups.

[0155] <R ２４ ~R ３１ > (Aromatic hydrocarbon group) R ２４ ~R ３１ A monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents represented by , is preferably a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 18 carbon atoms.

[0156] Examples of the above aromatic hydrocarbon groups include phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, chrysenyl group, triphenylenyl group, benzochrysenyl group, dibenzochrysenyl group, fluorenyl group, benzofluorenyl group, naphthylphenyl group, phenylnaphthyl group, naphthylnaphthyl group, phenanthrylphenyl group, phenylphenanthryl group, triphenylenylphenyl group, and phenyltriphenylenyl group.

[0157] (Heterocyclic aromatic group) R ２４ ~R ３１A heterocyclic aromatic group having 3 to 36 carbon atoms, which may have substituents represented by , is preferably a heterocyclic aromatic group having 3 to 36 carbon atoms, which contains at least one atom selected from the group consisting of oxygen, nitrogen, and sulfur atoms on the aromatic ring.

[0158] Examples of the above heterocyclic aromatic groups include dibenzofuranyl group, dibenzothienyl group, carbazolyl group, pyrrolyl group, thienyl group, furyl group, imidazolyl group, pyrazolyl group, thiazolyl group, isothiazolyl group, oxazolyl group, isoxazolyl group, pyridyl group, pyrimidyl group, pyrazyl group, indolyl group, benzothienyl group, benzofuranyl group, benzimidazolyl group, indazolyl group, benzothiazolyl group, benzoisothiazolyl group, 2,1,3-benzothiadiazolyl group, benzoxazolyl group, benzoisoxazolyl group, 2,1,3-benzoxadiazolyl group, quinolyl group, isoquinolyl group, quinoxalyl group, quinazolyl group, dibenzothienyl group, dibenzofuranyl group, phenoxazinyl group, phenothiazinyl group, phenazine group, thianthrenyl group, and the like.

[0159] (Alkyl group) R ２４ ~R ３１ Examples of linear or branched alkyl groups having 1 to 18 carbon atoms, represented by , include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, n-hexyl group, cyclohexyl group, octyl group, decyl group, dodecyl group, octadecyl group, 1-adamantyl group, 2-adamantyl group, and the like.

[0160] <Ar ７ > Ar ７ The aromatic hydrocarbon group having 6 to 25 carbon atoms, which may have substituents represented by Ar, is preferably a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 18 carbon atoms. ７A heterocyclic aromatic group having 6 to 30 carbon atoms, which may have substituents represented by , is preferably a heterocyclic aromatic group having 6 to 18 carbon atoms, which may have 6 to 18 carbon atoms, which may have 6 to 30 carbon atoms.

[0161] (Aromatic hydrocarbon groups) Examples of the above aromatic hydrocarbon groups include phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, triphenylel group, naphthylphenyl group, phenylnaphthyl group, naphthylnaphthyl group, phenanthrylphenyl group, dimethylfluorenyl group, diphenylfluorenyl group, spirobifluorenyl group, and the like.

[0162] (Heterocyclic aromatic groups) Examples of the above heterocyclic aromatic groups include dibenzofuranyl group, dibenzothienyl group, carbazolyl group, dibenzofuranylphenyl group, dibenzothienylphenyl group, and carbazolylphenyl group.

[0163] Ar ７ Specifically, it is preferable that the group is a phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, triphenylel group, naphthylphenyl group, phenylnaphthyl group, naphthylnaphthyl group, phenanthrylphenyl group, dimethylfluorenyl group, diphenylfluorenyl group, spirobifluorenyl group, dibenzofuranyl group, dibenzothienyl group, carbazolyl group, dibenzofuranylphenyl group, dibenzothienylphenyl group, or carbazolylphenyl group.

[0164] <Substituents> As mentioned above, R ２４ ~R ３１ The above aromatic hydrocarbon group and the above heterocyclic aromatic group, Ar ７ Either the aromatic hydrocarbon group represented by the above or the heterocyclic aromatic group may have substituents. The form of the substituent and specific examples are given in the above-mentioned "Compounds contained in the hole transport layer of a photoelectric conversion element for an image sensor", Ar １ Examples of substituents similar to those described above can be found when the aromatic hydrocarbon group represented by has substituents.

[0165] In the amine compound represented by the above formula (6), L ４ and L ５ However, each is preferably a single bond or a phenylene group, independently of the others.

[0166] ≪Amine Compounds≫ An amine compound according to one aspect of the present disclosure is represented by the following formula (8). In equation (8), D is the group represented by the following equation (9); In formula (9), R ３２ ~R ３９ Each independently represents a hydrogen atom, a deuterium atom, a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms (which may have substituents), a monocyclic, linked, or fused heterocyclic aromatic group having 3 to 36 carbon atoms (which may have substituents), or a linear or branched alkyl group having 1 to 18 carbon atoms, provided that R ３２ or R ３４ One of the groups is directly bonded to the nitrogen in formula (8), and Ar ８ This is a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 25 carbon atoms, which may have substituents, or a monocyclic, linked, or fused heterocyclic aromatic group having 6 to 30 carbon atoms, which may have substituents.

[0167] Having the above-described specific structure, the material containing the amine compound represented by formula (8) can provide a photoelectric conversion element with low dark current and excellent responsiveness. For this reason, the amine compound represented by formula (8) is suitably used as a material for photoelectric conversion elements for image sensors.

[0168] The preferred embodiment of the definition in formula (8) above is as follows:

[0169] <R ３２ ~R ３９ > (Aromatic hydrocarbon group) R ２４ ~R ３１ A monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents represented by , is preferably a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 18 carbon atoms.

[0170] Examples of the above aromatic hydrocarbon groups include phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, chrysenyl group, triphenylenyl group, benzochrysenyl group, dibenzochrysenyl group, fluorenyl group, benzofluorenyl group, naphthylphenyl group, phenylnaphthyl group, naphthylnaphthyl group, phenanthrylphenyl group, phenylphenanthryl group, triphenylenylphenyl group, and phenyltriphenylenyl group.

[0171] (Heterocyclic aromatic group) R ３２ ~R ３９ A heterocyclic aromatic group having 3 to 36 carbon atoms, which may have substituents represented by , is preferably a heterocyclic aromatic group having 3 to 36 carbon atoms, which contains at least one atom selected from the group consisting of oxygen, nitrogen, and sulfur atoms on the aromatic ring.

