Material for photoelectric conversion device, method for manufacturing fused ring compound, and fused ring compound

Abstract

To provide a novel material for a photoelectric conversion device, a method for manufacturing a fused ring compound, and a fused ring compound, which contain fused ring compounds having specific structures.SOLUTION: A photoelectric conversion device material is used, which contains a fused ring compound represented by the following formula (1). In the formula (1), R1 to R10 each independently represent a hydrogen atom or the like.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a material for a photoelectric conversion device containing a fused ring compound having a specific structure, a method for producing the fused ring compound, and the fused ring compound. [Background technology]

[0002] Currently, active efforts are being made to create new, highly functional devices using organic materials. Research and development is particularly active on organic electronic devices, such as photoelectric conversion devices and organic light-emitting diode (OLED) devices, with advances being made in materials and device design aimed at improving device performance. For example, in photoelectric conversion devices used for video recording, a problem exists in that slow transport of carriers (electrons and holes) generated in the light-receiving layer to the electrode can cause image retention. In organic EL devices, slow transport of carriers from the electrode to the light-emitting layer can increase the driving voltage. Therefore, highly efficient carrier movement within the device is essential for improving device performance. Incidentally, π-conjugated compounds having various skeletons and methods for synthesizing the same have been disclosed with the aim of providing novel π-conjugated compounds (see Patent Document 1). However, the compounds described in Patent Document 1 are limited to use as light-emitting materials for organic EL devices, and there is no mention whatsoever of the performance of photoelectric conversion devices. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] U.S. Publication No. 2018 / 0334459 Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention has been made in view of the above-mentioned background art, and an object of the present invention is to provide a novel material for a photoelectric conversion element, which contains a fused ring compound having a specific structure, a method for producing the fused ring compound, and the fused ring compound. [Means for solving the problem]

[0005] As a result of intensive research to solve the above problems, the present inventors have discovered a material for a photoelectric conversion element containing a fused ring compound having a specific structure, a method for producing the fused ring compound, and the fused ring compound, thereby completing the present invention.

[0006] That is, the present disclosure includes the following embodiments.

[0007] [1] A material for a photoelectric conversion element, comprising a fused ring compound represented by the following formula (1): [ka] In the above formula (1), R 1 ~R 10 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR 21 R 22 , or -OR 23 represents R 21 ~R 23 each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, an optionally substituted silyl group having 1 to 18 carbon atoms, an optionally substituted acyl group having 1 to 18 carbon atoms, or an optionally substituted methanesulfonyl group having 1 to 18 carbon atoms; Adjacent R 1 ~R 10 may be bonded to each other to form a ring, X 1 ~X 4 Among these, adjacent two represent carbon atoms bonded to a group represented by the following formula (2), and the remaining are each independently CR 11represents R 11 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR 24 R 25 , or -OR 26 represents R 24 ~R 26 each independently represents an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, an optionally substituted silyl group having 1 to 18 carbon atoms, an optionally substituted acyl group having 1 to 18 carbon atoms, or an optionally substituted methanesulfonyl group having 1 to 18 carbon atoms. However, in the above formula (1), R 1 ~R 10 at least one of the above alkyl group having 1 to 18 carbon atoms which may be substituted, the above aromatic hydrocarbon group having 6 to 30 carbon atoms which may be substituted, the above heteroaromatic group having 3 to 30 carbon atoms which may be substituted, and the above -NR 21 R 22 represents a group having at least one substituent selected from the group consisting of: [ka] In the above formula (2), R 12 ~R 15 each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR 21 R 22 , or -OR 23 represents Adjacent R 12 ~R 15 may be bonded to each other to form a ring, The carbon atom at the position * is X in the above formula (1). 1 ~X 4 The two adjacent carbon atoms represent the carbon atoms to which they are bonded. [2] In the above formula (1), adjacent R 1 ~R 15 The material for a photoelectric conversion element according to the above [1], wherein are not bonded to each other to form a ring. [3] In the above formula (1), R 1 ~R 15 each independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, an n-octadecyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, -NR 21 R 22 , and -OR 23 is at least one group selected from the group consisting of R 21 ~R 23are each independently at least one group selected from the group consisting of a hydrogen atom, a benzyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, an optionally substituted trimethylsilyl group, an optionally substituted phenyldimethylsilyl group, an optionally substituted diphenylmethylsilyl group, an optionally substituted acetyl group, an optionally substituted benzoyl group, and an optionally substituted methanesulfonyl group. [4] In the above formula (1), R 5 ~R 15 The material for a photoelectric conversion element according to any one of [1] to [3] above, wherein all of are hydrogen atoms. [5] The material for photoelectric conversion elements according to any one of [1] to [4] above, which is a material for photoelectric conversion elements for use in an imaging element. [6] The material for a photoelectric conversion element according to any one of [1] to [4] above, which is a hole transport material for a photoelectric conversion element for an imaging element or an electron blocking material for a photoelectric conversion element for an imaging element. [7] A fused ring compound represented by the following formula (5): [ka] In the above formula (5), R b1 ~R b10are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR b21 R b22 , or -OR b23 represents R b21 ~R b23 each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, an optionally substituted silyl group having 1 to 18 carbon atoms, an optionally substituted acyl group having 1 to 18 carbon atoms, or an optionally substituted methanesulfonyl group having 1 to 18 carbon atoms; Adjacent R b1 ~R b10 may be bonded to each other to form a ring, X b1 ~X b4 Among these, adjacent two represent carbon atoms bonded to a group represented by the following formula (6), and the remaining are each independently CR b11 represents R b11 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR b24 R b25 , or -OR b26 represents R b24 ~R b26each independently represents an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, an optionally substituted silyl group having 1 to 18 carbon atoms, an optionally substituted acyl group having 1 to 18 carbon atoms, or an optionally substituted methanesulfonyl group having 1 to 18 carbon atoms. However, in the above formula (5), R b1 ~R b10 at least one of the above alkyl group having 1 to 18 carbon atoms which may be substituted, the above aromatic hydrocarbon group having 6 to 30 carbon atoms which may be substituted, the above heteroaromatic group having 3 to 30 carbon atoms which may be substituted, and the above -NR b21 R b22 is a group having at least one substituent selected from the following: [ka] In the above formula (6), R b12 ~R b15 each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR b21 R b22 , or -OR b23 represents Adjacent R b12 ~R b15 may be bonded to each other to form a ring, The carbon atom at the position * is X in the above formula (5). b1 ~X b4 The two adjacent carbon atoms represent the carbon atoms to which they are bonded. [8] The fused ring compound according to [7] above, wherein the fused ring compound represented by the formula (5) above is represented by the following formula (7A) or formula (7B): [ka] In the above formula (7A) and formula (7B), R b1 ~R b10 is R in the above formula (5). b1 ~Rb 10 , which has the same definition as R b11 are each independently R in the above formula (5). a11 has the same definition as R b12 ~R b15 is R in the above formula (6) a12 ~R a15 is the same definition as [9] The fused ring compound represented by the above formula (7A) or formula (7B) is b1 ~R b15 are not bonded to each other to form a ring.

