Condensed ring compound, and material for image sensor photoelectric conversion element

Abstract

The present invention provides: a condensed ring compound contributing to the manufacture of an image sensor photoelectric conversion element having outstanding dark current characteristics and responsiveness; and a material for an image sensor photoelectric conversion element, said material containing the compound.　The condensed ring compound is represented by formula (1). In formula (1), R1 through R16 are each independently a hydrogen atom, a deuterium atom, or a group or the like represented by formula (2). Note that one or more of R1 through R16 are groups represented by formula (2).

Description

Condensed ring compounds and materials for photoelectric conversion elements for image sensors

[0001] The present invention relates to condensed ring compounds, materials for organic electronic devices, materials for photoelectric conversion devices, organic thin films, and organic electronic devices.

[0002] Materials for photoelectric conversion elements used in 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 photoelectric conversion elements for image sensors has been increasing, and materials with superior dark current, external quantum efficiency, and response speed are required. Under these circumstances, the potential of various polycyclic compounds as parent materials is being explored and investigated. As for polycyclic compounds, Patent Document 1 discloses derivatives based on benzothienobenzothiophene. Patent Document 2 discloses various parent materials in addition to benzothienobenzothiophene. Patent Document 3 discloses unsubstituted dibenzo[g,p]chrysene.

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

[0005] One aspect of the present invention aims to propose a material for a photoelectric conversion element and a photoelectric conversion element using a compound having a new polycyclic compound as a parent nucleus, given that the possibility of various polycyclic compounds as parent nuclei for new materials is being explored and investigated.

[0006] Another object of the present invention is to provide a material for a photoelectric conversion element for an image sensor that contributes to the fabrication of a photoelectric conversion element with low dark current and excellent responsiveness, a compound that contributes to the fabrication of a photoelectric conversion element with low dark current and excellent responsiveness, a material for an organic electronic element containing the compound, and a material for a photoelectric conversion element. Incidentally, Patent Document 3 describes using unsubstituted dibenzo[g,p]chrysene as a crystalline layer between the photoelectric conversion layer and the upper electrode. However, Patent Document 3 does not mention the molecular structural characteristics of dibenzo[g,p]chrysene or amorphous films containing dibenzo[g,p]chrysene at all. In addition, the dibenzo[g,p]chrysene described in Patent Document 3 does not provide any knowledge that improves the performance of a photoelectric conversion element for an image sensor.

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

[0008] Aspects of this disclosure relate to the following condensed ring compounds, materials for photoelectric conversion elements for image sensors containing said condensed ring compounds, etc.

[0009] [1] A condensed ring compound represented by the following formula (1). In the formula, R １ ~R １６ Each of these is independently a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a hydroxyl group, a thiol group, an allyl group, a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms which may have substituents, a monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms which may have substituents, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a group represented by the following formula (2). However, R １ ~R １６ At least one of these is a group represented by the following formula (2). In the formula, R ａrepresents a hydrogen atom, a deuterium atom, an aromatic hydrocarbon group composed only of a monocyclic, linked, or fused 6-membered ring having 6 to 30 carbon atoms which may have a substituent, or a heteroaromatic group of a monocyclic, linked, or fused ring having 3 to 36 carbon atoms which may have a substituent; R ｂ represents a hydrogen atom, a deuterium atom, an aromatic hydrocarbon group composed only of a monocyclic, linked, or fused 6-membered ring having 10 to 30 carbon atoms which may have a substituent, or a heteroaromatic group of a monocyclic, linked, or fused ring having 3 to 36 carbon atoms which may have a substituent; Y each independently represents an aromatic hydrocarbon group of a monocyclic, linked, or fused ring having 6 to 30 carbon atoms which may have a substituent, or a heteroaromatic group of a monocyclic, linked, or fused ring having 5 to 36 carbon atoms which may have a substituent; n represents 1 or 2, and when n is 2, the plurality of R ａ to R ｂ may be the same or different. [2] In formula (1), the condensed ring compound according to [1], wherein R ９ to R １６ is a hydrogen atom. [3] In formula (1), the condensed ring compound according to [1], wherein R ５ and R ８ to R １６ are hydrogen atoms. [4] In formula (1), the condensed ring compound according to [1], wherein R ５ to R １６ are hydrogen atoms.

[23] In formula (1), among R １ to R １６ , the group represented by formula (2) is at any one of R ２ to R ４ , the condensed ring compound according to [1]. [5] In formula (2), R ａA condensed ring compound according to any one of [1] to [4], wherein Y is an aromatic hydrocarbon group consisting only of a six-membered ring having 10 to 30 carbon atoms, which may have substituents, or a heteroaromatic group having 3 to 36 carbon atoms, which may have substituents, which is a condensed ring compound according to any one of [1] to [4]. [6] A condensed ring compound according to any one of [1] to [5], wherein in formula (2), Y is an aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents, which is a condensed ring compound according to any one of [1] to [5]. [7] A condensed ring compound according to [6], wherein in formula (2), the aromatic hydrocarbon group represented by Y is a 1,4-phenylene group, a 1,3-phenylene group, a 4,4'-biphenylene group, a 1,4-naphthylene group, a 1,5-naphthylene group, a 2,6-naphthylene group, or an anthracene-9,10-diyl group. [8] In formula (2), R ａ However, R is a phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, crisenyl group, benzocrisenyl group, dibenzocrisenyl group, dibenzofuranyl group, dibenzothionyl group, carbazolyl group, naphthylphenyl group, phenylnaphthyl group, naphthylnaphthyl group, phenanthrylphenyl group, dibenzofuranylphenyl group, dibenzothionylphenyl group, carbazolylphenyl group, or a group that is a combination of these. ｂA condensed ring compound according to any one of [1] to [7], wherein the compound is a biphenyl group, a terphenyl group, a naphthyl group, anthryl group, a phenanthryl group, a pyrenyl group, a crisenyl group, a benzocrisenyl group, a dibenzocrisenyl group, a dibenzofuranyl group, a dibenzothionyl group, a carbazolyl group, a naphthylphenyl group, a phenylnaphthyl group, a naphthylnaphthyl group, a phenanthrylphenyl group, a dibenzofuranylphenyl group, a dibenzothionylphenyl group, a carbazolylphenyl group, or a group being a combination thereof. [9] A material for an organic electronic device comprising a condensed ring compound according to any one of [1] to [8] or

[23] .

[10] A material for a photoelectric conversion device comprising a condensed ring compound according to any one of [1] to [8] or

[23] .

[11] A charge transport material or charge blocking material comprising a condensed ring compound according to any one of [1] to [8] or

[23] .

[12] A hole transport material or electron blocking material comprising a fused ring compound as described in any of [1] to [8] or

[23] .

[13] An organic thin film comprising a fused ring compound as described in any of [1] to [8] or

[23] .

[14] An organic electronic device comprising a fused ring compound as described in any of [1] to [8] or

[23] .

[15] A material for a photoelectric conversion element for an image sensor comprising a fused ring compound represented by the following formula (3). In the formula, R Ａ１ ~R Ａ１６ Each of these is independently a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a hydroxyl group, a thiol group, an allyl group, a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms which may have substituents, a monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms which may have substituents, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a group represented by the following formula (4). However, R Ａ１ ~R Ａ１６ At least one of these is a group represented by the following formula (4). In the formula, R ＡａR 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, or a monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms which may have substituents; Ａｂ This represents a hydrogen atom, a deuterium atom, a monocyclic, linked, or fused aromatic hydrocarbon group having 10 to 30 carbon atoms which may have substituents, or a monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms which may have substituents; Y Ａ Each independently represents a C6-C30 monocyclic, linked, or fused aromatic hydrocarbon group which may have substituents, or a C5-C36 monocyclic, linked, or fused heteroaromatic group which may have substituents; n represents 1 or 2, and if n is 2, multiple R Ａａ ~R Ａｂ They may be the same or different.

[16] In equation (3), R Ａ９ ~R Ａ１６ A material for an image sensor photoelectric conversion element, comprising the fused ring compound described in

[15] , wherein R is a hydrogen atom.

[17] In formula (3), R Ａ５ and R Ａ８ ~R Ａ１６ A material for an image sensor photoelectric conversion element, comprising the fused ring compound described in

[15] , wherein R is a hydrogen atom.

[18] In formula (3), R Ａ５ ~R Ａ１６ A material for an image sensor photoelectric conversion element, comprising the fused ring compound described in

[15] , wherein R is a hydrogen atom.

[24] In formula (3), R Ａ１ ~R Ａ１６ Of these, the group represented by formula (4) is R Ａ２ ~R Ａ４ A material for an image sensor photoelectric conversion element, comprising the condensed ring compound described in

[15] , which is one of the following locations.

[19] In formula (4), R ＡａA material for an image sensor photoelectric conversion element, comprising a fused ring compound according to any one of

[15] to

[18] , wherein the fused ring compound is a monocyclic, linked, or fused aromatic hydrocarbon group having 10 to 30 carbon atoms, which may have substituents, or a monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms, which may have substituents.

[20] In formula (4), Y Ａ A material for an image sensor photoelectric conversion element, comprising a fused ring compound according to any one of

[15] to

[19] , which is a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents.

[21] In formula (4), Y Ａ A material for a photoelectric conversion element for an image sensor, comprising the condensed ring compound described in

[20] , wherein the aromatic hydrocarbon group represented by is a 1,4-phenylene group, a 1,3-phenylene group, a 4,4'-biphenylene group, a 1,4-naphthylene group, a 1,5-naphthylene group, a 2,6-naphthylene group, or an anthracene-9,10-diyl group.

[22] In formula (4), R Ａａ However, R is a phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, crisenyl group, benzocrisenyl group, dibenzocrisenyl group, dibenzofuranyl group, dibenzothionyl group, carbazolyl group, naphthylphenyl group, phenylnaphthyl group, naphthylnaphthyl group, phenanthrylphenyl group, dibenzofuranylphenyl group, dibenzothionylphenyl group, carbazolylphenyl group, or a group that is a combination of these. Ａｂ A material for an image sensor photoelectric element, comprising a condensed ring compound as described in any of

[15] to

[21] , wherein the compound is a biphenyl group, a terphenyl group, a naphthyl group, anthryl group, a phenanthryl group, a pyrenyl group, a crisenyl group, a benzocrisenyl group, a dibenzocrisenyl group, a dibenzofuranyl group, a dibenzothionyl group, a carbazolyl group, a naphthylphenyl group, a phenylnaphthyl group, a naphthylnaphthyl group, a phenanthrylphenyl group, a dibenzofuranylphenyl group, a dibenzothionylphenyl group, a carbazolylphenyl group, or a combination thereof.

[0010] According to one aspect of the present invention, it is possible to provide a condensed ring compound that contributes to the fabrication of a photoelectric conversion element for an image sensor that has excellent dark current characteristics and responsiveness, and a material for a photoelectric conversion element for an image sensor containing the compound.

[0011] This is a schematic cross-sectional view showing an example of a laminated configuration of an image sensor photoelectric conversion element including a material for an image sensor photoelectric conversion element according to one aspect of the present invention.

[0012] The following describes in detail a condensed ring compound according to one aspect of this disclosure, and materials for photoelectric conversion elements for image sensors containing said compound.