[0172] Examples of the above heterocyclic aromatic groups include dibenzofuranyl group, dibenzothienyl group, carbazolyl group, pyrrolyl group, thienyl group, furyl group, imidazolyl group, pyrazolyl group, thiazolyl group, isothiazolyl group, oxazolyl group, isoxazolyl group, pyridyl group, pyrimidyl group, pyrazyl group, indolyl group, benzothienyl group, benzofuranyl group, benzimidazolyl group, indazolyl group, benzothiazolyl group, benzoisothiazolyl group, 2,1,3-benzothiadiazolyl group, benzoxazolyl group, benzoisoxazolyl group, 2,1,3-benzoxadiazolyl group, quinolyl group, isoquinolyl group, quinoxalyl group, quinazolyl group, dibenzothienyl group, dibenzofuranyl group, phenoxazinyl group, phenothiazinyl group, phenazine group, thianthrenyl group, and the like.

[0173] (Alkyl group) R ３２ ~R ３９Examples of linear or branched alkyl groups having 1 to 18 carbon atoms, represented by , include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, n-hexyl group, cyclohexyl group, octyl group, decyl group, dodecyl group, octadecyl group, 1-adamantyl group, 2-adamantyl group, and the like.

[0174] <Ar ８ > Ar ８ The aromatic hydrocarbon group having 6 to 25 carbon atoms, which may have substituents represented by Ar, is preferably a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 18 carbon atoms. ８ A heterocyclic aromatic group having 6 to 30 carbon atoms, which may have substituents represented by , is preferably a heterocyclic aromatic group having 6 to 18 carbon atoms, which may have 6 to 18 carbon atoms, which may have 6 to 30 carbon atoms.

[0175] (Aromatic hydrocarbon groups) Examples of the above aromatic hydrocarbon groups include phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, triphenylel group, naphthylphenyl group, phenylnaphthyl group, naphthylnaphthyl group, phenanthrylphenyl group, dimethylfluorenyl group, diphenylfluorenyl group, spirobifluorenyl group, and the like.

[0176] (Heterocyclic aromatic groups) Examples of the above heterocyclic aromatic groups include dibenzofuranyl group, dibenzothienyl group, carbazolyl group, dibenzofuranylphenyl group, dibenzothienylphenyl group, and carbazolylphenyl group.

[0177] Ar ８Specifically, it is preferable that the group is a phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, triphenylel group, naphthylphenyl group, phenylnaphthyl group, naphthylnaphthyl group, phenanthrylphenyl group, dimethylfluorenyl group, diphenylfluorenyl group, spirobifluorenyl group, dibenzofuranyl group, dibenzothienyl group, carbazolyl group, dibenzofuranylphenyl group, dibenzothienylphenyl group, or carbazolylphenyl group.

[0178] <Substituents> As mentioned above, R ３２ ~R ３９ The above aromatic hydrocarbon group and the above heterocyclic aromatic group, Ar ８ Either the aromatic hydrocarbon group represented by the above or the heterocyclic aromatic group may have substituents. The form of the substituent and specific examples are given in the above-mentioned "Compounds contained in the hole transport layer of a photoelectric conversion element for an image sensor", Ar １ Examples of substituents similar to those described above can be found when the aromatic hydrocarbon group represented by has substituents.

[0179] <Physical Properties of Amine Compounds> The preferred HOMO value, band gap, LUMO value, glass transition temperature, and molecular weight of the amine compounds represented by formulas (3), (4), (6), and (8) are the same as those of the compound represented by formula (1) in the aforementioned "Compounds contained in the hole transport layer of a photoelectric conversion element for an image sensor".

[0180] <Method for producing amine compounds> The method for producing the amine compounds represented by formulas (3), (4), (6), and (8) is the same as the method for producing the compound represented by formula (1) in the above-mentioned "Compounds contained in the hole transport layer of a photoelectric conversion element for an image sensor".

[0181] <Preferred Specific Examples of Amine Compounds> Preferred amine compounds represented by formulas (3), (4), (6), and (8) are the same as preferred compounds represented by formula (1) in the above-mentioned "Compounds contained in the hole transport layer of a photoelectric conversion element for an image sensor".

[0182] <Applications of Amine Compounds> The amine compounds represented by formulas (3), (4), (6), and (8) can be used as materials for photoelectric conversion elements. That is, the photoelectric conversion element material of this embodiment includes the amine compounds represented by formulas (3), (4), (6), and (8). Examples of photoelectric conversion element materials include photoelectric conversion element materials for image sensors. As examples of photoelectric conversion element materials for image sensors, charge transport materials or charge blocking materials for image sensors are preferred. As examples of charge transport materials for image sensors, hole transport materials for image sensors are preferred. As examples of charge blocking materials for image sensors, electron blocking materials for image sensors are preferred.

[0183] The image sensor equipped with the photoelectric conversion element according to this embodiment can be applied, for example, to image sensors in digital cameras, digital video cameras, and image sensors built into mobile phones, etc. Although preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments.

[0184] The present invention will be described in more detail below based on examples, but the present invention is not to be limited in any way by these examples.

[0185] [Synthesis Example 1] Synthesis of the compound (N-(phenanthrene-9-yl)-2-chlorocarbazole)

[0186] Under an argon stream, 2-chlorocarbazole (4.28 g, 21.2 mmol), 9-fluorophenanthrene (5.00 g, 25.5 mmol), tripotassium phosphate (9.01 g, 42.5 mmol), and DMSO (71 mL) were added to a 200 mL two-necked flask and heated and stirred at 150 °C for 20 hours. After cooling to room temperature, 120 mL of water was added to precipitate the solid, and a brown solid was obtained by suction filtration. Recrystallization with a mixed solvent of toluene and butanol yielded 4.41 g of a white solid of 2-chloro-9-(phenanthrene-9-yl)carbazole (11.8 mmol, yield 55%). The compound was identified as follows: １ This was performed using H-NMR measurement. １ H-NMR (d ６ -DMSO) δ (ppm): 9.05 (dd, J = 8.4Hz, 16.8Hz, 2H), 8.35-8.39 (m, 2H), 8,26 (s, 1H), 8.14 (d, J = 8.0Hz, 1H), 7.87 (t, J = 7. 6Hz, 1H), 7.76-7.80 (m, 2H), 7.51 (t, J = 7.6Hz, 1H), 7.30-7.40 (m, 3H), 7.02 (d, J = 1.6Hz, 1H), 7.00 (t, J = 7.2Hz, 2H).