[10] In the above formula (7A) and formula (7B), R b1 ~R b15 each independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, an n-octadecyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, -NR b21 R b22 , and -OR b23 is at least one group selected from the group consisting of R b21 ~R b23are each independently at least one group selected from the group consisting of a hydrogen atom, a benzyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, an optionally substituted trimethylsilyl group, an optionally substituted phenyldimethylsilyl group, an optionally substituted diphenylmethylsilyl group, an optionally substituted acetyl group, an optionally substituted benzoyl group, and an optionally substituted methanesulfonyl group.

[11] In the above formula (7A) and formula (7B), R b5 ~R b15 are all hydrogen atoms.

[12] An organic thin film comprising the material for photoelectric conversion devices according to any one of the above [1] to [6], or the material for photoelectric conversion devices containing the fused ring compound according to any one of the above [7] to

[11] .

[13] A photoelectric conversion element comprising the material for photoelectric conversion elements according to any one of the above [1] to [6], or the material for photoelectric conversion elements containing the fused ring compound according to any one of the above [7] to

[11] .

[14] A photoelectric conversion element for an imaging device, comprising the material for a photoelectric conversion element according to any one of the above [1] to [6], or the material for a photoelectric conversion element containing the fused ring compound according to any one of the above [7] to

[11] .

[15] A method for producing a fused ring compound represented by the following formula (3), which comprises mixing a compound represented by the following formula (A) with an alkali metal in the presence of a solvent using a grinder, and carrying out intramolecular cyclization by a mechanochemical reaction. [ka] In the above formula (A), R a1 ~R a10 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR a21 R a22 , or -OR a23 represents R a21 ~R a23 each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, an optionally substituted silyl group having 1 to 18 carbon atoms, an optionally substituted acyl group having 1 to 18 carbon atoms, or an optionally substituted methanesulfonyl group having 1 to 18 carbon atoms; Adjacent R a1 ~R a10 may be bonded to each other to form a ring, X a1 ~X a4 Among these, adjacent two represent carbon atoms bonded to a group represented by the following formula (4), and the remaining are each independently CR a11 represents R a11 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR a24 R a25 , or -OR a26 represents R a24 ~R a26each independently represents an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, an optionally substituted silyl group having 1 to 18 carbon atoms, an optionally substituted acyl group having 1 to 18 carbon atoms, or an optionally substituted methanesulfonyl group having 1 to 18 carbon atoms. [ka] In the above formula (4), R a12 ~R a15 each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR a21 R a22 , or -OR a23 represents Adjacent R a12 ~R a15 may be bonded to each other to form a ring, The carbon atom at the position * is X in the above formula (a). a1 ~X a4 The two adjacent carbon atoms represent the carbon atoms to which they are bonded. [ka] In the above formula (3), R a1 ~R a10 , and X a1 ~X a4 is R in the above formula (A) a1 ~R a10 , and X a1 ~X a4 is the same definition as

[16] The compound represented by the above formula (A) is a1 ~R a15 are not bonded to each other to form a ring.

[17] In the above formula (A), R a1 ~R a15 each independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, an n-octadecyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, -NR a21 R a22 and -ORa23, R a21 ~R a23are each independently at least one group selected from the group consisting of a hydrogen atom, a benzyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, an optionally substituted trimethylsilyl group, an optionally substituted phenyldimethylsilyl group, an optionally substituted diphenylmethylsilyl group, an optionally substituted acetyl group, an optionally substituted benzoyl group, and an optionally substituted methanesulfonyl group.

[18] In the above formula (A), R a5 ~R a15 are all hydrogen atoms.