[0013] ≪Condensed ring compounds represented by formula (1)≫ Condensed ring compounds are represented by the following formula (1).

[0014] In the formula, R １ ~R １６ Each of these is independently a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a hydroxyl group, a thiol group, an allyl group, a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms which may have substituents, a monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms which may have substituents, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a group represented by the following formula (2). However, R １ ~R １６ At least one of these is a group represented by the following formula (2). In the formula, R ａ R represents an aromatic hydrocarbon group composed only of a hydrogen atom, a deuterium atom, or a six-membered ring having 6 to 30 carbon atoms, which may have substituents, or a heteroaromatic group having 3 to 36 carbon atoms, which may have substituents; ｂR represents an aromatic hydrocarbon group consisting only of a hydrogen atom, a deuterium atom, or a six-membered ring having 10 to 30 carbon atoms that may have substituents, or a heteroaromatic group having 3 to 36 carbon atoms that may have substituents; Y independently represents an aromatic hydrocarbon group having 6 to 30 carbon atoms that may have substituents, or a heteroaromatic group having 5 to 36 carbon atoms that may have substituents; n represents 1 or 2, and if n is 2, multiple R ａ ~R ｂ They may be the same or different.

[0015] The condensed ring compound represented by formula (1) has a linker represented by formula (2) in which the N-containing substituent is Y. For this reason, the photoelectric conversion element for image sensors made using the above condensed ring compound has excellent dark current characteristics and responsiveness.

[0016] A preferred embodiment of the definition in formula (1) above is as follows:

[0017] <R １ ~R １６ >

[0018] (Aromatic hydrocarbon group) R １ ~R １６ 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.

[0019] Examples of the aromatic hydrocarbon group 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.

[0020] Furthermore, if the aromatic hydrocarbon group has substituents, it is preferable that each substituent independently be a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, an optionally substituted phosphine oxide group, an optionally substituted silyl group, a optionally substituted boronyl group having 2 to 10 carbon atoms, an alkyl group, an alkoxy group, an aromatic hydrocarbon group, a heteroaromatic group, or a trifluoromethylsulfonyloxy group. Among these, alkyl groups, aromatic hydrocarbon groups, and heteroaromatic groups are more preferred.

[0021] Examples of the substituted phosphine oxide group include unsubstituted phosphine oxide groups and substituted phosphine oxide groups. A substituted phosphine oxide group is preferred.

[0022] The phosphine oxide group having the above substituent is preferably a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 18 carbon atoms, or a fused heteroaromatic group. Specifically, examples include groups substituted with two aryl groups, such as diphenylphosphine oxide.

[0023] Examples of the substituted silyl group include an unsubstituted silyl group and a substituted silyl group. A substituted silyl group is preferred.

[0024] Preferred substituents for silyl groups include monocyclic, linked, or fused aromatic hydrocarbon groups having 6 to 18 carbon atoms, or fused heteroaromatic groups. Specifically, examples include groups substituted with three aryl groups, such as a triphenylsilyl group.

[0025] Examples of the above substituents, which may have saturated hydrocarbon groups having 2 to 10 carbon atoms, include a 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.

[0026] The alkyl group that is the substituent mentioned above 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.

[0027] 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.

[0028] Examples of the above-mentioned substituent aromatic hydrocarbon groups include phenyl group, biphenylyl group, terphenylyl group, naphthyl group, fluorenyl group, fluoranthenyl group, anthryl group, phenanthryl group, benzofluorenyl group, triphenylenyl group, spirobifluorenyl group, diphenylfluorenyl group, and dibenzo[g,p]crisenyl group.

[0029] Examples of the heteroaromatic substituents mentioned above include 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, 4,6-diphenyl-1,3,5-triazyl group, indolyl group, benzothienyl group, benzofuranyl group, and benzimi Examples include dazolyl 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, and the like.

[0030] (Heteroaromatic group) R １ ~R １６ A monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms, which may have substituents represented by , is preferably a monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms, containing at least one atom selected from the group consisting of oxygen, nitrogen, and sulfur atoms on the aromatic ring.

[0031] Examples of such heteroaromatic groups include dibenzofuranyl group, dibenzothionyl 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.

[0032] Furthermore, if the heteroaromatic group has substituents, it is preferable that each substituent is independently a cyano group, a fluorine atom, a trifluoromethyl group, an alkyl group, an alkoxy group, an aromatic hydrocarbon group, a heteroaromatic group, or a trifluoromethylsulfonyloxy group. Among these, alkyl groups, aromatic hydrocarbon groups, and heteroaromatic groups are more preferred.

[0033] The alkyl group that is the substituent is preferably a linear or branched alkyl group having 1 to 18 carbon atoms. １ ~R １６ When the aromatic hydrocarbon group represented by has substituents, examples of substituents include those similar to the alkyl groups exemplified above.

[0034] The alkoxy group that is a substituent is preferably a linear or branched alkoxy group having 1 to 18 carbon atoms. １ ~R １６ When the aromatic hydrocarbon group represented by has substituents, examples of substituents include those similar to the alkoxy group exemplified above.

[0035] The above substituent aromatic hydrocarbon group is R １ ~R １６When the aromatic hydrocarbon group represented by has substituents, examples of substituents include those similar to the aromatic hydrocarbon group exemplified above.

[0036] The heteroaromatic group which is the substituent mentioned above is R as described above. １ ~R １６ When the aromatic hydrocarbon group represented by has substituents, examples of substituents include those similar to the heteroaromatic groups exemplified above.

[0037] (Alkyl group) R １ ~R １６ 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, and the like.

[0038] (alkoxy group) R １ ~R １６ Examples of linear or branched alkoxy groups having 1 to 18 carbon atoms, represented by , include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, tert-butoxy, pentyloxy, n-hexyloxy, cyclohexyloxy, octyloxy, decyloxy, dodecyloxy, and octadecyloxy groups.

[0039] In equation (1), R ９ ~R １６ It is preferable that it is a hydrogen atom.

[0040] In equation (1), R ５ and R ８ ~R １６ It is preferable that it is a hydrogen atom.

[0041] In equation (1), R ５ ~R １６ It is preferable that it is a hydrogen atom.

[0042] ≪Base represented by formula (2)≫

[0043] <R ａ >

[0044] (Aryl group) R ａ The aryl group having 6 to 30 carbon atoms, which may have a substituent represented by ａ and is composed only of monocyclic, linked, or condensed 6-membered rings, is preferably an aryl group having 10 to 30 carbon atoms, which may have a substituent and is composed only of monocyclic, linked, or condensed 6-membered rings. Specific examples of the above aryl group include phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, chrysenyl group, triphenylenyl group, benzochrysenyl group, dibenzochrysenyl group, naphthylphenyl group, phenylnaphthyl group, naphthylnaphthyl group, phenanthrylphenyl group, phenylphenanthryl group, triphenylenylphenyl group, phenyltriphenylenyl group, etc. The above aryl group composed only of 6-membered rings is also an aryl group containing 6-membered rings but not containing 5-membered rings.

[0045] (Heteroaryl group) R ａ Preferred embodiments and specific examples of the heteroaryl group having 3 to 36 carbon atoms, which may have a substituent represented by ａ and is monocyclic, linked, or condensed, and specific examples of the substituent when the heteroaryl group has a substituent are the same as those described for the heteroaryl group in the aforementioned R １ to R １６ are as described above.

[0046] In formula (2), among the groups represented by R ａ , R ａ is preferably the above aryl group having 10 to 30 carbon atoms, which may have a substituent and is composed only of monocyclic, linked, or condensed 6-membered rings, or the above heteroaryl group having 3 to 36 carbon atoms, which may have a substituent and is monocyclic, linked, or condensed.

[0047] <R ｂ >

[0048] (Aryl group) R ｂ Specific examples of the aryl group having 10 to 30 carbon atoms, which may have a substituent and is composed only of monocyclic, linked, or condensed 6-membered rings, are the same as those of the aforementioned R ａAmong the aromatic hydrocarbon groups described, which may have substituents represented by , examples include substituents other than the phenyl group, and which consist only of six-membered rings having 6 to 30 carbon atoms, such as monocyclic, linked, or fused rings.

[0049] (Heteroaromatic group) R ｂ Preferred embodiments and specific examples of a monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms, which may have substituents represented by the above, and specific examples of substituents when the heteroaromatic group has substituents are as follows: １ ~R １６ Examples similar to those described for heteroaromatic groups can be found.

[0050] In formula (2), preferably, R ａ However, R is a phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, crisenyl group, benzocrisenyl group, dibenzocrisenyl group, dibenzofuranyl group, dibenzothionyl group, carbazolyl group, naphthylphenyl group, phenylnaphthyl group, naphthylnaphthyl group, phenanthrylphenyl group, dibenzofuranylphenyl group, dibenzothionylphenyl group, carbazolylphenyl group, or a group that is a combination of these. ｂ However, these are biphenyl groups, terphenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, pyrenyl groups, crisenyl groups, benzocrisenyl groups, dibenzocrisenyl groups, dibenzofuranyl groups, dibenzothionyl groups, carbazolyl groups, naphthylphenyl groups, phenylnaphthyl groups, naphthylnaphthyl groups, phenanthrylphenyl groups, dibenzofuranylphenyl groups, dibenzothionylphenyl groups, carbazolylphenyl groups, or combinations thereof.

[0051] <Y>

[0052] Among a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents represented by Y, and a monocyclic, linked, or fused heteroaromatic group having 5 to 36 carbon atoms, which may have substituents, the former is preferred for Y.

[0053] Examples of the aromatic hydrocarbon group represented by Y include phenylene group, biphenylene group, terphenylene group, naphthylene group, fluorenylene group, spirobifluorenylene group, phenanthrene-diyl group, triphenylene-diyl group, pyrene-diyl group, anthracene-diyl group, and the like.

[0054] Examples of the heteroaromatic groups represented by Y 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, and the like.