[0187] [Synthesis Example 1] Synthesis of Compound (B-9y)

[0188] Under an argon stream, N-(phenanthren-9-yl)-2-chlorocarbazole (1.31 g, 3.48 mmol), N,N-di([1,1':4',1''-terphenyl]-4-yl)amine (1.50 g, 3.48 mmol), palladium acetate (28.4 mg, 127 μ mmol), SPhos (104 mg, 253 μ mmol), sodium tert-butoxide (350 mg, 3.64 mmol), and xylene (106 mL) were added to a 200 mL two-necked flask and stirred at 140 °C for 40 hours. After cooling to room temperature, pure water and methanol were added, and the precipitated solid was collected. The mixture was then stirred with activated carbon in chlorobenzene at 140 °C. The solution obtained by hot filtration was concentrated, and 1.90 g of compound (B-9y) was obtained by recrystallization in a mixed solvent of chlorobenzene and butanol (2.48 mmol, yield 78%). The sublimation temperature of compound (B-9y) was 360°C, and it was confirmed that the sublimated compound (B-9y) was glassy. The identification of the compound was as follows: １ This was performed using H-NMR measurement. １ H-NMR (d ６ -DMSO) δ (ppm): 8.97 (d, J = 8.4Hz, 1H), 8.92 (d, J = 8.4Hz, 1H), 8.29 (t, J = 8.4Hz, 2H), 8.20 (s, 1H), 8.11 (d, 8.4Hz, 1H) ), 7.56-7.78 (m, 20H), 7.48 (t, 8.4Hz, 3H), 7.32-7.50 (m, 4H), 7.19 (d, 8.4Hz, 1H), 7.04-7.11 (m, 6H), 6.69 (s, 1H).

[0189] [Synthesis Example 2] Synthesis of compound (B-19at)

[0190] Under an argon stream, 9-(dibenzo[b,d]furan-2-yl)-9H-carbazole-2-hydrochloride (1.54 g, 4.00 mmol), 2-bromophenanthrene (2.26 g, 8.80 mmol), palladium acetate (18.0 mg, 80.0 μmol), SPhos (65.7 mg, 160 μmol), sodium tert-butoxide (1.35 g, 14.0 mmol), and xylene (40.0 mL) were added to a 100 mL two-necked flask and stirred at 140 °C for 5 hours. After cooling to room temperature, pure water and hexane were added, and the precipitated solid was collected. The mixture was then stirred in toluene at 100 °C with activated carbon added. The solution obtained by hot filtration was concentrated, and purification by silica gel chromatography in a mixed solvent of hexane and toluene yielded 1.75 g of a white solid of compound (B-19at) (2.50 mmol, yield 62%). The sublimation temperature of compound (B-19at) was confirmed to be 360°C, and the sublimated compound (B-19at) was confirmed to be glassy. The identification of the compound is １ This was performed using H-NMR measurement. １ H-NMR (d ６ -DMSO) δ (ppm): 8.77 (d, J = 9.3 Hz, 2H), 8.69 (d, J = 8.1 Hz, 2H), 8.34 (d, J = 2.2 Hz, 1H), 8.26 (d, J = 8. 6Hz, 1H), 8.23 ​​(d, J = 7.6Hz, 1H), 7.94 (d, J = 7.8Hz, 3H), 7.84 (d, J = 8.8Hz, 1H), 7.7 7-7.73 (m, 3H), 7.71-7.62 (m, 7H), 7.61-7.57 (m, 2H), 7.54 (dd, J=8.8, 2.4Hz, 2H) , 7.47-7.39 (m, 3H), 7.34-7.30 (m, 1H), 7.25 (d, J=2.0Hz, 1H), 7.15-7.12 (m, 2H).

[0191] [Synthesis Example 2] Synthesis of the compound (N-(triphenylene-1-yl)-2-chlorocarbazole)

[0192] Under an argon stream, 2-chlorocarbazole (1.50 g, 7.44 mmol), 1-fluorotriphenylene (2.20 g, 8.93 mmol), tripotassium phosphate (3.16 g, 14.9 mmol), and DMSO (25 mL) were added to a 100 mL two-necked flask and heated and stirred at 150 °C for 11 hours. After cooling to room temperature, 75 mL of water was added to precipitate the solid, and a brown solid was obtained by suction filtration. Recrystallization with a mixed solvent of toluene and butanol yielded 2.45 g of a white solid of 2-chloro-9-(triphenylene-1-yl)carbazole (5.73 mmol, yield 77%). The compound was identified as follows: １ This was performed using H-NMR measurement. １ H-NMR (d ６ -DMSO) δ (ppm): 9.13 (d, J = 7.6 Hz, 1H), 8.92-8.97 (m, 1H), 8.80-8.84 (m, 1H), 8.74 (d, J = 8.0Hz, 1H), 8.33-8.38 (m, 2H), 7.95 (t, J = 8.0 Hz, 1H), 7.74-7.82 (m, 3H), 7.43 (t, J=7.6Hz, 1H), 7.29-7.34 (m, 3H ), 7.00 (d, J=1.6Hz, 1H), 6.92-6.97 (m, 2H), 6.82 (t, J=7.6Hz, 1H).