[19] The method for producing a fused ring compound according to any one of

[15] to

[18] above, wherein the pulverizer is at least one selected from the group consisting of a ball mill, a bead mill, a rod mill, a jet mill, and a rocking mill.

[20] The method for producing a fused ring compound according to any one of

[15] to

[19] above, wherein the alkali metal is at least one selected from the group consisting of lithium, sodium, and potassium.

[21] The production method according to any one of

[15] to

[20] above, wherein the solvent is at least one selected from the group consisting of tetrahydrofuran, toluene, hexane, diethylene glycol dimethyl ether, 1,2-dimethoxyethane, diethyl ether, triethylamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, and N,N,N',N",N"-pentamethyldiethylenetriamine. [Effects of the Invention]

[0008] According to the present disclosure, there are provided a novel material for a photoelectric conversion device including a fused ring compound having a specific structure, a method for producing the fused ring compound, and the fused ring compound. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a schematic cross-sectional view showing an example of a stacked structure of a photoelectric conversion element according to one embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0010] <Photoelectric conversion element materials> A material for a photoelectric conversion device according to one embodiment of the present disclosure includes a fused ring compound represented by the following formula (1). [ka] In the above formula (1), R 1 ~R 10 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR 21 R 22 , or -OR 23 represents R 21 ~R 23each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, an optionally substituted silyl group having 1 to 18 carbon atoms, an optionally substituted acyl group having 1 to 18 carbon atoms, or an optionally substituted methanesulfonyl group having 1 to 18 carbon atoms; Adjacent R 1 ~R 10 may be bonded to each other to form a ring, X 1 ~X 4 Among these, adjacent two represent carbon atoms bonded to a group represented by the following formula (2), and the remaining are each independently CR 11 represents R 11 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR 24 R 25 , or -OR 26 represents R 24 ~R 26 each independently represents an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, an optionally substituted silyl group having 1 to 18 carbon atoms, an optionally substituted acyl group having 1 to 18 carbon atoms, or an optionally substituted methanesulfonyl group having 1 to 18 carbon atoms. However, in the above formula (1), R 1 ~R 10 at least one of the above alkyl group having 1 to 18 carbon atoms which may be substituted, the above aromatic hydrocarbon group having 6 to 30 carbon atoms which may be substituted, the above heteroaromatic group having 3 to 30 carbon atoms which may be substituted, and the above -NR 21 R 22 represents a group having at least one substituent selected from the group consisting of: [ka] In the above formula (2), R 12 ~R 15 each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR 21 R 22 , or -OR 23 represents Adjacent R 12 ~R 15 may be bonded to each other to form a ring, The carbon atom at the position * is X in the above formula (1). 1 ~X 4 The two adjacent carbon atoms represent the carbon atoms to which they are bonded.

[0011] By having the above-mentioned specific structure, the material for photoelectric conversion devices can be suitably applied to organic thin films, photoelectric conversion devices, and the like.

[0012] In the above formula (1), adjacent R 1 ~R 15 are preferably fused ring compounds in which the groups are not bonded to each other to form a ring.

[0013] In the above formula (1), R 1 ~R 15are each independently a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, an n-octadecyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, -NR 21 R 22 , and -OR 23 At least one group selected from the group consisting of R 21 ~R 23are each independently at least one group selected from the group consisting of a hydrogen atom, a benzyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, an optionally substituted trimethylsilyl group, an optionally substituted phenyldimethylsilyl group, an optionally substituted diphenylmethylsilyl group, an optionally substituted acetyl group, an optionally substituted benzoyl group, and an optionally substituted methanesulfonyl group.

[0014] Above R 1 ~R 15 , R 21 ~R 23 When the group has a substituent, the substituent is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an amino group, an aromatic hydrocarbon group, and a heteroaromatic group, and an alkoxy group, an amino group, an aromatic hydrocarbon group, or a heteroaromatic group is more preferred.

[0015] The alkyl group as the substituent is preferably a linear, branched, or cyclic alkyl group having 1 to 4 carbon atoms. Examples of such alkyl groups include a methyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, and a tert-butyl group.

[0016] The aromatic hydrocarbon group as the substituent is preferably a monocyclic, linked ring, or fused ring aromatic hydrocarbon group having a carbon number of 6 to 30. Examples of such aromatic hydrocarbon groups include a phenyl group, a biphenyl group, and a naphthyl group.

[0017] The heteroaromatic group as the substituent is preferably a monocyclic, linked ring, or fused ring heteroaromatic group having 3 to 36 carbon atoms. Examples of such heteroaromatic groups include a pyridyl group, a pyrimidyl group, a triazyl group, a dibenzofuranyl group, a dibenzothiophenyl group, and a carbazolyl group.

[0018] In the above formula (1), R 5 ~R 15 is preferably a hydrogen atom from the viewpoint of obtaining the fused ring compound in good yield.

[0019] In the above formula (1), adjacent X 1 ~X 4 When they are bonded to each other to form a ring, X 1 and X 2 , or X 3 and X 4 The ring formed here is preferably, for example, benzene, naphthalene, anthracene, or phenanthrene, and more preferably benzene, naphthalene, or phenanthrene.

[0020] The material for a photoelectric conversion device according to one aspect of the present disclosure is used, for example, as an organic thin film containing the material for a photoelectric conversion device.