[0055] Specific examples of the aromatic hydrocarbon group represented by Y and the heteroaromatic group represented by Y include, for example, 1,4-phenylene group, 1,3-phenylene group, 4,4'-biphenylene group, 4,3'-biphenylene group, 3,3'-biphenylene group, 4,4''-p-terphenylene group, 4,3''-p-terphenylene group, 3,3''-p-terphenylene group, 4,3'-p-terphenylene group, 3,3'-p-terphenylene group, 4,4''-m-terphenylene group, 4,3''-m-terphenylene group, 3,3''-m-terphenylene group, 4,4'-m-terphenylene group, 4,5'-m-terphenylene group, 3,4' -m-terphenylene group, 3,5'-m-terphenylene group, 1,3-naphthylene group, 1,4-naphthylene group, 1,5-naphthylene group, 1,6-naphthylene group, 1,7-naphthylene group, 1,8-naphthylene group, 2,4-naphthylene group, 2,5-naphthylene group, 2,6-naphthylene group, 2,7-naphthylene group, 2,8-naphthylene group, 9,9-dimethylfluorene-2,7-diyl group, 9,9-dimethylfluorene-2,8-diyl group, 9,9-dimethylfluorene-2,4-diyl group, 9,9-dimethylfluorene -2,5-diyl group, 9,9-dimethylfluorene-2,6-diyl group, 9,9-dimethylfluorene-3,6-diyl group, 9,9-diphenylfluorene-2,7-diyl group, 9,9-diphenylfluorene-2,8-diyl group, 9,9-diphenylfluorene-2,4-diyl group, 9,9-diphenylfluorene-2,5-diyl group, 9,9-diphenylfluorene-2,6-diyl group, 9,9-diphenylfluorene-3,6-diyl group, spirobifluorene-2,7-diyl group, spirobifluorene n-2,8-diyl group, spirobifluorene-2,4-diyl group, spirobifluorene-2,5-diyl group, spirobifluorene-2,6-diyl group, spirobifluorene-3,6-diyl group, phenanthrene-2,9-diyl group, phenanthrene-2,10-diyl group, phenanthrene-2,8-diyl group, phenanthrene-2,7-diyl group, phenanthrene-2,6-diyl group, phenanthrene-2,5-diyl group, phenanthrene-2,4-diyl group, phenanthrene-3,10-diyl group, phenanthrene-3,9-diyl group, phenanthrene-3,8-diyl group, phenanthrene-3,7-diyl group, phenanthrene-3,6-diyl group, phenanthrene-3,5-diyl group, phenanthrene-4,10-diyl group, phenanthrene-4,9-diyl group, phenanthrene-4,8-diyl group, phenanthrene-4,7-diyl group, phenanthrene-4,6-diyl group, riphenylene-1,3-diyl group, triphenylene-1,4-diyl group, triphenylene-1,5-diyl group, triphenylene-1,6-diyl group, triphenylene-1,7-diyl group, triphenylene-1,8-diyl group, triphenylene-2,4-diyl group, triphenylene-2,5-diyl group, triphenylene-2,6-diyl group, triphenylene-2,7 Examples include the -diyl group, triphenylene-3,5-diyl group, triphenylene-3,6-diyl group, triphenylene-4,6-diyl group, pyrene-1,3-diyl group, pyrene-1,6-diyl group, pyrene-1,8-diyl group, pyrene-2,7-diyl group, anthracene-2,6-diyl group, anthracene-9,10-diyl group, 9,10-diphenylanthracenediyl group, dibenzofuran-4,5-diyl group, dibenzofuran-3,6-diyl group, dibenzofuran-2,7-diyl group, dibenchofen-4,5-diyl group, dibenzothiophene-3,6-diyl group, dibenzothiophene-2,7-diyl group, 9-phenylcarbazole-2,7-diyl group, and 9-phenylcarbazole-3,6-diyl group.

[0056] Among the aromatic hydrocarbon groups represented by Y, 1,4-phenylene group, 1,3-phenylene group, 4,4'-biphenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6-naphthylene group, and anthracene-9,10-diyl group are preferred.

[0057] <Physical Properties of Condensed Ring Compounds> The preferred physical properties of the condensed ring compound represented by formula (1) are described below.

[0058] (HOMO value) The HOMO value of the condensed ring compound represented by formula (1) is not particularly limited, but from the viewpoint of suitability for use as a material for photoelectric conversion elements, it is preferably 5.0 to 6.5 eV. This HOMO value is obtained from measurements of the deposited film using an atmospheric photoelectron yield spectrometer.

[0059] (Band Gap) The band gap of the condensed ring compound represented by formula (1) is not particularly limited, but from the viewpoint of suitability for use as a material for photoelectric conversion elements, 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 condensed ring compound represented by formula (1) is not particularly limited, but from the viewpoint of suitability for use as a material for photoelectric conversion elements, 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 condensed ring compound represented by formula (1) is not particularly limited, but from the viewpoint of suitability for photoelectric conversion elements, 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 condensed ring 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 620 or more, and more preferably 620 or more and less than 1000.

[0063] <Preferred Specific Examples of Condensed Ring Compounds> The following are examples of preferred compounds for the condensed ring compound represented by formula (1), but the condensed ring compound is not limited to these compounds.

[0064] Compounds in which the substituent R is one group n selected from the groups shown in Tables 2 to 7 among the (A) to (D) skeletons shown in Table 1 are defined as (X-n). Compounds in which the substituent R is one group n selected from the groups shown in Tables 2 to 7 among the (E) to (H) skeletons shown in Table 1 and the substituent A is one group m selected from the groups shown in Table 8 are defined as (X-nm). Here, X represents any symbol from A to H, n represents any integer from 1 to 110, and m represents any lowercase letter from a to t. For example, the compound (B-12) has the skeleton of (B), and the substituent R on the skeleton is a 4-[di(2-naphthyl)amino]phenyl group. The compound (H-3f) has the skeleton of (H), and the substituent R on the skeleton is a 4-[di(p-biphenyl)amino]phenyl group, and the substituent A is a phenyl group.

[0065] [Skeletal Correspondence Chart]

[0066] [Correspondence table for substituent R]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072] [Correspondence table for substituent A]

[0073] <Method for Producing Condensed Ring Compound> The condensed ring compound represented by formula (1) is produced by introducing the group represented by the aforementioned formula (2) into dibenzo[g,p]chrysene or its derivative as the parent nucleus. The method for introducing the group represented by formula (2) may be appropriately selected from known methods and is not particularly limited. For example, a method in which N,N-di(4-biphenylyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline, palladium acetate, Xphos, 2M aqueous potassium phosphate solution, and xylene are added to dibenzo[g,p]chrysene or its derivative and reacted at 100 °C is preferred.

[0074] <Use of Condensed Ring Compound> The condensed ring compound represented by formula (1) can be used as a material for an organic electronic device or a material for a photoelectric conversion device. That is, the material for an organic electronic device or a material for a photoelectric conversion device of the present embodiment contains the condensed ring compound represented by formula (1). Examples of the material for a photoelectric conversion device include a material for a photoelectric conversion device for an imaging device. As the material for a photoelectric conversion device for an imaging device, for example, a charge transport material for a photoelectric conversion device for an imaging device or a charge blocking material for a photoelectric conversion device for an imaging device is preferred. As the charge transport material for a photoelectric conversion device for an imaging device, for example, a hole transport material for a photoelectric conversion device for an imaging device is preferred. As the charge blocking material for a photoelectric conversion device for an imaging device, for example, an electron blocking material for a photoelectric conversion device for an imaging device is preferred.

[0075] Examples of the organic electronic device include an organic electroluminescence device and an organic photoelectric conversion device. Examples of the material for an organic electronic device include a material for an organic electroluminescence device and a material for an organic photoelectric conversion device. The material for an organic electronic device containing the condensed ring compound represented by formula (1) is preferably used as an organic thin film. The aforementioned organic thin film or organic electronic device preferably contains the condensed ring compound represented by formula (1).

[0076] <<Material for Photoelectric Conversion Device for Imaging Device>> The material for a photoelectric conversion device for an imaging device contains a condensed ring compound represented by the following formula (3).

[0077] In the formula, R Ａ１~R Ａ１６ Each of these is independently a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a hydroxyl group, a thiol group, an allyl group, a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms which may have substituents, a monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms which may have substituents, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a group represented by the following formula (4). However, R Ａ１ ~R Ａ１６ At least one of these is a group represented by the following formula (4). In the formula, R Ａａ R represents an aromatic hydrocarbon group composed only of a hydrogen atom, a deuterium atom, or a six-membered ring having 6 to 30 carbon atoms, which may have substituents, or a heteroaromatic group having 3 to 36 carbon atoms, which may have substituents; Ａｂ This represents an aromatic hydrocarbon group composed only of a hydrogen atom, a deuterium atom, or a six-membered ring having 10 to 30 carbon atoms, which may have substituents, or a heteroaromatic group having 3 to 36 carbon atoms, which may have substituents; Y Ａ Each independently represents a C6-C30 monocyclic, linked, or fused aromatic hydrocarbon group which may have substituents, or a C5-C36 monocyclic, linked, or fused heteroaromatic group which may have substituents; n represents 1 or 2, and if n is 2, multiple R Ａａ ~R Ａｂ They may be the same or different.

[0078] The condensed ring compound represented by formula (3) above has an N-containing substituent represented by formula (4) above. Ａ It has a linker represented by [formula]. For this reason, the photoelectric conversion element for image sensors made using the above condensed ring compound has excellent dark current characteristics and responsiveness.

[0079] A preferred embodiment of the definition in formula (3) above is as follows:

[0080] <R Ａ１ ~R Ａ１６ >

[0081] (Aromatic hydrocarbon group) R Ａ１ ~R Ａ１６ 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.

[0082] Examples of the aromatic hydrocarbon group 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.

[0083] Furthermore, if the aromatic hydrocarbon group has substituents, it is preferable that each substituent independently be a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, an optionally substituted phosphine oxide group, an optionally substituted silyl group, a optionally substituted boronyl group having 2 to 10 carbon atoms, an alkyl group, an alkoxy group, an aromatic hydrocarbon group, a heteroaromatic group, or a trifluoromethylsulfonyloxy group. Among these, alkyl groups, aromatic hydrocarbon groups, and heteroaromatic groups are more preferred.

[0084] Examples of the substituted phosphine oxide group include unsubstituted phosphine oxide groups and substituted phosphine oxide groups. A substituted phosphine oxide group is preferred.

[0085] The phosphine oxide group having the above substituent is preferably a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 18 carbon atoms, or a fused heteroaromatic group. Specifically, examples include groups substituted with two aryl groups, such as diphenylphosphine oxide.

[0086] Examples of the substituted silyl group include an unsubstituted silyl group and a substituted silyl group. A substituted silyl group is preferred.

[0087] Preferred substituents for silyl groups include monocyclic, linked, or fused aromatic hydrocarbon groups having 6 to 18 carbon atoms, or fused heteroaromatic groups. Specifically, examples include groups substituted with three aryl groups, such as a triphenylsilyl group.

[0088] Examples of the above substituents, which may have saturated hydrocarbon groups having 2 to 10 carbon atoms, include a 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.

[0089] The alkyl group that is the substituent mentioned above 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.

[0090] 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.

[0091] Examples of the above-mentioned substituent aromatic hydrocarbon groups include phenyl group, biphenylyl group, terphenylyl group, naphthyl group, fluorenyl group, fluoranthenyl group, anthryl group, phenanthryl group, benzofluorenyl group, triphenylenyl group, spirobifluorenyl group, diphenylfluorenyl group, and dibenzo[g,p]crisenyl group.

[0092] Examples of the heteroaromatic substituents mentioned above include 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, 4,6-diphenyl-1,3,5-triazyl group, indolyl group, benzothienyl group, benzofuranyl group, and benzimi Examples include dazolyl 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, and the like.

[0093] (Heteroaromatic group) R Ａ１ ~R Ａ１６ A monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms, which may have substituents represented by , is preferably a monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms, containing at least one atom selected from the group consisting of oxygen, nitrogen, and sulfur atoms on the aromatic ring.

[0094] Examples of such heteroaromatic groups include dibenzofuranyl group, dibenzothionyl 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.

[0095] Furthermore, if the heteroaromatic group has substituents, it is preferable that each substituent is independently a cyano group, a fluorine atom, a trifluoromethyl group, an alkyl group, an alkoxy group, an aromatic hydrocarbon group, a heteroaromatic group, or a trifluoromethylsulfonyloxy group. Among these, alkyl groups, aromatic hydrocarbon groups, and heteroaromatic groups are more preferred.