[0193] [Synthesis Example 3] Synthesis of compound (B-29aa)

[0194] Under an argon stream, N-(triphenylene-1-yl)-2-chlorocarbazole (2.10 g, 4.91 mmol), bis(4-(naphthalene-2-yl)phenyl)amine (1.88 g, 4.46 mmol), palladium acetate (20.0 mg, 89.2 μ mmol), SPhos (104 mg, 253 μ mmol), sodium tert-butoxide (73.3 mg, 178 mmol), and xylene (45 mL) were added to a 200 mL two-necked flask and stirred at 140 °C for 5 hours. After cooling to room temperature, pure water and methanol were added, and the precipitated solid was collected. The mixture was then stirred in chlorobenzene at 140 °C with activated carbon added. The solution obtained by hot filtration was concentrated, and recrystallization was performed with a mixed solvent of chlorobenzene and butanol to obtain 3.25 g of compound (B-29aa) (4.00 mmol, yield 90%). The sublimation temperature of compound (B-29aa) was 360°C, and it was confirmed that the sublimated compound (B-29aa) was glassy. The identification of the compound was as follows: １ This was performed using H-NMR measurement. １ H-NMR (d ６ -DMSO) δ (ppm): 8.98 (d, J=8.0Hz, 1H), 9.89 (d, J=8.0Hz, 1H), 8.79 (dd, J=8.0H z, 2.8Hz, 2H), 8.28 (d, J=8.0Hz, 1H), 8.21 (d, J=8.0Hz, 1H), 8. 06 (s, 1H), 8.72-8.00 (m, 8H), 7.48-7.65 (m, 13H), 7.33-7.44 (m, 3H), 6.85-6.90 (m, 2H), 6.78 (d, J=8.0Hz, 5H), 6.38 (d, 1H).

[0195] [Synthesis Example 4] Synthesis of compound (B-55a)

[0196] Under an argon stream, N-phenyl-2-bromocarbazole (2.03 g, 6.29 mmol), N-(phenanthrene-2-yl)triphenylene-2-amine (2.40 g, 5.72 mmol), palladium acetate (12.8 mg, 57.2 μ mmol), SPhos (47.0 mg, 114 μ mmol), sodium tert-butoxide (715 mg, 7.44 mmol), and xylene (29 mL) were added to a 200 mL two-necked flask and stirred at 140 °C for 1 hour. After cooling to room temperature, pure water and hexane were added, and the precipitated solid was collected. The mixture was then stirred in toluene at 100 °C with activated carbon. The solution obtained by hot filtration was concentrated, and recrystallization was performed in a mixed solvent of toluene and butanol to obtain 3.12 g of compound (B-55a) (4.72 mmol, yield 83%). The sublimation temperature of compound (B-55a) was confirmed to be 340°C, and the sublimated product of compound (B-55a) was confirmed to be glassy. The identification of the compound is １ This was performed using H-NMR measurement. １ H-NMR (d ６ -DMSO) δ (ppm): 8.80-8.68 (m, 6H), 8.47 (d, J = 2.2Hz, 1H), 8.33 (d, J = 8.3Hz, 1H), 8.26 ( d, J=8.3Hz, 1H), 8.21 (d, J=7.8Hz, 1H), 7.94 (d, J=8.1Hz, 1H), 7.77 (d, J=9.0Hz, 1H), 7.72-7.64 (m, 6H), 7.61-7.52 (m, 5H), 7.48-7.39 (m, 4H) , 7.35-7.28 (m, 3H), 7.26 (d, J=1.7Hz, 1H), 7.16 (dd, J=8.3, 2.0Hz, 1H).

[0197] [Synthesis Example 5] Synthesis of compound (C-9a)

[0198] Under an argon stream, di([1,1':4',1''-terphenyl]-4-yl)amine (45.7 mg, 96.5 μmol), 3-bromo-9-phenyl-9H-carbazole (93.3 mg, 290 μmol), palladium acetate (4.33 mg, 19.3 μmol), SPhos (15.8 mg, 38.6 μmol), (92.8 mg, 965 μmol), and mesitylene (64 mL) were added to a 100 mL two-necked flask and stirred at 165 °C for 15 hours. After cooling to room temperature, pure water and hexane were added, and the precipitated solid was collected. The mixture was then stirred in toluene at 100 °C with activated carbon. The solution obtained by hot filtration was concentrated, and recrystallization was performed in a mixed solvent of toluene and butanol to obtain 1.22 g of a white solid of compound (C-9a) (1.71 mmol, yield 89%). The sublimation temperature of compound (C-9a) was confirmed to be 360°C, and the sublimated compound (C-9a) was confirmed to be glassy. １ H-NMR (d ６ -DMSO) δ (ppm): 8.26 (d, J=7.8Hz, 1H), 8.19 (d, J=1.7Hz, 1H), 7.77-7.74 (m, 8H), 7.73-7.67 (m, 12H), 7.5 6 (s, 1H), 7.50-7.43 (m, 6H), 7.39-7.31 (m, 4H), 7.26 (d, J=1.0Hz, 1H), 7.19-7.16 (m, 4H).

[0199] [Synthesis Example 6] Synthesis of Compound (D-9v)

[0200] Regarding the synthesis of compound (D-9v), the same method as in Synthesis Example 1 was used, except that N-(naphthalene-1-yl)-4-chlorocarbazole was used as a starting material instead of N-(phenanthren-9-yl)-2-chlorocarbazole, and compound (D-9v) was obtained in a yield of 91%. The sublimation temperature of compound (D-9v) was 350°C, and it was confirmed that the sublimated compound (D-9v) was glassy. The identification of the compound is as follows: １ This was performed using H-NMR measurement. １ H-NMR (d ６-DMSO) δ (ppm) = 8.61 (d, J = 2.0Hz, 1H), 8.47 (d, J = 8.3Hz, 1H), 8.21-8 .31 (m, 5H), 8.07 (d, J=8.1Hz, 1H), 7.75 (d, J=8.4Hz, 1H), 7.71-7.73 (m, 8H), 7.64-7.68 (m, 8H), 7.55 (t, J=7.1Hz, 1H), 7.36-7.51 (m, 8H) , 7.31 (t, J = 6.7Hz, 1H), 7.24 (d, J = 8.9Hz, 4H), 7.16 (d, J = 2.0Hz, 1H).

[0201] [Synthesis Example 7] Synthesis of Compound (D-9w)

[0202] Regarding the synthesis of compound (D-9w), the same method as in Synthesis Example 1 was used, except that N-(naphthalene-2-yl)-4-chlorocarbazole was used instead of N-(phenanthren-9-yl)-2-chlorocarbazole as a starting material, and compound (D-9w) was obtained in a yield of 73%. The sublimation temperature of compound (D-9w) was 355°C, and it was confirmed that the sublimated product of compound (D-9w) was glassy. The identification of the compound is as follows: １ This was performed using H-NMR measurement. １ H-NMR (d ６ -DMSO) δ (ppm) = 8.35 (d, J = 2.8 Hz, 1H), 8.27 (d, J = 9.2 Hz, 1H), 8.13 (d, J = 9.8Hz, 2H), 7.89 (d, J = 8.2Hz, 1H), 7.83 (d, J = 9.5Hz, 1H), 7.66-7.75 ( m, 18H), 7.57 (d, J = 8.1Hz, 1H), 7.44-7.51 (m, 6H), 7.39 (d, J = 7.3Hz, 3H ), 7.22 (t, J = 8.7Hz, 4H), 7.16 (d, J = 7.3Hz, 1H), 7.10 (d, J = 7.0Hz, 1H).