[0021] The material for a photoelectric conversion device according to one aspect of the present disclosure is suitably used as a material for a photoelectric conversion device for an imaging device, particularly as a hole transport material for a photoelectric conversion device for an imaging device or an electron blocking material for a photoelectric conversion device for an imaging device.

[0022] [Fused ring compounds] The fused ring compound according to one embodiment of the present disclosure is represented by the following formula (5). [ka] In the above formula (5), R b1 ~R b10are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR b21 R b22 , or -OR b23 represents R b21 ~R b23 each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, an optionally substituted silyl group having 1 to 18 carbon atoms, an optionally substituted acyl group having 1 to 18 carbon atoms, or an optionally substituted methanesulfonyl group having 1 to 18 carbon atoms; Adjacent R b1 ~R b10 may be bonded to each other to form a ring, X b1 ~X b4 Among these, adjacent two represent carbon atoms bonded to a group represented by the following formula (6), and the remaining are each independently CR b11 represents R b11 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR b24 R b25 , or -OR b26 represents R b24 ~R b26each independently represents an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, an optionally substituted silyl group having 1 to 18 carbon atoms, an optionally substituted acyl group having 1 to 18 carbon atoms, or an optionally substituted methanesulfonyl group having 1 to 18 carbon atoms. However, in the above formula (5), R b1 ~R b10 at least one of the above-mentioned alkyl group having 1 to 18 carbon atoms which may be substituted, the above-mentioned aromatic hydrocarbon group having 6 to 30 carbon atoms which may be substituted, the above-mentioned heteroaromatic group having 3 to 30 carbon atoms which may be substituted, and the above-mentioned -NR b21 R b22 is a group having at least one substituent selected from the following: [ka] In the above formula (6), R b12 ~R b15 each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR b21 R b22 , or -OR b23 represents Adjacent R b12 ~R b15 may be bonded to each other to form a ring, The carbon atom at the position * is X in the above formula (5). b1 ~X b4 The two adjacent carbon atoms represent the carbon atoms to which they are bonded.

[0023] By having the above-mentioned specific structure, the above-mentioned fused ring compound can be suitably applied to organic thin films, photoelectric conversion elements, and the like.

[0024] The fused ring compound represented by the above formula (5) is preferably a fused ring compound represented by the following formula (7A) or formula (7B). [ka] In the above formula (7A) and formula (7B), R b1 ~R b10 is R in the above formula (5). b1 ~Rb 10 , which has the same definition as R b11 are each independently R in the above formula (5). a11 has the same definition as R b12 ~R b15 is R in the above formula (6) a12 ~R a15 is the same definition as

[0025] The fused ring compound represented by the above formula (7A) or (7B) may be a compound having adjacent R b1 ~R b15 are preferably fused ring compounds in which the groups are not bonded to each other to form a ring.

[0026] In the above formula (7A) and formula (7B), R b1 ~R b15each independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, an n-octadecyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, -NR b21 R b22 , and -OR b23 At least one group selected from the group consisting of R b21 ~R b23 are each independently at least one group selected from the group consisting of a hydrogen atom, a benzyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, an optionally substituted trimethylsilyl group, an optionally substituted phenyldimethylsilyl group, an optionally substituted diphenylmethylsilyl group, an optionally substituted acetyl group, an optionally substituted benzoyl group, and an optionally substituted methanesulfonyl group.

[0027] In the above formula (7A) and formula (7B), R b5 ~R b15 are preferably all hydrogen atoms.

[0028] <Preferred specific examples of fused ring compounds> Preferred examples of the fused ring compound represented by the above formula (5) are shown below, but the fused ring compound is not limited to these compounds. The fused ring compound represented by the above formula (5) is preferably a compound (LM-N) having a skeleton of any one of (AA) to (CN) shown in Tables 1 and 2, and the substituent R of the skeleton is any one of the groups corresponding to N shown in Tables 3 to 5. Here, N represents any integer from 1 to 120. That is, the compound (LM-N) represents the compounds (LM-1) to (LM-120). Furthermore, L represents any symbol from A to C, and M represents any symbol from A to N. Therefore, for example, in the case of a compound (LM-2) where N=2, when L=A and M=B, it indicates a compound (AB-2) which has a skeleton of (AB) and the substituent R of the skeleton is a methyl group.

[0029] [Table 1]

[0030] [Table 2]

[0031] [Table 3]

[0032] [Table 4]

[0033] [Table 5]

[0034] The fused ring compound according to one embodiment of the present disclosure is suitably used, for example, as a material for a photoelectric conversion element, preferably as a material for a photoelectric conversion element for an imaging element, and more preferably as a hole transport material for a photoelectric conversion element for an imaging element or an electron blocking material for a photoelectric conversion element for an imaging element.

[0035] [Photoelectric conversion element] A photoelectric conversion device according to one embodiment of the present disclosure includes the above-described material for a photoelectric conversion device according to one embodiment of the present disclosure, or a material for a photoelectric conversion device containing a fused ring compound represented by the above general formula (5).

[0036] Such a photoelectric conversion element is not particularly limited, but may include, for example, an element including an upper electrode, a lower electrode, and one or more organic layers disposed between the upper electrode and the lower electrode, at least one of the organic layers including the above-mentioned material for a photoelectric conversion element. Note that each of the organic layers in the above-mentioned photoelectric conversion element can also be regarded as an organic thin film. In the present disclosure, the configuration of the photoelectric conversion element is not particularly limited, but examples thereof include the following configurations (i) to (v).