[0096] The alkyl group that is the substituent is preferably a linear or branched alkyl group having 1 to 18 carbon atoms. Ａ１ ~R Ａ１６ When the aromatic hydrocarbon group represented by has substituents, examples of substituents include those similar to the alkyl groups exemplified above.

[0097] The alkoxy group that is a substituent is preferably a linear or branched alkoxy group having 1 to 18 carbon atoms. Ａ１ ~R Ａ１６ When the aromatic hydrocarbon group represented by has substituents, examples of substituents include those similar to the alkoxy group exemplified above.

[0098] The above substituent aromatic hydrocarbon group is R Ａ１ ~R Ａ１６When the aromatic hydrocarbon group represented by has substituents, examples of substituents include those similar to the aromatic hydrocarbon group exemplified above.

[0099] The heteroaromatic group which is the substituent mentioned above is R as described above. Ａ１ ~R Ａ１６ When the aromatic hydrocarbon group represented by has substituents, examples of substituents include those similar to the heteroaromatic groups exemplified above.

[0100] (Alkyl group) R Ａ１ ~R Ａ１６ 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, and the like.

[0101] (alkoxy group) R Ａ１ ~R Ａ１６ Examples of linear or branched alkoxy groups having 1 to 18 carbon atoms, represented by , include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, sec-butoxy, tert-butoxy, pentyloxy, n-hexyloxy, cyclohexyloxy, octyloxy, decyloxy, dodecyloxy, and octadecyloxy groups.

[0102] In equation (3), R Ａ９ ~R Ａ１６ It is preferable that it is a hydrogen atom.

[0103] In equation (3), R Ａ５ and R Ａ８ ~R Ａ１６ It is preferable that it is a hydrogen atom.

[0104] In equation (3), R Ａ５ ~R Ａ１６ It is preferable that it is a hydrogen atom.

[0105] ≪Base represented by formula (4)≫

[0106] <R Ａａ >

[0107] (Aromatic hydrocarbon group) R Ａａ Aromatic hydrocarbon groups consisting only of six-membered rings of monocyclic, linked, or fused rings having 6 to 30 carbon atoms, which may have substituents, are preferably aromatic hydrocarbon groups consisting only of six-membered rings of monocyclic, linked, or fused rings having 10 to 30 carbon atoms, which may have substituents. Specific examples of the aromatic hydrocarbon group, and specific examples of substituents when the aromatic hydrocarbon group has substituents, are as described above in R Ａ１ ~R Ａ１６ Examples include those similar to those described for aromatic hydrocarbon groups.

[0108] (Heteroaromatic group) R Ａａ Preferred embodiments and specific examples of a monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms, which may have substituents represented by the above, and specific examples of substituents when the heteroaromatic group has substituents are as follows: Ａ１ ~R Ａ１６ Examples similar to those described for heteroaromatic groups can be found.

[0109] In equation (4), R Ａａ Among the groups represented by R, Ａａ Preferably, the above aromatic hydrocarbon group is a monocyclic, linked, or fused ring having 10 to 30 carbon atoms, which may have substituents, or a heteroaromatic group is a monocyclic, linked, or fused ring having 3 to 36 carbon atoms, which may have substituents.

[0110] <R Ａｂ >

[0111] (Aromatic hydrocarbon group) R Ａｂ Specific examples of aromatic hydrocarbon groups consisting only of six-membered rings having 10 to 30 carbon atoms, which may have substituents represented by R, and specific examples of substituents when the aromatic hydrocarbon group has substituents are as described above. Ａ１ ~R Ａ１６ Examples include those similar to those described for aromatic hydrocarbon groups.

[0112] (Heteroaromatic group) R ＡｂPreferred embodiments and specific examples of a monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms, which may have substituents represented by the above, and specific examples of substituents when the heteroaromatic group has substituents are as follows: Ａ１ ~R Ａ１６ Examples similar to those described for heteroaromatic groups can be found.

[0113] In formula (4), preferably, R Ａａ However, R is a phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, crisenyl group, benzocrisenyl group, dibenzocrisenyl group, dibenzofuranyl group, dibenzothionyl group, carbazolyl group, naphthylphenyl group, phenylnaphthyl group, naphthylnaphthyl group, phenanthrylphenyl group, dibenzofuranylphenyl group, dibenzothionylphenyl group, carbazolylphenyl group, or a group that is a combination of these. Ａｂ However, these are biphenyl groups, terphenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, pyrenyl groups, crisenyl groups, benzocrisenyl groups, dibenzocrisenyl groups, dibenzofuranyl groups, dibenzothionyl groups, carbazolyl groups, naphthylphenyl groups, phenylnaphthyl groups, naphthylnaphthyl groups, phenanthrylphenyl groups, dibenzofuranylphenyl groups, dibenzothionylphenyl groups, carbazolylphenyl groups, or combinations thereof.

[0114] <Y Ａ >

[0115] Y Ａ Among monocyclic, linked, or fused aromatic hydrocarbon groups having 6 to 30 carbon atoms that may have substituents represented by Y, Ａ The former is preferable.

[0116] Y ＡExamples of the aromatic hydrocarbon groups represented by the above include phenylene group, biphenylene group, terphenylene group, naphthylene group, fluorenylene group, spirobifluorenylene group, phenanthrene-diyl group, triphenylene-diyl group, pyrene-diyl group, anthracene-diyl group, and the like.

[0117] Y Ａ Examples of the heteroaromatic groups represented by the above 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, and the like.

[0118] Y Ａ The above aromatic hydrocarbon group represented by Y ＡSpecific examples of the heteroaromatic groups represented by the above formula include, for example, 1,4-phenylene group, 1,3-phenylene group, 4,4'-biphenylene group, 4,3'-biphenylene group, 3,3'-biphenylene group, 4,4''-p-terphenylene group, 4,3''-p-terphenylene group, 3,3''-p-terphenylene group, 4,3'-p-terphenylene group, 3,3'-p-terphenylene group, 4,4''-m-terphenylene group, 4,3''-m-terphenylene group, 3,3''-m-terphenylene group, 4,4'-m-terphenylene group, 4,5'-m-terphenylene group, 3,4'-m-terphenylene group Lenyl group, 3,5'-m-terphenylene group, 1,3-naphthylene group, 1,4-naphthylene group, 1,5-naphthylene group, 1,6-naphthylene group, 1,7-naphthylene group, 1,8-naphthylene group, 2,4-naphthylene group, 2,5-naphthylene group, 2,6-naphthylene group, 2,7-naphthylene group, 2,8-naphthylene group, 9,9-dimethylfluorene-2,7-diyl group, 9,9-dimethylfluorene-2,8-diyl group, 9,9-dimethylfluorene-2,4-diyl group, 9,9-dimethylfluorene-2,5-diyl group, 9,9-dimethyl 9,9-fluorene-2,6-diyl group, 9,9-dimethylfluorene-3,6-diyl group, 9,9-diphenylfluorene-2,7-diyl group, 9,9-diphenylfluorene-2,8-diyl group, 9,9-diphenylfluorene-2,4-diyl group, 9,9-diphenylfluorene-2,5-diyl group, 9,9-diphenylfluorene-2,6-diyl group, 9,9-diphenylfluorene-3,6-diyl group, spirobifluorene-2,7-diyl group, spirobifluorene-2,8-diyl group, spirobifluorene-2,4- Diyl group, spirobifluorene-2,5-diyl group, spirobifluorene-2,6-diyl group, spirobifluorene-3,6-diyl group, phenanthrene-2,9-diyl group, phenanthrene-2,10-diyl group, phenanthrene-2,8-diyl group, phenanthrene-2,7-diyl group, phenanthrene-2,6-diyl group, phenanthrene-2,5-diyl group, phenanthrene-2,4-diyl group, phenanthrene-3,10-diyl group, phenanthrene-3,9-diyl group, phenanthrene-3,8-diyl group, phenanthrene-3,7-diyl group, phenanthrene-3,6-diyl group, phenanthrene-3,5-diyl group, phenanthrene-4,10-diyl group, phenanthrene-4,9-diyl group, phenanthrene-4,8-diyl group, phenanthrene-4,7-diyl group, phenanthrene-4,6-diyl group, triphenylene-1,3-diyl group, triphenylene-1,4-diyl group, triphenylene-1,5-diyl group, triphenylene-1,6-diyl group, triphenylene-1,7-diyl group, triphenylene-1,8-diyl group, triphenylene-2,4-diyl group, triphenylene-2,5-diyl group, triphenylene-2,6-diyl group, triphenylene-2,7-diyl group, triphenylene-3,5 Examples of diyl groups include triphenylene-3,6-diyl group, triphenylene-4,6-diyl group, pyrene-1,3-diyl group, pyrene-1,6-diyl group, pyrene-1,8-diyl group, pyrene-2,7-diyl group, anthracene-2,6-diyl group, anthracene-9,10-diyl group, 9,10-diphenylanthracenediyl group, dibenzofuran-4,5-diyl group, dibenzofuran-3,6-diyl group, dibenzofuran-2,7-diyl group, dibenchofen-4,5-diyl group, dibenzothiophene-3,6-diyl group, dibenzothiophene-2,7-diyl group, 9-phenylcarbazole-2,7-diyl group, 9-phenylcarbazole-3,6-diyl group, etc.

[0119] Y Ａ Among the aromatic hydrocarbon groups represented above, 1,4-phenylene group, 1,3-phenylene group, 4,4'-biphenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,6-naphthylene group, and anthracene-9,10-diyl group are preferred.

[0120] <Physical Properties of Condensed Ring Compounds> The preferred HOMO value, band gap, LUMO value, glass transition temperature, and molecular weight of the condensed ring compound represented by formula (3) are the same as those of the condensed ring compound represented by formula (1) in the above-mentioned <Condensed Ring Compound Represented by Formula (1)>.

[0121] <Preferred Specific Examples of Condensed Ring Compounds> The preferred compounds of the condensed ring compound represented by formula (3) are the same as the preferred compounds of the condensed ring compound represented by formula (1) in the above-mentioned <Condensed Ring Compound Represented by Formula (1)>.

[0122] <Method for producing condensed ring compounds> The condensed ring compound represented by formula (3) is produced by introducing the group represented by formula (4) described above into the parent dibenzo[g,p]chrysene or a derivative thereof. The method for introducing the group represented by formula (4) is not particularly limited and any known method may be used as appropriate. For example, a preferred method involves adding N,N-di(4-biphenylyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline, palladium acetate, Xphos, a 2M aqueous potassium phosphate solution, and xylene to dibenzo[g,p]chrysene or a derivative thereof and reacting them at 100°C.

[0123] <Applications of Condensed Ring Compounds> Condensed ring compounds represented by formula (3) are suitably used as materials for photoelectric conversion elements in image sensors. As materials for photoelectric conversion elements in image sensors, for example, charge transport materials or charge blocking materials for photoelectric conversion elements in image sensors are preferred. As charge transport materials for photoelectric conversion elements in image sensors, for example, hole transport materials for photoelectric conversion elements in image sensors are preferred. As charge blocking materials for photoelectric conversion elements in image sensors, for example, electron blocking materials for photoelectric conversion elements in image sensors are preferred.

[0124] The following describes, as an example, a photoelectric conversion element for an image sensor according to this embodiment.

[0125] <<Photoelectric Conversion Element for Image Sensor>> The photoelectric conversion element for image sensor in this embodiment includes the aforementioned material for the photoelectric conversion element for image sensor.