[0203] [Synthesis Example 8] Synthesis of Compound (D-19a)

[0204] Under an argon stream, N-phenylcarbazole-4-amine (1.08 g, 4.20 mmol), 2-bromophenanthrene (2.27 g, 8.82 mmol), palladium acetate (28.3 mg, 126 μ mmol), SPhos (103 mg, 252 μ mmol), sodium tert-butoxide (1.21 g, 12.6 mmol), and xylene (21 mL) were added to a 50 mL two-necked flask and stirred at 140 °C for 2 hours. After cooling to room temperature, pure water and hexane were added, and the precipitated solid was collected. The mixture was then stirred in toluene at 100 °C with activated carbon. The solution obtained by hot filtration was concentrated, and hexane was added to crystallize the solid, yielding 1.73 g of compound (D-19a) (2.83 mmol, yield 67%). The sublimation temperature of compound (D-19a) was 305°C, and it was confirmed that the sublimated compound (D-19a) was glassy. The identification of the compound was １ This was performed using H-NMR measurement. １ H-NMR (d ６ -DMSO) δ (ppm): 8.75 (d, J = 8.8Hz, 2H), 8.68 (d, J=8.4Hz, 2H), 7.92 (d, J=7.2Hz, 2H), 7.83 (d, J=8.0Hz, 1H), 7.70-7.75 (m, 5H), 7.50-7.6 7 (m, 12H), 7.39 (d, J = 7.2Hz, 1H), 7.26-7.34 (m, 2H), 7.14 (d, J = 7.2Hz, 1H), 6.96 (t, J = 7.2Hz, 1H).

[0205] [Synthesis Example 9] Synthesis of Compound (D-35a)

[0206] Under an argon stream, N-phenylcarbazole-4-amine (1.03 g, 4.00 mmol), 2-(4-chlorophenyl)phenanthrene (2.43 g, 8.40 mmol), palladium acetate (26.9 mg, 120 μ mmol), SPhos (98.5 mg, 240 μ mmol), sodium tert-butoxide (1.15 g, 12.0 mmol), and xylene (20 mL) were added to a 50 mL two-necked flask and stirred at 140 °C for 2 hours. After cooling to room temperature, pure water and hexane were added, and the precipitated solid was collected. The mixture was then stirred in toluene at 100 °C with activated carbon added. The solution obtained by hot filtration was concentrated, and recrystallization was performed in a mixed solvent of toluene and ethanol to obtain 2.80 g of compound (D-35a) (3.66 mmol, yield 92%). The sublimation temperature of compound (D-35a) was confirmed to be 360°C, and the sublimated product of compound (D-35a) was confirmed to be glassy. The identification of the compound is １ This was performed using H-NMR measurement. １ H-NMR (d ６ -DMSO) δ (ppm): 8.84 (dd, J = 8.4Hz, 13.2Hz, 4H), 8.26 (d, J = 2.0Hz, 2H), 7.98 (d, J = 8.4Hz, 4H), 7.82-7.90 (m, 4H), 7.55-7.76 (m, 10H), 7.36-7.40 (m, 3H), 7.26 (d, J = 8.4Hz, 4H), 7.15 (d, J = 6.8Hz, 1H), 7.07-7.11 (m, 1H).

[0207] [Synthesis Example 10] Synthesis of compound (D-37w)

[0208] Under an argon stream, N-(naphthalene-2-yl)-4-chlorocarbazole (2.90 g, 7.22 mmol), bis(9,9-dimethylfluoren-2-yl)amine (2.60 g, 7.94 mmol), palladium acetate (32.4 mg, 144 μ mmol), xylene solution of 25% by weight of tert-butylphosphine (234 mg, 289 μ mmol), sodium tert-butoxide (1.04 g, 10.8 mmol), and xylene (36 mL) were added to a 50 mL two-necked flask and stirred at 140 °C for 8 hours. After cooling to room temperature, pure water was added and the mixture was transferred to a separatory funnel for extraction with toluene. After brine washing and dehydration with anhydrous magnesium sulfate, a brown solid was obtained by vacuum concentration. Activated carbon was added to toluene at 100 °C and stirred. The solution obtained by hot filtration was concentrated, and 1.60 g of compound (D-37w) was obtained by recrystallization in a mixed solvent of toluene and ethanol (2.31 mmol, yield 32%). The sublimation temperature of compound (D-37w) was 290°C, and it was confirmed that the sublimated compound (D-37w) was glassy. The identification of the compound was as follows: １ This was performed using H-NMR measurement. １ H-NMR (d ６ -DMSO) δ (ppm) = 8.30 (d, J = 2.0 Hz, 1H), 8.24 (d, J = 8.8 Hz, 1H), 8.09-8.13 (m , 1H), 7.90 (dd, J = 8.8Hz, 2.0Hz, 1H), 7.74 (d, J = 8.0Hz, 1H), 7.63-7.68 (m, 6 H), 7.48-7.54 (m, 5H), 7.35-7.39 (m, 2H), 7.22-7.31 (m, 5H), 7.09 (d, J = 6.8 Hz, 1H), 6.93 (t, J=7.6Hz, 1H), 8.83 (dd, J=8.0Hz, 2.0Hz, 2H), 3.34 (s, 6H).