[0037] (i) Lower electrode / photoelectric conversion layer / upper electrode (ii) Lower electrode / electron transport layer (hole blocking layer) / photoelectric conversion layer / upper electrode (iii) Lower electrode / photoelectric conversion layer / hole transport layer (electron blocking layer) / upper electrode (iv) Lower electrode / electron transport layer (hole blocking layer) / photoelectric conversion layer / hole transport layer (electron blocking layer) / upper electrode (v) Lower electrode / electron transport layer (hole blocking layer) / photoelectric conversion layer / hole transport layer (electron blocking layer) / buffer layer / upper electrode

[0038] The buffer layer may be replaced with a layer having a different name or function, as needed, such as a hole injection layer or a work function adjustment layer.

[0039] A preferred layer configuration of a photoelectric conversion element for an imaging device includes, for example, an upper electrode, a lower electrode, a photoelectric conversion layer, and a hole transport layer, in which the photoelectric conversion layer is disposed between the upper electrode and the lower electrode, and the hole transport layer is disposed between the photoelectric conversion layer and the upper electrode. Another preferred layer configuration of the photoelectric conversion element for an imaging device includes, for example, an upper electrode, a lower electrode, a photoelectric conversion layer, a hole transport layer, and a buffer layer, in which the photoelectric conversion layer is disposed between the upper electrode and the lower electrode, the hole transport layer is disposed between the photoelectric conversion layer and the upper electrode, and the buffer layer is disposed between the hole transport layer and the upper electrode and adjacent to the hole transport layer.

[0040] The photoelectric conversion element for an imaging device preferably contains the above-described material for a photoelectric conversion element for an imaging device in at least one layer selected from the group consisting of an electron transport layer (hole blocking layer), a photoelectric conversion layer, a hole transport layer (electron blocking layer), and a buffer layer. The photoelectric conversion element for an imaging device preferably contains the above-described material for a photoelectric conversion element for an imaging device in the photoelectric conversion layer and / or the hole transport layer (electron blocking layer), and more preferably contains the above-described material for a photoelectric conversion element for an imaging device in the hole transport layer (electron blocking layer). The material for a photoelectric conversion element for an imaging device may be contained in multiple layers of the photoelectric conversion element for an imaging device.

[0041] Hereinafter, the photoelectric conversion element for an image sensor according to this embodiment will be described in more detail using the above configuration (v) as an example, with reference to Fig. 1. Fig. 1 is a schematic cross-sectional view showing an example of the layered configuration of a photoelectric conversion element for an image sensor including a hole transport material for a photoelectric conversion element for an image sensor or an electron blocking material for a photoelectric conversion element for an image sensor according to this embodiment.

[0042] 1 includes, in this order, a substrate 1, a lower 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 an upper electrode 7. Note that in the photoelectric conversion element for an image sensor of this embodiment, some of these layers may be omitted, and other layers may be added.

[0043] In the photoelectric conversion element 100 for an imaging device, light is incident from below the transparent lower electrode 2. Furthermore, a voltage is applied to the photoelectric conversion element 100 for an imaging device so that, of the charges (holes and electrons) generated in the photoelectric conversion layer 4, the electrons move to the lower electrode 2 and the holes move to the upper electrode 7. That is, in the photoelectric conversion element 100 for an imaging device, the lower electrode 2 serves as an electron collecting electrode and the upper electrode 7 serves as a hole collecting electrode.

[0044] [Layer containing charge transport material for photoelectric conversion element for imaging element] The photoelectric conversion element 100 for an imaging device contains a material for a photoelectric conversion element for an imaging device in at least one layer selected from the group consisting of an electron transport layer (hole blocking layer) 3, a photoelectric conversion layer 4, a hole transport layer (electron blocking layer) 5, and a buffer layer 6. The photoelectric conversion element 100 for an imaging device preferably contains a charge transport material for a photoelectric conversion element for an imaging device or a charge blocking material for a photoelectric conversion element for an imaging device in the photoelectric conversion layer 4 and / or the hole transport layer (electron blocking layer) 5, and more preferably contains a charge transport material for a photoelectric conversion element for an imaging device or a charge blocking material for a photoelectric conversion element for an imaging device in the hole transport layer (electron blocking layer) 5. The charge transport material for a photoelectric conversion element for an imaging device or the charge blocking material for a photoelectric conversion element for an imaging device may be contained in multiple layers of the photoelectric conversion element 100 for an imaging device.

[0045] Hereinafter, a photoelectric conversion element 100 for an imaging element in which the hole transport layer (electron blocking layer) 5 contains a hole transport material for a photoelectric conversion element for an imaging element or an electron blocking material for a photoelectric conversion element for an imaging element will be described.

[0046] [Board 1] The substrate is not particularly limited, and examples thereof include a glass plate, a quartz plate, a plastic plate, etc. In a configuration in which light is incident from the substrate 1 side, it is preferable that the substrate 1 has high transmittance to the wavelength of light (for example, a transmittance of 80% or more, preferably a transmittance of 90% or more).

[0047] [Bottom electrode 2] A lower electrode 2 is provided on a substrate 1 . In the case of a photoelectric conversion element for an imaging device configured so that light passes through the lower electrode 2 and enters the photoelectric conversion layer, it is preferable that the lower electrode 2 has high transparency (for example, a transmittance of 80% or more, preferably a transmittance of 90% or more) to the wavelength of the incident light.