[0126] The layer configuration of the photoelectric conversion element for the image sensor is not particularly limited, but for example, the following configurations (A) to (F) can be cited. (A) A photoelectric conversion layer is provided between the first electrode and the second electrode. (B) An electron transport layer and a photoelectric conversion layer are provided between the first electrode and the second electrode in that order. (C) A photoelectric conversion layer and a hole transport layer are provided between the first electrode and the second electrode in that order. (D) An electron transport layer, a photoelectric conversion layer, and a hole transport layer are provided between the first electrode and the second electrode in that order. (E) 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 that order. (F) An auxiliary layer, 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 that order. Here, the photoelectric conversion element for the image sensor can be injected with light from either the first electrode or the second electrode.

[0127] The configuration of the photoelectric conversion element for the image sensor is not particularly limited, but for example, the following configurations (i) to (vi) can be cited: (i) First electrode / photoelectric conversion layer / second electrode (ii) First electrode / electron transport layer (hole blocking layer) / photoelectric conversion layer / second electrode (iii) First electrode / photoelectric conversion layer / hole transport layer (electron blocking layer) / second electrode (iv) First electrode / electron transport layer (hole blocking layer) / photoelectric conversion layer / hole transport layer (electron blocking layer) / second electrode (v) First electrode / electron transport layer (hole blocking layer) / photoelectric conversion layer / hole transport layer (electron blocking layer) / buffer layer / second electrode (vi) First electrode / auxiliary layer / electron transport layer (hole blocking layer) / photoelectric conversion layer / hole transport layer (electron blocking layer) / buffer layer / second electrode

[0128] The buffer layer may be replaced with another layer having a different name or function, if necessary. Examples of other layers with different names or functions include a hole injection layer and a work function adjustment layer. The auxiliary layer is a layer provided between the first electrode and the electron transport layer (hole blocking layer) described later, and is a layer that assists in the transport of electrons from the electron transport layer (hole blocking layer) to the first electrode.

[0129] The photoelectric conversion element for an image sensor preferably contains the aforementioned material for image sensor photoelectric conversion elements in at least one layer selected from the group consisting of an electron transport layer (hole blocking layer), a photoelectric conversion layer, a hole transport layer (electron blocking layer), and a buffer layer. Furthermore, it is preferable that the photoelectric conversion element for an image sensor contains the aforementioned material for image sensor photoelectric conversion elements in the photoelectric conversion layer and / or the hole transport layer (electron blocking layer), and more preferably that the hole transport layer (electron blocking layer) contains the aforementioned material for image sensor photoelectric conversion elements. Note that the material for image sensor photoelectric conversion elements may be included in multiple layers of the photoelectric conversion element for an image sensor.

[0130] Hereinafter, the photoelectric conversion element for image sensors according to this embodiment will be described in more detail with reference to Figure 1, using the configuration of (v) above as an example. Figure 1 is a schematic cross-sectional view showing an example of a stacked configuration of a photoelectric conversion element for image sensors, including the material for the photoelectric conversion element for image sensors according to this embodiment. Note that for the layers that are the same as the configurations of (i) to (iv) and (vi) above, the same embodiments as for each layer below will apply.

[0131] 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.

[0132] 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 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 uses the first electrode 2 as an electron collection electrode and the second electrode 7 as a hole collection electrode.

[0133] The photoelectric conversion element 100 for the image sensor preferably contains the material for the photoelectric conversion element for the image sensor in at least one layer selected from the group consisting of an electron transport layer (hole blocking layer) 3, a photoelectric conversion layer 4, a hole transport layer (electron blocking layer) 5, and a buffer layer 6. More preferably, the photoelectric conversion element 100 contains the material for the photoelectric conversion element for the image sensor in the photoelectric conversion layer 4 and / or the hole transport layer (electron blocking layer) 5, and even more preferably, the material for the photoelectric conversion element for the image sensor is included in the hole transport layer (electron blocking layer) 5. The material for the photoelectric conversion element for the image sensor may be included in multiple layers of the photoelectric conversion element 100 for the image sensor.

[0134] The following describes a photoelectric conversion element 100 for an image sensor, in which the hole transport layer (electron blocking layer) 5 contains a material for photoelectric conversion elements for image sensors.

[0135] [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).

[0136] [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).

[0137] The transparent material used for the first electrode 2 is not particularly limited. From the viewpoint of excellent light transmittance, the material constituting the first electrode 2 may be, for example, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide, aluminum-doped tin oxide, magnesium-indium oxide, nickel-tungsten oxide, other metal oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, metal sulfides such as zinc sulfide, etc.

[0138] 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 sodium, 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.

[0139] [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.

[0140] 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.

[0141] 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 first electrode 2 made of a material specialized for electron transport.

[0142] 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.

[0143] [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.

[0144] The photoelectric conversion layer 4 may be made of organic or inorganic material, as long as it can generate a signal charge corresponding to the amount of light received. If the photoelectric conversion layer 4 is made of organic material, it may be a single-layer structure consisting of one or more types of materials, or a laminated structure consisting of multiple layers of the same or different compositions.

[0145] 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.

[0146] 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 its derivatives, and two or more 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.

[0147] The photoelectric conversion layer 4, made of these materials, may be formed, for example, by vapor deposition using a mixed powder obtained by mixing the powders of each material, or by co-depositing each material in any proportion.

[0148] 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.

[0149] Specific examples of hole transport materials include 9,9'-(9,9'-spirobi[9H-fluorene]-2,7'-diyl)bis[9H-carbazole], 2,7-diphenyl[1]benzothieno[3,2-b][1]benzothiophene (DiPh-BTBT), benzo[1,2-b:3,4-b':5,6-b'']trifuran compounds, benzo[1,2-b:3,4-b':5,6-b'']trithiophene compounds, naphtho[1,2-b:5,6-b']dithiophene, naphtho[2,3-b]naphtho[2',3' 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 formula (ic-2), etc.

[0150]

[0151] 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.

[0152] [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.

[0153] 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 blocking electrons generated in the photoelectric conversion layer 4 from moving to the second electrode 7. Preferably, the hole transport layer (electron blocking layer) 5 contains the above-mentioned material for the image sensor photoelectric conversion element.

[0154] The hole transport layer (electron blocking layer) 5 may be a single-layer structure made of one or more materials, or it may be a laminated structure made 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.

[0155] The hole transport layer (electron blocking layer) 5 may further contain conventionally known hole transport materials in addition to the above-mentioned material for the photoelectric conversion element of the image sensor. Preferred compounds and specific examples of conventionally known hole transport materials are the same as those described in the section on the photoelectric conversion layer 4.

[0156] [Buffer Layer 6] A buffer layer 6 is provided between the hole transport layer (electron blocking layer) 5 and the second electrode 7, which will be described later. When the second electrode 7 is formed by sputtering, 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. It also plays a role in efficiently receiving holes from the hole transport layer (electron blocking layer) 5 by adjusting the work function of the buffer layer 6, and is also called a hole injection layer or work function adjustment layer.

[0157] The material constituting the buffer layer 6 may be a known material, for example, naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN), etc.

[0158] [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, magnesium / silver mixture, aluminum, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ２ O ３) may be mixtures, indium, lithium / aluminum mixtures, rare earth metals, etc.

[0159] [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.

[0160] 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.

[0161] 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.

[0162] 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.

[0163] In the above embodiments, the photoelectric conversion element for the image sensor preferably comprises an electrode, a photoelectric conversion layer, and a hole transport layer, wherein the photoelectric conversion layer contains a fullerene and the hole transport layer contains the aforementioned material for the photoelectric conversion element for the image sensor.

[0164] 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.

[0165] Although preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments.

[0166] 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.

[0167] <Examples of synthesis of condensed ring compounds>

[0168] [Synthesis Example 1] Synthesis of Compound (B-3)

[0169] (Synthesis of compound (IM-1-1)) Under a nitrogen stream, 3-chlorodibenzo[g,p]chrysene (4.72 g, 13.0 mmol), N-(tert-butoxycarbonyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (4.56 g, 14.3 mmol), palladium acetate (0.058 g, 0.026 mmol), Xphos (0.025 g, 0.052 mmol), 2 M aqueous potassium phosphate solution (9.75 mL, 19.5 mmol), and 1,4-dioxane (65 mL) were added to a 200 mL glass container and stirred at 100 °C for 6 hours. After cooling to room temperature, the solvent was removed under reduced pressure, and the mixture was separated by adding toluene and pure water. The resulting organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained crude material was heated and stirred in a toluene / ethanol mixed solvent, cooled to room temperature, and then filtered to obtain 5.65 g (10.9 mmol, yield 83.6%) of the yellow solid compound (IM-1-1).

[0170] (Synthesis of compound (IM-1-2)) Under a nitrogen atmosphere, compound (IM-1-1) (5.20 g, 10.0 mmol) and 1,4-dioxane (30 mL) were added to a 100 mL glass container. The solution was cooled to 0°C while stirring, and trifluoromethanesulfonic acid (1.54 mL, 20.0 mmol) was added. The mixture was stirred at room temperature for 24 hours. After cooling to room temperature, the precipitate was collected by filtration. The obtained crude material was stirred in THF, and sodium bicarbonate was added. After adding ethyl acetate and stirring, the aqueous layer and organic layer were separated. The obtained organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain 3.60 g (8.58 mmol, yield 85.7%) of the brown solid compound (IM-1-2). The obtained compound (IM-1-2) was identified by FDMS. m / z = 419

[0171] (Synthesis of Compound (B-3)) Under an argon stream, compound (IM-1-2) (1.68 g, 4.00 mmol), 4-bromoviphenyl (2.05 g, 8.80 mmol), palladium acetate (18.0 mg, 0.080 mmol), Xantphos (92.6 mg, 0.16 mmol), sodium tert-butoxide (1.15 g, 12.0 mmol), and xylene (40 mL) were added to a 100 mL glass container and stirred at 140 °C for 4 hours. After cooling to room temperature, the reaction mixture was added to hexane, and the precipitate was collected by filtration. The obtained crude product was dissolved in toluene, passed through a small amount of silica gel, and then concentrated under reduced pressure. The obtained crude product was recrystallized (in toluene solvent) to obtain 2.70 g (3.73 mmol, yield 93.2%) of the yellow solid compound (B-3). The identification of the obtained compound (B-3) is as follows: １ This was performed using H-NMR. １ H-NMR (DMSO-d ６ ) δ (ppm): 8.97 (d, 1H), 8.93-8.89 (m, 3H), 8.85 (s, 1H), 8.75 (dd, 1H), 8.67 (dd, 2H), 8. 08 (d, 1H), 7.85-7.73 (m, 8H), 7.67 (d, 8H), 7.46 (t, 4H), 7.34 (t, 2H), 7.24-7.20 (m, 6H)

[0172] [Synthesis Example 2] Synthesis of Compound (B-15)

[0173] (Synthesis of compound (IM-2-1)) Under a nitrogen atmosphere, 3-chlorodibenzo[g,p]chrysene (5.00 g, 13.8 mmol), N-(4-(4,4,5,5,-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,1'-biphenyl]-4-amine (6.14 g, 16.5 mmol), palladium acetate (30.9 mg, 138 μmol), XPhos (131 mg, 276 μmol), 4 M aqueous potassium phosphate (5.17 mL, 20.7 mmol), and 1,4-dioxane (67 mL) were added to a 200 mL glass container and stirred at 70°C for 6 hours. After cooling to room temperature, water and methanol were added and stirred, and the precipitated solid was collected. The compound was dissolved in chlorobenzene at 140°C, activated carbon was added and stirred, and the activated carbon was removed by Celite filtration. The resulting solution was concentrated under reduced pressure. Recrystallization was performed with chlorobenzene and then a mixed solvent of DMF / butanol to obtain 6.50 g (11.4 mmol, yield 83%) of the white solid compound (IM-2-1). The identification of the obtained compound (IM-2-1) was as follows: １ This was performed using H-NMR. １ H-NMR (DMSO-d ６ ) δ (ppm): 8.98-8.85 (m, 4H), 8.81 (s, 1H), 8.80-8.72 (m, 1H), 8.72-8.60 (m, 2H), 8.55 (s, 1H), 8.04 (dd, J=1.8, 8.6Hz, 1H), 7.88-7.68 (m, 8H), 7.68-7.53 (m, 4H), 7.49-7.37 (m2H), 7.34-7.11 (m, 5H).