[0209] [Synthesis Example 11] Synthesis of Compound (D-55a)

[0210] Under an argon stream, N-phenyl-4-bromocarbazole (1.68 g, 5.20 mmol), N-(phenanthrene-2-yl)triphenylene-2-amine (2.40 g, 5.72 mmol), palladium acetate (11.7 mg, 52.0 μmol), SPhos (42.7 mg, 104 μmol), sodium tert-butoxide (650 mg, 6.76 mmol), and xylene (26 mL) were added to a 100 mL two-necked flask and stirred at 140 °C for 1 hour. After cooling to room temperature, pure water and hexane were added, and the precipitated solid was collected. The mixture was then stirred in toluene at 100 °C with activated carbon added. The solution obtained by hot filtration was concentrated, and 1.15 g of compound (D-55a) was obtained by silica gel chromatography in a mixed solvent of hexane and toluene (1.74 mmol, yield 34%). The sublimation temperature of compound (D-55a) was confirmed to be 360°C, and the sublimated product of compound (D-55a) was confirmed to be glassy. The identification of the compound is １ This was performed using H-NMR measurement. １ H-NMR (d ６ -DMSO) δ (ppm): 8.81-8.66 (m, 6H), 8.48 (d, J = 2.2Hz, 1H), 8.23 ​​(d, J = 7.6Hz, 1H), 7.91 (m, 2H), 7.76-7.5 3 (m, 16H), 7.46-7.41 (m, 2H), 7.35-7.27 (m, 2H), 7.24-7.22 (m, 1H), 6.98-6.94 (m, 1H).

[0211] [Synthesis Example 12] Synthesis of Compound (D-66a)

[0212] Under an argon stream, N-(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1':4',1''-terphenyl]-4-amine (2.20 g, 4.51 mmol), 4-bromo-9-phenyl-9H-carbazole (1.60 g, 4.96 mmol), palladium acetate (10.1 mg, 45.1 μmol), NaOtBu (564 mg, 1.5.87 mmol), SPhos (37.0 mg, 90.2 μmol), and xylene (23 mL) were added to a 100 mL two-necked flask and stirred at 140 °C for 3 hours. After cooling to room temperature, pure water and hexane were added to collect the precipitated solid, and activated carbon was added and stirred in toluene at 100 °C. The solution obtained by hot filtration was concentrated and purified by silica gel chromatography using a mixed solvent of hexane and toluene to obtain 1.22 g of a white solid of compound (D-66a) (1.67 mmol, yield 37.1%). The sublimation temperature of compound (D-66a) was 350°C, and it was confirmed that the sublimated compound (D-66a) was glassy. The identification of the compound was as follows: １ This was performed using H-NMR measurement. １ H-NMR (d ６ -DMSO) δ (ppm): 8.19 (d, J=7.1Hz, 1H), 8.10 (dd, J=7.8, 1.2Hz, 1H), 7.92-7.88 (m, 3H), 7.76-7.67 (m, 14H), 7.62-7.35 (m, 11H), 7.26 (m, 4H), 7.18-7.16 (m, 1H), 7.13-7.09 (m, 1H).

[0213] [Synthesis Example 13] Synthesis of compound (H-19a)

[0214] Under an argon stream, 4-(di(phenanthrene-2-yl)amino)phenyl trifluoromethanesulfonate (2.67 g, 4.50 mmol), (9-phenyl-9H-carbazole-4-yl)boronic acid (1.94 g, 6.75 mmol), [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride dichloromethane adduct (36.7 mg, 45.0 μmol), tripotassium phosphate aqueous solution (3.37 mL, 4 molar, 13.5 mmol), and THF (23 mL) were added to a 100 mL two-necked flask and stirred at 70°C for 5 hours. After cooling to room temperature, pure water and hexane were added to collect the precipitated solid, and the mixture was stirred with activated carbon in toluene at 100°C. The solution obtained by hot filtration was concentrated and purified by silica gel chromatography using a mixed solvent of hexane and toluene to obtain 1.50 g of a white solid compound (H-19a) (2.18 mmol, yield 49%). The sublimation temperature of compound (H-19a) was 350°C, and it was confirmed that the sublimated compound (H-19a) was glassy. The identification of the compound was １ This was performed using H-NMR measurement. １ H-NMR (d ６ -DMSO) δ (ppm): 8.87 (d, J=9.3Hz, 1H), 8.77 (d, J=8.3Hz, 1H), 7.97 (d, J=6.8Hz, 1H), 7.83- 7.59 (m, 10H), 7.51-7.47 (m, 1H), 7.42-7.33 (m, 3H), 7.20 (d, J=6.6Hz, 1H).

[0215] [Synthesis Reference Example 1] Synthesis of Compound (B-3k) As Synthesis Reference Example 1, Compound (B-3k), represented by the following formula, was used. Compound (B-3k) was synthesized according to the method disclosed in Japanese Patent Application Publication No. 2011-1349.

[0216] (Comparative Example 1) As Comparative Example 1, compound (X1) represented by the following formula was used. Compound (X1) was synthesized according to the method disclosed in Japanese Patent Application Publication No. 2019-034939.

[0217] (Comparative Example 2) As Comparative Example 2, compound (X2) represented by the following formula was used. Compound (X2) was synthesized according to the method disclosed in (International Publication No. WO2024 / 204559A1).

[0218] (Comparative Example 3) As Comparative Example 3, compound (X3) represented by the following formula was used. Compound (X3) was synthesized according to the method disclosed in (International Publication No. WO2023 / 286816A1).

[0219] (Comparative Example 4) As Comparative Example 4, compound (X4) represented by the following formula was used. Compound (X4) was synthesized according to the method disclosed in (International Publication No. WO2023 / 286817A1).

[0220] (Comparative Example 5) As Comparative Example 5, compound (X5) represented by the following formula was used. Compound (X5) was synthesized according to the method disclosed in (International Publication No. WO2012 / 114928A1).

[0221] (Glass transition temperature) This was measured using a DSC7020 manufactured by Hitachi High-Tech Science Corporation. The results are shown in Table 7.

[0222]

[0223] (Example A-1 of the element: Fabrication of a photoelectric conversion element for an image sensor using compound (B-9y)) As shown in Figure 1, a photoelectric conversion element 100 for an image sensor was fabricated having a laminated 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, and its characteristics were evaluated.

[0224] (Preparation of Substrate 1 and First Electrode 2) A glass substrate with a transparent ITO electrode was prepared, on which a 2 mm wide indium-tin (ITO) film (thickness 110 nm) was patterned in stripes, with the first electrode mounted on its surface. Next, this substrate was cleaned with isopropyl alcohol and then surface-treated by ozone ultraviolet cleaning.