[0048] There are no particular limitations on the transparent material used for the lower electrode 2. From the viewpoint of excellent light transmittance, the material constituting the lower electrode 2 may be, for example, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide, aluminum-doped tin oxide, magnesium-indium oxide, nickel-tungsten oxide, other metal oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, metal sulfides such as zinc sulfide, etc.

[0049] In the case of a photoelectric conversion element for an imaging device configured so that light enters the photoelectric conversion layer only from the upper electrode 7 side, the transmission characteristics of the lower electrode 2 are not important. Therefore, examples of materials used for the lower electrode 2 in this case may include gold, iridium, molybdenum, palladium, platinum, etc.

[0050] [Electron transport layer (hole blocking layer) 3] Between the lower electrode 2 and the photoelectric conversion layer 4, an electron transport layer (hole blocking layer) 3 is provided.

[0051] The electron transport layer (hole blocking layer) 3 has the role of transporting electrons generated in the photoelectric conversion layer 4 to the lower electrode 2 and the role of blocking holes generated in the photoelectric conversion layer 4 from moving to the lower electrode 2.

[0052] The electron transport layer (hole blocking layer) 3 may have a single layer structure made of one or more materials, or a laminate structure made of multiple layers of the same or different compositions. The electron transport layer (hole blocking layer) 3 may have, for example, a two-layer structure including a layer made of a material specialized for hole blocking properties and adjacent to the photoelectric conversion layer 4, and a layer made of a material specialized for electron transport properties and adjacent to the lower electrode 2.

[0053] The electron transport layer (hole blocking layer) 3 may be a layer containing a conventionally known electron transport material, such as bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis(2-methyl-8-quinolinolato)-4-(phenylphenolato)aluminum), 4,6-bis(3,5-di(pyridin-4-yl)phenyl)-2-methylpyrimidine, N,N'-diphenyl-1,4,5,8-naphthalenetetracarboxylic acid diimide, and N,N'-di(4-pyridyl)-1,4,5,8-naphthalenetetracarboxylic acid diimide.

[0054] [Photoelectric conversion layer 4] The photoelectric conversion layer 4 is provided between the electron transport layer (hole blocking layer) 3 and a hole transport layer (electron blocking layer) 5 described later. The photoelectric conversion layer 4 contains a material having a photoelectric conversion function.

[0055] The photoelectric conversion layer 4 may be made of either an organic or inorganic material as long as it can generate signal charges according to the amount of light received. When the photoelectric conversion layer 4 is made of an organic material, it may have a single layer structure made of one or more materials, or a laminate structure made of multiple layers of the same or different compositions. Materials used for the photoelectric conversion layer 4 include n-type semiconductors and p-type semiconductors. N-type semiconductors are organic semiconductors with acceptor properties, and compounds that easily accept electrons and have high electron transport properties are used. P-type semiconductors are organic semiconductors with donor properties, and compounds that easily donate electrons and have high hole transport properties are used. When multiple materials are used in the photoelectric conversion layer 4, the combinations include, for example, an n-type semiconductor and a p-type semiconductor, an n-type semiconductor and a compound having lower acceptor properties than the n-type semiconductor, a p-type semiconductor and a compound having lower donor properties than the p-type semiconductor, etc. One type of each material may be used, or two or more types of materials may be used. The photoelectric conversion layer 4 may contain a dye compound that is excellent at absorbing specific light. The dye compound may be a compound that has lower acceptor properties than the n-type semiconductor, or a compound that has lower donor properties than the p-type semiconductor. In terms of increasing photoelectric conversion efficiency, it is desirable that the photoelectric conversion layer 4 further contains a dye compound in addition to the n-type semiconductor and the p-type semiconductor. Examples of compounds contained in the photoelectric conversion layer 4 include coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, fullerene and its derivatives, azole derivatives such as imidazole, thiazole, thiadiazole, oxazole, oxadiazole, and triazole, naphthalenetetracarboxylic acid diimide, and hole transport materials. The photoelectric conversion layer 4 made of these materials may be formed, for example, by vapor deposition using a mixed powder obtained by mixing powders of the respective materials, or by co-depositing the respective materials in any ratio.

[0056] 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 derivatives thereof include

[60] fullerene,

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

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

[0057] Specific examples of hole transport materials include 9,9'-(9,9'-spirobi[9H-fluorene]-2,7'-diyl)bis[9H-carbazole], 2,7-diphenyl[1]benzothieno[3,2-b][1]benzothiophene (DiPh-BTBT), benzo[1,2-b:3,4-b':5,6-b'']trifuran compounds, benzo[1,2-b:3,4-b':5,6-b'']trithiophene compounds, naphtho[1,2-b:5,6-b']dithiophene, naphtho[2,3-b]naphtho[2',3' :4,5]thieno[2,3-d]thiophene, benzo[1,2-b:4,5-b']difuran, benzo[1,2-b:4,5-b']dithiophene, benzo[1,2-b:4,5-b']bis[1]benzothiophene, naphtho[1,2-b:5,6-b']bis[1]benzothiophene, chryseno[1,2-b:8,7-b']dithiophene, [1]benzothieno[3,2-b][1]benzothiophene, compounds represented by the following formula (ic-1), compounds represented by the following formula (ic-2), and the like.