[0174] (Synthesis of compound (B-15)) Under an argon stream, compound (IM-2-1) (1.14 g, 4.43 mmol), 2-bromophenanthrene (1.14 g, 4.43 mmol), palladium acetate (13.5 mg, 60.3 μmol), a 25 wt% solution of tri(tert)butylphosphine in xylene (147 mg, 0.181 mmol), sodium-tert-butoxide (503 mg, 5.23 mmol), and xylene (40 mL) were added to a 100 mL glass container and stirred at 140 °C for 4 hours. After cooling to room temperature, water was added to quench the mixture, and the organic layer was extracted using toluene. Activated carbon was added and stirred, and the resulting filtrate was filtered by Celite and concentrated under reduced pressure. The obtained crude material was recrystallized in a mixed solvent of toluene and ethanol to obtain 1.65 g (4.02 mmol, yield 55%) of a white solid of compound (B-15). The identification of the obtained compound (B-15) was as follows: １ This was performed using H-NMR. １ H-NMR (DMSO-d ６ ) δ (ppm): 9.00-8.80 (m, 5H), 8.76 (d, J = 9.1Hz, 1H), 8.74-8.67 (m, 2H), 8.64 (t, J = 6.5Hz, 2H), 8.03 (d, J = 8.5Hz, 1H), 7.94 (d, J =7.9Hz, 1H), 7.85-7.6 (m, 16H), 7.59 (d, J = 7.3Hz, 1H), 7.48-7.39 (m, 3H), 7.33 (t, J = 7.4Hz, 1H), 7.22 (dd, J = 6.4, 8.5Hz, 4H).

[0175] [Synthesis Example 3] Synthesis of Compound (B-29)

[0176] (Synthesis of compound (B-29)) Under an argon stream, compound (IM-2-1) (1.90 g, 3.32 mmol), 2-bromo-9-phenylcarbazole (1.18 g, 3.66 mmol), palladium acetate (7.46 mg, 33.2 μmol), a 25 wt% solution of tri(tert)butylphosphine in xylene (80.7 mg, 99.7 μmol), sodium-tert-butoxide (415 mg, 4.32 mmol), and xylene (20 mL) were added to a 50 mL glass container and stirred at 140 °C for 1 hour. After cooling to room temperature, water was added to quench the mixture, and the organic layer was extracted using toluene. Anhydrous magnesium sulfate and activated carbon were added and stirred, and the resulting filtrate was filtered by Celite and concentrated under reduced pressure. Silica gel chromatography yielded 1.10 g (1.35 mmol, 41% yield) of the yellow solid compound (B-29). The identification of the obtained compound (B-29) was as follows: １ This was performed using H-NMR. １ H-NMR (DMSO-d ６ ) δ (ppm): 8.96-8.82 (m, 4H), 8.79 (s, 1H), 8.76-8.67 (m, 1H), 8.64 (t, J = 6.4, 2H), 8.26-8.10 (m, 2H), 8.00 (d, J = 8.5, 1H), 7.86-7.66 (m, 8H), 7.66-7.50 (m, 8H), 7.48-7.35 (m, 4H), 7.35-7.21 (m, 3H), 7.15 (dd, J = 4.9, 8.7, 4H), 7.09 (d, J = 2.2, 1H), 7.04 (dd, J = 1.9, 8.4, 1H).

[0177] [Synthesis Example 4] Synthesis of Compound (B-41)

[0178] (Synthesis of compound (IM-4-1)) Under a nitrogen atmosphere, 3-chlorodibenzo[g,p]chrysene (2.50 g, 6.89 mmol), (3-aminophenyl)boronic acid (2.83 g, 20.7 mmol), palladium acetate (30.9 mg, 138 μmol), SPhos (113 mg, 276 μmol), 4 M aqueous potassium phosphate solution (3.44 mL, 13.8 mmol), and butanol (70 mL) were added to a 200 mL glass container and stirred at 100 °C for 3 hours. After cooling to room temperature, water and methanol were added and stirred, and the precipitated solid was collected. It was dissolved in toluene at 140 °C, activated carbon was added and stirred, and the activated carbon was removed by Celite filtration. The obtained solution was concentrated under reduced pressure. Recrystallization in a mixed solvent of DMF / butanol yielded 1.76 g (4.20 mmol, 61% yield) of the compound (IM-4-1) as a white solid. The identification of the obtained compound (IM-4-1) was as follows: １ This was performed using H-NMR. １ H-NMR (DMSO-d ６ ) δ (ppm): 9.02-8.83-9.02 (m, 4H), 8.79 (s, 1H), 8.75-8.56 (m, 3H), 7.97 (dd, J = 1.8, 8.7Hz, 1H) , 7.86-7.64 (m, 6H), 7.17 (t, J=7.7Hz, 1H), 7.05-6.92 (m, 2H), 6.70-6.48 (m, 1H), 5.23 (s, 2H).

[0179] (Synthesis of Compound (B-41)) Under an argon stream, compound (IM-4-1) (1.76 g, 4.20 mmol), 4-bromoviphenyl (2.15 g, 9.23 mmol), palladium acetate (47.1 mg, 210 μmol), SPhos (172 mg, 420 μmol), sodium tert-butoxide (1.01 g, 10.5 mmol), and xylene (43 mL) were added to a 100 mL glass container and stirred at 140 °C for 6 hours. After cooling to room temperature, the reaction mixture was added to hexane, and the precipitate was collected by filtration. The obtained crude product was dissolved in toluene, passed through a small amount of silica gel, and then concentrated under reduced pressure. The obtained crude product was recrystallized (in toluene solvent) to obtain 2.30 g (3.20 mmol, yield 76%) of the yellow solid compound (B-41). The identification of the obtained compound (B-41) is as follows: １ This was performed using H-NMR. １ H-NMR (DMSO-d ６ ) δ (ppm): 8.90 (d, J = 8.4Hz, 1H), 8.87-8.75 (m, 3H), 8.68 (s, 1H), 8.61 (d, J = 8.0Hz, 2H), 8.54 (d, J = 7.6Hz, 1H), 7.98 (d, J = 8.5Hz) , 1H), 7.80-7.67 (m, 4H), 7.67-7.57 (m, 8H), 7.55-7.41 (m, 9H), 7.39-7.32 (m, 2H), 7.20 (d, J = 8.6Hz, 4H), 7.10 (d, J = 7.5Hz, 1H).

[0180] [Synthesis Example 5] Synthesis of Compound (B-62)

[0181] (Synthesis of compound (IM-5-1)) Under a nitrogen atmosphere, in a 200 mL glass container, combine 4-Bdan-1-bromonaphthalene (3.92 g, 10.5 mmol), di([1,1'-diphenyl]-4-yl)amine (3.21 g, 10.0 mmol), palladium acetate (44.9 mg, 200 μmol), Xantphos (231 mg, 400 μmol), and NaO2. ｔBu (1.44 G, 15.0 mmol) and xylene (105 mL) were added, and the mixture was stirred at 140°C for 2 hours. After cooling to room temperature, water and methanol were added and the mixture was stirred, and the precipitated solid was collected. The obtained crude material was dissolved in toluene, passed through a small amount of silica gel, and then concentrated under reduced pressure. The obtained crude material was recrystallized in a mixed solvent of toluene and hexane to obtain 6.06 g (9.88 mmol, yield 99%) of the yellow solid compound (IM-5-1). The obtained compound (IM-5-1) was identified by FDMS. m / z = 613

[0182] (Synthesis of compound (IM-5-2)) Under a nitrogen atmosphere, compound (IM-5-1) (4.50 g, 7.33 mmol), 4 M hydrochloric acid (11.0 mL, 44.0 mmol), and THF (2 mL) were added to a 20 mL glass container and stirred at 60°C for 6 hours. After cooling to room temperature, the mixture was neutralized with aqueous sodium hydroxide solution, and the organic layer was extracted using toluene. Anhydrous magnesium sulfate and activated carbon were added and stirred, and the resulting filtrate was filtered using Celite. The filtrate was concentrated under reduced pressure to obtain 3.00 ml (6.11 mmol, yield 83%) of pale yellow solid compound (IM-5-2). The obtained compound (IM-5-2) was identified by FDMS. m / z = 491

[0183] (Synthesis of compound (B-62)) Under an argon stream, compound (IM-5-2) (2.70 g, 5.49 mmol), 3-chlorodibenzo[g,p]chrysene (1.33 g, 3.66 mmol), palladium acetate (16.4 mg, 73.3 μmol), SPhos (60.2 mg, 147 μmol), 4 M tripotassium phosphate aqueous solution (1.83 mL, 7.33 mmol), and 1,4-dioxane (55 mL) were added to a 100 mL glass container and stirred at 70°C for 2 hours. After cooling to room temperature, the organic layer was extracted with toluene. Anhydrous magnesium sulfate and activated carbon were added and stirred, and the filtrate obtained by Celite filtration was concentrated under reduced pressure. After adding the reaction mixture to hexane, the precipitate was filtered and recovered. The obtained crude material was dissolved in toluene, passed through a small amount of silica gel, and then concentrated under reduced pressure. The obtained crude material was recrystallized in a mixed solvent of toluene and hexane to obtain 1.48 g (3.66 mmol, yield 52%) of the yellow solid compound (B-62). The identification of the obtained compound (B-62) was as follows: １ This was performed using H-NMR. １ H-NMR (DMSO-d ６ ) δ (ppm) 9.07 (d, J = 8.6Hz, 1H), 9.01-8.96 (m, 1H), 8.89 (t, J = 7.6Hz, 2H ), 8.77-8.70 (m, 4H), 8.16 (d, J = 8.1Hz, 1H), 8.07 (d, J = 8.6Hz, 1H), 7.99 (d, J=10.3Hz, 1H), 7.84-7.70 (m, 7H), 7.63-7.60 (m, 9H), 7.57-7.54 (m, 2H), 7.43 (t, J = 7.7Hz, 4H), 7.31 (t, J = 7.3Hz, 2H), 7.13 (d, J = 8.8Hz, 4H)

[0184] [Synthesis Example - 6] Synthesis of Compound (C-3)