[0225] (Vacuum deposition) After cleaning and surface treatment, each layer was deposited using the vacuum deposition method on the substrate. Specifically, a glass substrate with ITO transparent electrodes was introduced into the vacuum deposition chamber, and a 7.0 × 10 －５ The pressure was reduced to 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(pyridine-4-yl)phenyl)-2-methylpyrimidine was deposited at a rate of 0.10 nm / second to create an electron transport layer (hole blocking layer) 3. (2) Fabrication of photoelectric conversion layer 4 2Ph-BTBT, F6-SubPc-OC6F5, and fullerene (C60) were co-deposited at a deposition rate ratio of 4:4:2 to create a 200 nm film. The deposition rate was 0.15 nm / second. (3) Fabrication of hole transport layer (electron blocking layer) 5 Sublimation-purified compound (B-9y) was deposited at a rate of 0.10 nm / second to create a 10 nm film. (4) Preparation of buffer layer 6 A buffer layer 6 was prepared by depositing 10 nm of sublimation-purified 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN) at a rate of 0.10 nm / second.

[0226] (5) (Fabrication of the second electrode 7) A metal mask was placed perpendicular to the ITO stripe on the substrate, and the second electrode 7 was deposited. Gold was deposited on the second electrode to a thickness of 80 nm. The gold deposition rate was 0.1 nm / second.

[0227] Using the method described above, the area is 4 mm². ２ Photoelectric conversion elements for image sensors were fabricated. The thickness of each layer was measured using a stylus-type film thickness gauge (DEKTAK, Bruker). The fabricated elements were 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 (Nagase ChemteX).

[0228] (Element Example A-2) to (Element Reference Example-1) The photoelectric conversion elements for image sensors of Element Example A-2 to Element Reference Example-1 were fabricated in the same manner as Element Example A-1, except that compounds (B-29aa) to (B-3k) were used instead of compound (B-9y) in the fabrication of the hole transport layer 104 of Element Example A-1.

[0229] (Element Comparative Example 1) to (Element Comparative Example 5) The photoelectric conversion elements for image sensors of Element Comparative Examples 1 to 5 were fabricated in the same manner as Element Example A-1, except that in the fabrication of the hole transport layer 104 of Element Example 1, (X1) to (X5) were used instead of compound (B-9y).

[0230] (Measurement of dark current, external quantum efficiency, and response time) When a voltage of 2.5V (absolute value) was applied to the photoelectric conversion element for the image sensor fabricated as described above, such that electrons were transported to the lower electrode 2 side and holes to the upper electrode 7 side, the dark current, external quantum efficiency, and response time in the dark were evaluated. The dark current was evaluated using a Keithley source measure unit 2636B. The external quantum efficiency was measured using a solar cell spectroscopic sensitivity measuring device (manufactured by Soma Optical Co., Ltd.), with an illumination wavelength of 560 nm and an intensity of 50 μW / cm². ２ The measurement was performed using the following method. Response time was measured by applying a light pulse and then measuring the time it took for the current value to return to its pre-irradiation state.

[0231] The results are shown in Table 8. Note that the results shown in Table 8 are relative values, with the results from Comparative Example 1 set as the baseline value (1.00). Lower dark current values ​​indicate better performance, higher external quantum efficiency values ​​indicate better performance, and shorter response times indicate better performance. The obtained measurement results are shown in Table 8.

[0232] The compounds used in the examples are listed below.

[0233]

[0234] As shown in Table 8, the device in the example using a specific compound as the hole transport layer exhibited suppressed dark current and superior responsiveness compared to the device in the comparative example.

[0235] 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 image sensor

Claims

1. A photoelectric conversion element for an imaging device, including a photoelectric conversion layer and a hole transport layer between a first electrode and a second electrode, wherein the photoelectric conversion layer contains at least two kinds of organic materials, and the hole transport layer contains a compound represented by the following formula (1). A photoelectric conversion element for an imaging device. In formula (1), Ar １ is an aromatic hydrocarbon group of a monocyclic or condensed ring of 3 rings or less having 6 to 30 carbon atoms which may have a substituent, Ar ２ is an aromatic hydrocarbon group of a monocyclic or condensed ring of 4 rings or less having 6 to 30 carbon atoms which may have a substituent, or a heteroaromatic group of a monocyclic or condensed ring of 4 rings or less having 6 to 30 carbon atoms which may have a substituent, L １ is an aromatic hydrocarbon group of a monocyclic or condensed ring of 3 rings or less having 6 to 30 carbon atoms which may have a substituent, L ２ is an aromatic hydrocarbon group of a monocyclic or condensed ring of 4 rings or less having 6 to 30 carbon atoms which may have a substituent, or a heteroaromatic group of a monocyclic or condensed ring of 4 rings or less having 6 to 30 carbon atoms which may have a substituent, n １ and n ２ are each independently represented by an integer of 0 to 2, L ３ is a single bond, or an aromatic hydrocarbon group of a monocyclic, linked ring, or condensed ring having 6 to 20 carbon atoms which may have a substituent, and A is a group represented by the following formula (2); In formula (2), Ar ３ is an aromatic hydrocarbon group of a monocyclic, linked ring, or condensed ring having 6 to 30 carbon atoms which may have a substituent, or a heteroaromatic group of a monocyclic, linked ring, or condensed ring having 6 to 30 carbon atoms composed of carbon, hydrogen, oxygen, and sulfur atoms which may have a substituent, R １ ~R ８ Each independently represents a hydrogen atom, a deuterium atom, a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms (which may have substituents), a monocyclic, linked, or fused heterocyclic aromatic group having 3 to 36 carbon atoms (which may have substituents), or a linear or branched alkyl group having 1 to 18 carbon atoms, provided that R １ ~R ８ Any one of the groups is L ３ , or L ３ It is directly bonded to an adjacent nitrogen atom.

2. Ar １ The photoelectric conversion element for an image sensor according to claim 1, wherein the group is a phenyl group, a naphthyl group, anthryl group, a phenanthryl group, or a dimethylfluorenyl group.

3. Ar ２ The photoelectric conversion element for an image sensor according to claim 1, wherein the group is a phenyl group, a naphthyl group, anthryl group, a phenanthryl group, a dimethylfluorenyl group, a triphenylenyl group, a dibenzofuranyl group, a dibenzothienyl group, or a carbazolyl group.