[0058] [ka]

[0059] The material having the photoelectric conversion function described above may be contained only in the photoelectric conversion layer 4, or may also be contained in layers other than the photoelectric conversion layer 4. For example, layers adjacent to the photoelectric conversion layer 4 (electron transport layer (hole blocking layer) 3, hole transport layer (electron blocking layer) 5) may contain a material having the photoelectric conversion function.

[0060] [Hole transport layer (electron blocking layer) 5] A hole transport layer (electron blocking layer) 5 is provided between the photoelectric conversion layer 4 and a buffer layer 6 described later.

[0061] The hole transport layer (electron blocking layer) 5 has the role of transporting holes generated in the photoelectric conversion layer 4 toward the upper electrode 7 and the role of blocking electrons generated in the photoelectric conversion layer 4 from moving toward the upper electrode 7. The hole transport layer (electron blocking layer) 5 preferably contains the above-mentioned charge transport material for a photoelectric conversion element for an imaging device or the charge blocking material for a photoelectric conversion element for an imaging device.

[0062] The hole transport layer (electron blocking layer) 5 may have a single layer structure made of one or more materials, or a laminate structure made of multiple layers of the same or different compositions. The hole transport layer (electron blocking layer) 5 may have, for example, a two-layer structure including a layer made of a material specialized for electron blocking properties and adjacent to the photoelectric conversion layer 4, and a layer made of a material specialized for hole transport properties and adjacent to the buffer layer 6.

[0063] The hole transport layer (electron blocking layer) 5 may further contain a conventionally known hole transport material in addition to the above-mentioned materials for a photoelectric conversion element for an imaging device. Preferred compounds and specific examples of the conventionally known hole transport material include the same as the hole transport materials described in the section on the photoelectric conversion layer 4.

[0064] [Buffer layer 6] A buffer layer 6 is provided between the hole transport layer (electron blocking layer) 5 and the upper electrode 7, which will be described later. When the upper electrode 7 is formed by sputtering, the buffer layer 6 serves to reduce damage to the organic layer (for example, the hole transport layer (electron blocking layer) 5) during sputtering. The buffer layer 6 also serves to efficiently accept holes from the hole transport layer (electron blocking layer) 5 by adjusting the work function of the buffer layer 6, and is also called a hole injection layer or a work function adjustment layer.

[0065] The material forming the buffer layer 6 may be a known material, such as naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN), or the like.

[0066] [Top electrode 7] An upper electrode 7 is provided on the buffer layer 6 . The material of the upper electrode 7 is not particularly limited, and may be, for example, sodium, sodium-potassium alloy, magnesium, lithium, a magnesium / copper mixture, silver, a magnesium / silver mixture, aluminum, a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al2O3) mixture, indium, a lithium / aluminum mixture, or a rare earth metal.

[0067] [How each layer is formed] Each layer other than the lower electrode 2 and the upper electrode 7 can be formed by thinning the material of each layer (and, if necessary, materials such as binder resin, solvent, etc.) using a known method such as vacuum deposition, spin coating, casting, or LB (Langmuir-Blodgett) method. The thickness of each layer other than the lower electrode 2 and the upper electrode 7 is not particularly limited and can be selected appropriately depending on the situation. The thickness of each layer other than the lower electrode 2 and the upper electrode 7 is usually in the range of 5 nm to 5 μm.

[0068] The lower electrode 2 and the upper electrode 7 can be formed by thinning the electrode material by a method such as vapor deposition or sputtering. When the lower electrode 2 and the upper electrode 7 have a pattern, the pattern can be formed, for example, through a mask of a desired shape. Alternatively, after forming a thin film by vapor deposition, sputtering, or the like, a pattern of a desired shape can be formed by photolithography.

[0069] The film thickness of the lower electrode 2 and the upper electrode 7 may be 1 μm or less, and is preferably 10 nm or more and 200 nm or less.

[0070] The materials constituting the lower electrode 2 and the upper electrode 7 may be interchanged as necessary (also called an inverted structure). In such a structure, light passes through the upper electrode 7 and enters the photoelectric conversion layer 4, forming a photoelectric conversion element for an imaging device.

[0071] An imaging device including the photoelectric conversion element according to this embodiment can be applied to, for example, imaging devices in digital cameras, digital video cameras, and the like, and imaging devices built into mobile phones and the like. Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments.

[0072] [Method for producing fused ring compounds] A method for producing a fused ring compound according to one embodiment of the present disclosure is a method for producing a fused ring compound represented by the following formula (3), which comprises mixing a compound represented by the following formula (A) with an alkali metal in the presence of a solvent using a grinder, and carrying out intramolecular cyclization by a mechanochemical reaction. [ka] In the above formula (A), R a1 ~R a10 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR a21 R a22 , or -OR a23 represents R a21 ~R a23 each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, an optionally substituted silyl group having 1 to 18 carbon atoms, an optionally substituted acyl group having 1 to 18 carbon atoms, or an optionally substituted methanesulfonyl group having 1 to 18 carbon atoms; Adjacent R a1 ~R a10 may be bonded to each other to form a ring, X a1 ~X a4Among these, adjacent two represent carbon atoms bonded to a group represented by the following formula (4), and the remaining are each independently CR a11 represents R a11 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR a24 R a25 , or -OR a26 represents R a24 ~R a26 each independently represents an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, an optionally substituted silyl group having 1 to 18 carbon atoms, an optionally substituted acyl group having 1 to 18 carbon atoms, or an optionally substituted methanesulfonyl group having 1 to 18 carbon atoms. [ka] In the above formula (4), R a12 ~R a15 each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR a21 R a22 , or -OR a23 represents Adjacent R a12 ~R a15 may be bonded to each other to form a ring, The carbon atom at the position * is X in the above formula (a). a1 ~X a4 The two adjacent carbon atoms represent the carbon atoms to which they are bonded. [ka] In the above formula (3), R a1 ~R a10 , and X a1 ~X a4 is R in the above formula (A) a1 ~R a10 , and X a1 ~X a4 is the same definition as

[0073] The compound represented by the above formula (A) is a compound having adjacent R a1 ~R a15 are preferably compounds in which the groups are not bonded to each other to form a ring.