[0185] (Synthesis of compound (C-3)) Under an argon stream, 2-chlorodibenzo[g,p]chrysene (2.18 g, 6.00 mmol), N,N-di(4-biphenylyl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (3.45 g, 6.60 mmol), palladium acetate (26.9 mg, 0.12 mmol), Xphos (114 mg, 0.24 mmol), 2M aqueous potassium phosphate solution (4.50 mL, 9.00 mmol), and xylene (60 mL) were added to a 100 mL glass container and stirred at 100°C for 24 hours. After cooling to room temperature, the solvent was removed under reduced pressure, and the mixture was separated by adding toluene and pure water. The resulting organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained crude material was recrystallized with toluene to obtain 2.86 g (3.95 mmol, yield 65.8%) of the yellow solid compound (C-3). The identification of the obtained compound (C-3) was as follows: １ This was performed using H-NMR. １ H-NMR (DMSO-d ６ ) δ (ppm): 9.12 (s, 1H), 9.08 (d, 1H), 8.90 (d, 2H), 8.73-8.65 (m, 4H), 8.06 (d, 1H), 8.02 (d, 2H) ), 7.81-7.72 (m, 6H), 7.71-7.68 (m, 8H), 7.47 (t, 4H), 7.35 (t, 2H), 7.27 (d, 2H), 7.23 (d, 4H)

[0186] [Synthesis Example - 7] Synthesis of Compound (D-3)

[0187] (Synthesis of compound (IM-7-1)) Under a nitrogen atmosphere, 1-chlorodibenzo[g,p]chrysene (5.00 g, 13.8 mmol), N-(4-(4,4,5,5,-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,1'-biphenyl]-4-amine (6.14 g, 16.5 mmol), palladium acetate (30.9 mg, 138 μmol), XPhos (131 mg, 276 μmol), 4 M aqueous potassium phosphate (5.17 mL, 20.7 mmol), and 1,4-dioxane (67 mL) were added to a 200 mL glass container and stirred at 70°C for 6 hours. After cooling to room temperature, water and methanol were added and stirred, and the precipitated solid was collected. The compound was dissolved in chlorobenzene at 140°C, activated carbon was added and the mixture was stirred. The activated carbon was then removed by Celite filtration, and the resulting solution was concentrated under reduced pressure. Recrystallization was performed with chlorobenzene and then a mixed solvent of DMF / butanol to obtain 4.21 g (7.38 mmol, yield 54%) of the white solid compound (IM-7-1). The obtained compound (IM-7-1) was identified by FDMS. m / z = 571

[0188] (Synthesis of compound (D-3)) Under an argon stream, compound (IM-7-1) (3.30 mg, 5.77 mmol), 4-bromo-1,1'-biphenyl (1.41 g, 6.06 mmol), palladium acetate (25.9 mg, 115 μmol), SPhos (94.8 mg, 231 mmol), sodium tert-butoxide (832 mg, 8.66 mmol), and xylene (25 mL) were added to a 100 mL glass container and stirred at 140 °C for 2 hours. After cooling to room temperature, water was added to quench the mixture, and the organic layer was extracted using toluene. Activated carbon was added and stirred, and the mixture was filtered by Celite filtration. The resulting filtrate was concentrated under reduced pressure. The crude mixture was recrystallized in a mixed solvent of toluene and hexane to obtain 3.50 g (4.83 mmol, yield 84%) of compound (D-3) as a white solid. The identification of the obtained compound (D-3) is as follows: １ This was performed using H-NMR. １ H-NMR (DMSO-d ６) δ (ppm): 9.02-8.70 (m, 2H), 8.76-8.60 (m, 3H), 8.51 (d, J = 8.3Hz, 1H), 7.85-7.67 (m, 14H), 7.64 (d, J = 7.3 Hz, 1H), 7.58 (d, J = 7.6Hz, 1H), 7.53-7.44 (m, 4H), 7.40 (s, 2H), 7.35 (t, J = 7.4Hz, 3H), 7.31-7.18 (m, 6H).

[0189] [Synthesis Example 8] Synthesis of Compound (G-3b)

[0190] (Synthesis of compound (IM-8-1)) Under a nitrogen atmosphere, 3-chloro-14-methyldibenzo[g,p]chrysene (3.00 g, 7.96 mmol), N-(4-(4,4,5,5,-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,1'-biphenyl]-4-amine (3.55 g, 9.55 mmol), palladium acetate (35.7 mg, 159 μmol), XPhos (152 mg, 318 μmol), 2 M potassium carbonate aqueous solution (5.97 mL, 11.9 mmol), and 1,4-dioxane (80 mL) were added to a 200 mL glass container and stirred at 70°C for 14 hours. After cooling to room temperature, water and methanol were added and stirred, and the precipitated solid was collected. The compound (IM-8-1) was dissolved in chlorobenzene at 140°C, activated carbon was added and the mixture was stirred. The activated carbon was then removed by Celite filtration, and the resulting solution was concentrated under reduced pressure. Recrystallization was performed with chlorobenzene and then a mixed solvent of DMF / butanol to obtain 3.21 g (5.48 mmol, yield 69%) of the white solid compound (IM-8-1). The obtained compound (IM-8-1) was identified by FDMS. m / z = 585

[0191] (Synthesis of compound (G-3b)) Under an argon stream, compound (IM-8-1) (2.00 g, 3.41 mmol), 4-bromo-1,1'-biphenyl (876 mg, 3.76 mmol), palladium acetate (15.3 mg, 68.3 μmol), a 25 wt% solution of tri(tert)butylphosphine in xylene (111 mg, 0.137 mmol), sodium-tert-butoxide (492 mg, 5.12 mmol), and xylene (30 mL) were added to a 100 mL glass container and stirred at 140 °C for 4 hours. After cooling to room temperature, water was added to quench the mixture, and the organic layer was extracted using toluene. Activated carbon was added and stirred, and the resulting filtrate was filtered by Celite and concentrated under reduced pressure. The obtained crude material was recrystallized in a mixed solvent of toluene and ethanol to obtain 2.10 g (2.84 mmol, yield 83%) of a white solid of compound (G-3b). The identification of the obtained compound (G-3b) was as follows: １ This was performed using H-NMR. １ H-NMR (DMSO-d ６ ) δ (ppm): 8.88 (d, J = 8.5Hz, 3H), 8.82-8.74 (m, 2H), 8.74-8.61 (m, 2H), 8.44 (s, 1H), 8.01 (d, J = 8.5Hz, 1H), 7 .84-7.70 (m, 6H), 7.70-7.54 (m, 9H), 7.51-7.39 (m, 4H), 7.39-7.28 (m, 2H), 7.24-7.07 (m, 6H), 2.56 (s, 3H).

[0192] [Synthesis Example 9] Synthesis of Compound (G-3f)

[0193] (Synthesis of compound (IM-9-1)) Under a nitrogen atmosphere, 3-chloro-14-phenyldibenzo[g,p]chrysene (3.00 g, 6.86 mmol), N-(4-(4,4,5,5,-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,1'-biphenyl]-4-amine (2.66 g, 7.18 mmol), palladium acetate (30.7 mg, 137 μmol), XPhos (1.30 mg, 270 μmol), 4 M tripotassium phosphate aqueous solution (5.13 mL, 20.5 mmol), and 1,4-dioxane (68 mL) were added to a 200 mL glass container and stirred at 70°C for 14 hours. After cooling to room temperature, water and methanol were added and stirred, and the precipitated solid was collected. The compound was dissolved in chlorobenzene at 140°C, activated carbon was added and the mixture was stirred. The activated carbon was then removed by Celite filtration, and the resulting solution was concentrated under reduced pressure. Recrystallization was performed with chlorobenzene and then a mixed solvent of DMF / butanol to obtain 3.71 g (5.74 mmol, yield 84%) of the white solid compound (IM-9-1). The obtained compound (IM-9-1) was identified by FDMS. m / z = 647

[0194] (Synthesis of compound (G-3f)) Under an argon stream, compound (IM-9-1) (2.00 g, 3.09 mmol), 4-bromo-1,1'-biphenyl (792 mg, 3.40 mmol), palladium acetate (13.9 mg, 61.7 μmol), a 25 wt% solution of tri(tert)butylphosphine in xylene (99.9 mg, 123 μmol), sodium-tert-butoxide (445 mg, 4.63 mmol), and xylene (30 mL) were added to a 100 mL glass container and stirred at 140 °C for 4 hours. After cooling to room temperature, water was added to quench the mixture, and the organic layer was extracted using toluene. Activated carbon was added and stirred, and the resulting filtrate was filtered by Celite and concentrated under reduced pressure. The obtained crude material was recrystallized in a mixed solvent of toluene and ethanol to obtain 2.05 g (2.56 mmol, yield 83%) of a white solid of compound (G-3f). The identification of the obtained compound (G-3f) was as follows: １ This was performed using H-NMR. １ H-NMR (DMSO-d ６) δ (ppm): 8.97 (dd, J = 5.3, 8.8 Hz, 1H), 8.94-8.88 (m, 1H), 8.84 (s, 1H), 8.79-8.69 (m, 1H), 8.07 (d, J = 8.5Hz, 1H), 7.88-7 71 (m, 4H), 7.66 (d, J = 8.6Hz, 4H), 7.53 (t, J = 7.6Hz, 1H), 7.50-7.38 (m, 3H), 7.34 (t, J = 7.4Hz, 1H), 7.25-7.115 (m, 3H).

[0195] (Comparative Example 1) As Comparative Example 1, compound (X-1) represented by the following formula was used. Compound (X-1) was synthesized according to the method disclosed in Japanese Patent Application Publication No. 2019-034939.

[0196] (Comparative Example 2) As Comparative Example 2, compound (X-2) represented by the following formula was used. Compound (X-2) was synthesized according to the method disclosed in CN110526825A. The identification of the obtained compound (X-2) was as follows: １ This was performed using H-NMR.

[0197] １ H-NMR (DMSO-d ６ ) δ (ppm): 8.98 (s, 1H), 8.91 (d, J = 8.1Hz, 1H), 8.86 (d, J = 8.0Hz, 2H), 8.75-8.48 (m, 4H), 7.86 (d, J = 8.6Hz, 1H), 7.83-7.57 (m, 1 2H) 7.57-7.46 (m, 3H), 7.40 (d, J = 2.1Hz, 2H), 7.37-7.22 (m, 4H), 7.22-7.14 (m, 1H), 7.12 (dd, J = 2.1, 8.2Hz, 2H), 1.40 (s, 12H).

[0198] (Comparative Example 3) As Comparative Example 3, a compound (X-3) represented by the following formula was used.