4. Ar ３ The photoelectric conversion element for an image sensor according to claim 1, wherein the group is a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, anthryl group, a phenanthryl group, a triphenylel group, a naphthylphenyl group, a phenylnaphthyl group, a naphthylnaphthyl group, a phenanthrylphenyl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a spirobifluorenyl group, a dibenzofuranyl group, a dibenzothienyl group, a dibenzofuranylphenyl group, or a dibenzothienylphenyl group.

5. R １ ~R ８ The photoelectric conversion element for an image sensor according to claim 1, wherein each of the members is independently a hydrogen atom, a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, a methyl group, a tert-butyl group, a cyclohexyl group, a 1-adamantyl group, or a 2-adamantyl group.

6. L １ and L ２ However, each is independently a phenylene group, a naphthylene group, or a biphenylene group, n １ and n ２ However, each is independently represented by an integer between 0 and 2, Ar １ and L １ The total number of carbon atoms and Ar ２ and L ２ The photoelectric conversion element for an image sensor according to claim 1, wherein the total number of carbon atoms is 30 or less.

7. L ３ The photoelectric conversion element for an image sensor according to claim 1, wherein the element is a single bond, a phenylene group, or a naphthylene group.

8. (L １ )n １ -Ar １ , and (L ２ )n ２ -Ar ２ The photoelectric conversion element for an image sensor according to claim 1, wherein the total number of carbon atoms of each element is independently 13 to 24.

9. A photoelectric conversion element for an image sensor according to any one of claims 1 to 8, wherein the glass transition temperature of the compound represented by formula (1) is 140°C or higher.

10. A photoelectric conversion element for an image sensor according to any one of claims 1 to 8, wherein the molecular weight of the compound represented by formula (1) is less than 1000.

11. The photoelectric conversion element for an image sensor according to claim 1, wherein the photoelectric conversion layer comprises at least three materials.

12. A photoelectric conversion element for an image sensor according to claim 1, comprising a photoelectric conversion layer, a hole transport layer, and a buffer layer in this order between a first electrode and a second electrode, wherein the buffer layer contains an organic material.

13. The photoelectric conversion element for an image sensor according to claim 1, wherein the photoelectric conversion layer contains a fullerene.

14. An amine compound represented by the following formula (3). In formula (3), Ar ４ and Ar ５ Each is independently a monocyclic or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents, or a monocyclic or fused heterocyclic aromatic group having 6 to 30 carbon atoms, which may have substituents, L ４ and L ５ Each is independently a monocyclic or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents, or a monocyclic or fused heterocyclic aromatic group having 6 to 30 carbon atoms, which may have substituents, n ４ and n ５ Each of these is independently represented by an integer between 0 and 2, L ６ R is a monocyclic, linking, or fused aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have single bonds or substituents. ９ ~R １５ Each of these independently represents a hydrogen atom, a deuterium atom, a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms (which may have substituents), a monocyclic, linked, or fused heterocyclic aromatic group having 3 to 36 carbon atoms (which may have substituents), or a linear or branched alkyl group having 1 to 18 carbon atoms.

15. Ar ４ and Ar ５ The amine compound according to claim 14, wherein each of these groups may independently be substituted with a methyl group: a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, anthryl group, a phenanthryl group, a triphenylel group, a naphthylphenyl group, a phenylnaphthyl group, a naphthylnaphthyl group, a phenanthrylphenyl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a spirobifluorenyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, a dibenzofuranylphenyl group, a dibenzothienylphenyl group, or a carbazolylphenyl group.

16. R ９ ~R １５ The amine compound according to claim 14, wherein each is independently a hydrogen atom, a phenyl group, or a naphthyl group.

17. L ６ The amine compound according to claim 14, wherein is a single bond, a phenylene group, or a naphthylene group.

18. An amine compound represented by the following formula (4). In equation (4), B is a base represented by the following equation (5): In formula (5), R １６ ~R ２３ Each independently represents a hydrogen atom, a deuterium atom, a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms (which may have substituents), a monocyclic, linked, or fused heterocyclic aromatic group having 3 to 36 carbon atoms (which may have substituents), or a linear or branched alkyl group having 1 to 18 carbon atoms, provided that R １７ or R １９ One of the groups is directly bonded to the nitrogen atom in formula (4), Ar ６ This represents an aromatic hydrocarbon group having 6 to 25 carbon atoms, consisting of a monocycle, linking ring, or fused ring, which may have substituents.

19. R １６ , R １８ , and R ２０ ~R ２３ The amine compound according to claim 18, wherein is a hydrogen atom.

20. An amine compound represented by the following formula (6). Formula (in 6), L ５ , and L ６ Each is independently a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have single bonds or substituents, or a monocyclic, linked, or fused heterocyclic aromatic group having 6 to 30 carbon atoms, which may have substituents, n ５ and n ６ Each of these is independently represented by an integer between 0 and 2, L ４ is a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have single bonds or substituents, where C is a group represented by the following formula (7); In formula (7), R ２４ ~R ３１ Each independently represents a hydrogen atom, a deuterium atom, a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms (which may have substituents), a monocyclic, linked, or fused heterocyclic aromatic group having 3 to 36 carbon atoms (which may have substituents), or a linear or branched alkyl group having 1 to 18 carbon atoms, provided that R ２５ or R ２７ One of the groups is directly bonded to the L4 group in formula (6), and Ar ７ This is a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 25 carbon atoms, which may have substituents, or a monocyclic, linked, or fused heterocyclic aromatic group having 6 to 30 carbon atoms, which may have substituents.

21. The amine compound according to claim 20, wherein L4 and L5 are each independently a single bond or a phenylene group.

22. An amine compound represented by the following formula (8). In equation (8), D is the group represented by the following equation (9); In formula (9), R ３２ ~R ３９ Each independently represents a hydrogen atom, a deuterium atom, a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms (which may have substituents), a monocyclic, linked, or fused heterocyclic aromatic group having 3 to 36 carbon atoms (which may have substituents), or a linear or branched alkyl group having 1 to 18 carbon atoms, provided that R ３２ or R ３４ One of the groups is directly bonded to the nitrogen in formula (8), and Ar ８ This is a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 25 carbon atoms, which may have substituents, or a monocyclic, linked, or fused heterocyclic aromatic group having 6 to 30 carbon atoms, which may have substituents.

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