[0199] ​Under a nitrogen atmosphere, 3-chlorodibenzo[g,p]chrysene (1.63 g, 4.50 mmol), (4-(diphenylamino)phenyl)boronic acid (1.43 g, 4.95 mmol), palladium acetate (20.2 mg, 90.0 μmol), XPhos (85.8 mg, 180 μmol), 4 M tripotassium phosphate aqueous solution (2.81 mL, 11.3 mmol), and THF (22 mL) were added to a 200 mL glass container and stirred at 70°C for 11 hours. After cooling to room temperature, water and methanol were added and stirred, and the precipitated solid was collected. It was dissolved in chlorobenzene at 140°C, activated carbon was added and stirred, and the activated carbon was removed by Celite filtration. The resulting solution was concentrated under reduced pressure. Recrystallization in a mixed solvent of toluene and ethanol yielded 2.30 g (4.02 mmol, 89% yield) of a white solid of compound (X-3). The identification of the obtained compound (X-3) was as follows: １ This was performed using H-NMR. １ H-NMR (DMSO-d ６ ) δ (ppm) 8.94-8.88 (m, 4H), 8.81 (d, J = 1.7Hz, 1H), 8.74-8.72 (m, 1H), 8.68-8.64 (m, 2H) , 8.03 (dd, J=8.6, 1.7Hz, 1H), 7.80-7.72 (m, 8H), 7.36-7.32 (m, 4H), 7.11-7.07 (m, 8H).

[0200] (Glass transition temperature) This was measured using a DSC7020 manufactured by Hitachi High-Tech Science Corporation. The results are shown in Table 9.

[0201] (Bandgap) The bandgap was calculated from the HOMO value of the vapor-deposited compound film (a 100 nm thick film deposited on a quartz substrate at a rate of 0.10 nm / second) and the wavelength edge of the absorption spectrum. The HOMO value of the vapor-deposited film was measured using an airborne photoelectron spectrometer (AC-3) manufactured by RIKEN KEKI Co., Ltd., and the absorption spectrum was measured using an ultraviolet-visible-near-infrared spectrophotometer (V-750) manufactured by JASCO Corporation. The results are shown in Table 9.

[0202]

[0203] <Example of element>

[0204] (Example of element - 1: Fabrication of photoelectric conversion element for image sensor using compound (B-3)) 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.

[0205] (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.

[0206] (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 DiPh-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-3) was deposited at a rate of 0.10 nm / second to create an electron transport layer 5. (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.

[0207] (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 deposition rate of silver was 0.1 nm / second.

[0208] Using the method described above, the area is 4 mm². ２ A photoelectric conversion element for imaging was fabricated. The thickness of each layer was measured using a stylus-type film thickness gauge (DEKTAK, Bruker). The fabricated element was sealed in a nitrogen atmosphere glove box with oxygen and moisture concentrations of 1 ppm or less. Sealing was performed using a glass sealing cap and bisphenol F type epoxy resin (Nagase ChemteX).

[0209] (Element Example 2) to (Element Example 9) Except for using compounds (B-15) to (G-3f) instead of (B-3) in the preparation of the hole transport layer 104 of Element Example 1, the photoelectric conversion elements for image sensors of Element Example 2 to Element Example 9 were fabricated in the same manner as Element Example 1.

[0210] (Element Comparative Example 1) to (Element Comparative Example 3) The photoelectric conversion elements for image sensors of Element Comparative Examples 1 to 3 were fabricated in the same manner as in Element Example 1, except that compounds (X-1) to (X-3) were used instead of compound (B-3) in the fabrication of the hole transport layer 104 of Element Example 1.

[0211] (Measurement of Dark Current and Response Time) The current (dark current) and response time in the dark were evaluated 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 first electrode 2 side and holes to the second electrode 7 side. The dark current was evaluated using a Keithley source measure unit 2636B. The response time was measured by irradiating with a light pulse and taking the time until the current value returned to the value before irradiation.

[0212] The results are shown in Table 10. Note that the results in Table 10 are relative values, with the results in Element Comparative Example 1 set as the baseline value (1.0). A lower dark current value indicates better performance, and a shorter response time indicates better performance.

[0213] The compounds used in the examples are listed below.

[0214]

[0215] As shown in Table 10, the elements in the examples using a specific photoelectric conversion element material for image sensors exhibited superior response speed and suppressed dark current compared to the elements in the comparative examples.

[0216] 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 condensed ring compound represented by the following formula (1). In the formula, R １ ~R １６ Each of these is independently a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a hydroxyl group, a thiol group, an allyl group, a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms which may have substituents, a monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms which may have substituents, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a group represented by the following formula (2). However, R １ ~R １６ At least one of these is a group represented by the following formula (2). In the formula, R ａ R represents an aromatic hydrocarbon group composed only of a hydrogen atom, a deuterium atom, or a six-membered ring having 6 to 30 carbon atoms, which may have substituents, or a heteroaromatic group having 3 to 36 carbon atoms, which may have substituents; ｂ R represents an aromatic hydrocarbon group consisting only of a hydrogen atom, a deuterium atom, or a six-membered ring having 10 to 30 carbon atoms that may have substituents, or a heteroaromatic group having 3 to 36 carbon atoms that may have substituents; Y independently represents an aromatic hydrocarbon group having 6 to 30 carbon atoms that may have substituents, or a heteroaromatic group having 5 to 36 carbon atoms that may have substituents; n represents 1 or 2, and if n is 2, multiple R ａ ~R ｂ They may be the same or different.

2. In formula (1), R ９ ~R １６ is a hydrogen atom, the condensed ring compound according to claim 1.

3. In equation (1), R ５ and R ８ ~R １６ The fused ring compound according to claim 1, wherein is a hydrogen atom.

4. In equation (1), R １ , R ５ and R ８ ~R １６ The fused ring compound according to claim 1, wherein is a hydrogen atom.

5. In equation (2), R ａ The fused ring compound according to claim 1, wherein the aromatic hydrocarbon group is composed only of a six-membered ring having 10 to 30 carbon atoms, which may have substituents, or a heteroaromatic group having 3 to 36 carbon atoms, which may have substituents, which may have substituents.

6. The condensed ring compound according to claim 1, wherein in formula (2), Y is a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents.

7. The condensed ring compound according to claim 6, wherein in formula (2), the aromatic hydrocarbon group represented by Y is a 1,4-phenylene group, a 1,3-phenylene group, a 4,4'-biphenylene group, a 1,4-naphthylene group, a 1,5-naphthylene group, a 2,6-naphthylene group, or an anthracene-9,10-diyl group.

8. In equation (2), R ａ However, R is a phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, crisenyl group, benzocrisenyl group, dibenzocrisenyl group, dibenzofuranyl group, dibenzothionyl group, carbazolyl group, naphthylphenyl group, phenylnaphthyl group, naphthylnaphthyl group, phenanthrylphenyl group, dibenzofuranylphenyl group, dibenzothionylphenyl group, carbazolylphenyl group, or a group that is a combination of these. ｂ The condensed ring compound according to claim 1, wherein the group is a biphenyl group, a terphenyl group, a naphthyl group, anthryl group, a phenanthryl group, a pyrenyl group, a crisenyl group, a benzocrisenyl group, a dibenzocrisenyl group, a dibenzofuranyl group, a dibenzothionyl group, a carbazolyl group, a naphthylphenyl group, a phenylnaphthyl group, a naphthylnaphthyl group, a phenanthrylphenyl group, a dibenzofuranylphenyl group, a dibenzothionylphenyl group, a carbazolylphenyl group, or a group that is a combination thereof.

9. A material for an organic electronic device comprising a condensed ring compound according to any one of claims 1 to 8.

10. A material for a photoelectric device comprising a condensed ring compound according to any one of claims 1 to 8.

11. A charge transport material or charge blocking material comprising a condensed ring compound according to any one of claims 1 to 8.

12. A hole transport material or electron blocking material comprising a condensed ring compound according to any one of claims 1 to 8.

13. An organic thin film comprising a condensed ring compound according to any one of claims 1 to 8.

14. An organic electronic device comprising a condensed ring compound according to any one of claims 1 to 8.

15. A material for a photoelectric conversion element for an image sensor, comprising a condensed ring compound represented by the following formula (3). In the formula, R Ａ１ ~R Ａ１６ Each of these is independently a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a hydroxyl group, a thiol group, an allyl group, a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms which may have substituents, a monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms which may have substituents, a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, or a group represented by the following formula (4). However, R Ａ１ ~R Ａ１６ At least one of these is a group represented by the following formula (4). In the formula, R Ａａ R represents an aromatic hydrocarbon group composed only of a hydrogen atom, a deuterium atom, or a six-membered ring having 6 to 30 carbon atoms, which may have substituents, or a heteroaromatic group having 3 to 36 carbon atoms, which may have substituents; Ａｂ This represents an aromatic hydrocarbon group composed only of a hydrogen atom, a deuterium atom, or a six-membered ring having 10 to 30 carbon atoms, which may have substituents, or a heteroaromatic group having 3 to 36 carbon atoms, which may have substituents; Y Ａ Each independently represents a C6-C30 monocyclic, linked, or fused aromatic hydrocarbon group which may have substituents, or a C5-C36 monocyclic, linked, or fused heteroaromatic group which may have substituents; n represents 1 or 2, and if n is 2, multiple R Ａａ ~R Ａｂ They may be the same or different.

16. In equation (3), R Ａ９ ~R Ａ１６ A material for a photoelectric conversion element for an image sensor, comprising the condensed ring compound according to claim 15, wherein the compound is a hydrogen atom.

17. In equation (3), R Ａ５ and R Ａ８ ~R Ａ１６ A material for a photoelectric conversion element for an image sensor, comprising the condensed ring compound according to claim 15, wherein the compound is a hydrogen atom.

18. In equation (3), R Ａ１ , R Ａ５ , and R Ａ８ ~R Ａ１６ A material for a photoelectric conversion element for an image sensor, comprising the condensed ring compound according to claim 15, wherein the compound is a hydrogen atom.

19. In equation (4), R Ａａ A material for a photoelectric conversion element for an image sensor, comprising the fused ring compound according to claim 15, wherein the fused ring compound is a monocyclic, linked, or fused aromatic hydrocarbon group having 10 to 30 carbon atoms, which may have substituents, or a monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms, which may have substituents.

20. In equation (4), Y Ａ A material for a photoelectric conversion element for an image sensor, comprising the fused ring compound according to claim 15, wherein the fused ring compound is a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have substituents.

21. In equation (4), Y Ａ A material for a photoelectric conversion element for an image sensor, comprising the fused ring compound according to claim 20, wherein the aromatic hydrocarbon group represented by is a 1,4-phenylene group, a 1,3-phenylene group, a 4,4'-biphenylene group, a 1,4-naphthylene group, a 1,5-naphthylene group, a 2,6-naphthylene group, or an anthracene-9,10-diyl group.

22. In equation (4), R Ａａ However, R is a phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, pyrenyl group, crisenyl group, benzocrisenyl group, dibenzocrisenyl group, dibenzofuranyl group, dibenzothionyl group, carbazolyl group, naphthylphenyl group, phenylnaphthyl group, naphthylnaphthyl group, phenanthrylphenyl group, dibenzofuranylphenyl group, dibenzothionylphenyl group, carbazolylphenyl group, or a group that is a combination of these. Ａｂ A material for a photoelectric element for an image sensor, comprising a condensed ring compound according to claim 15, wherein the group is a biphenyl group, a terphenyl group, a naphthyl group, anthryl group, a phenanthryl group, a pyrenyl group, a crisenyl group, a benzocrisenyl group, a dibenzocrisenyl group, a dibenzofuranyl group, a dibenzothionyl group, a carbazolyl group, a naphthylphenyl group, a phenylnaphthyl group, a naphthylnaphthyl group, a phenanthrylphenyl group, a dibenzofuranylphenyl group, a dibenzothionylphenyl group, a carbazolylphenyl group, or a group having these combinations.

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