[0074] In the above formula (A), R a1 ~R a15 each independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, an n-octadecyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, -NR a21 R a22 and -ORa23, R a21 ~R a23are each independently at least one group selected from the group consisting of a hydrogen atom, a benzyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, an optionally substituted trimethylsilyl group, an optionally substituted phenyldimethylsilyl group, an optionally substituted diphenylmethylsilyl group, an optionally substituted acetyl group, an optionally substituted benzoyl group, and an optionally substituted methanesulfonyl group.

[0075] In the above formula (A), R a5 ~R a15 are preferably all hydrogen atoms.

[0076] The above-mentioned pulverizer is not particularly limited, but is preferably at least one selected from the group consisting of a ball mill, a bead mill, a rod mill, a jet mill, and a rocking mill.

[0077] The alkali metal is not particularly limited, but is preferably at least one selected from the group consisting of lithium, sodium, and potassium.

[0078] The solvent is not particularly limited, but is preferably at least one selected from the group consisting of tetrahydrofuran, toluene, hexane, diethylene glycol dimethyl ether, 1,2-dimethoxyethane, diethyl ether, triethylamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, and N,N,N',N",N"-pentamethyldiethylenetriamine. Of these, tetrahydrofuran, diethylene glycol dimethyl ether, 1,2-dimethoxyethane, diethyl ether, and triethylamine are preferred from the viewpoint of improving the yield of the fused ring compound represented by formula (3).

[0079] From the viewpoint of improving the yield of the fused ring compound represented by formula (3), the amount of the solvent used is preferably more than 6.0 equivalents and not more than 20.0 equivalents relative to 1.0 equivalent of the compound represented by formula (A), more preferably 8.0 equivalents or more and 20.0 equivalents or less, and even more preferably 10.0 equivalents or more and 20.0 equivalents or less. [Example]

[0080] The present invention will be described in more detail below with reference to examples, but the present invention should not be construed as being limited to these examples.

[0081] <Synthesis Examples 1 to 10: Synthesis of Compound (A) by Dehydrocyclization Using Mechanochemical Method. Examination of the Amounts of Lithium and Solvent-Based Additives Used> [Synthesis Example 1] [ka] A 7 mm diameter stainless steel ball was placed in a 1.5 mL stainless steel container, and 132.2 mg (0.40 mmol, 1.00 eq) of compound (a) was weighed into it. Next, lithium wire (3.2 mm diameter, 99.9% purity) was washed with hexane in air to remove the mineral oil, cut with a knife, and weighed to a total of 16.7 mg (2.40 mmol, 6.0 eq) on an electronic balance and placed in the stainless steel container. 0.39 mL of dehydrated THF (specific gravity 0.889, 4.8 mmol, 12.0 eq) was weighed with a microsyringe and similarly placed in the stainless steel container. An O-shaped polyethylene packing was placed between the wire and the container, and the container was sealed with a stainless steel lid and attached to a mixer mill reactor (Retsch, MM400). A 7 mm diameter stainless steel ball was placed in a stainless steel vessel of the same weight, and the lid was closed with a polyethylene gasket. The vessel was then fixed as a counterpart to a mixer mill reactor. The two vessels were shaken and stirred at a frequency of 30 Hz (equivalent to 1800 rpm) at room temperature for 30 minutes. The black, wet, clay-like reaction mixture and the 0.25 M iodine THF solution were then thoroughly mixed. Water and saturated aqueous sodium thiosulfate were added to the resulting mixture in air. The mixture was then extracted three times with chloroform. The organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure using a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: chloroform:hexane = 1:9) to obtain compound (A) as a white solid. The amounts of compound (a) used as the substrate, Li, and THF used, and the yield are shown in Table 6.

[0082] [Synthesis Examples 2 to 5] Compound (A) was synthesized in the same manner as in Synthesis Example 1 of Compound (A), except that the amounts of Li and THF used in Synthesis Example 1 were changed to those shown in Table 6. The results are shown in Table 6.

[0083] [Synthesis Examples 6 and 8] Compound (A) was synthesized in the same manner as in Synthesis Example 1 of Compound (A), except that the amounts of substrate charged, Li, and THF used were changed to those shown in Table 6, the volume of the stainless steel solution was changed from 1.5 mL to 5.0 mL, the stainless steel ball with a diameter of 7 mm was changed to a stainless steel ball with a diameter of 9 mm, and the shaking stirring time was changed from 30 minutes to 1 hour. The results are shown in Table 6.

[0084] [Synthesis Example 7] Compound (A) was synthesized in the same manner as in Synthesis Example 1 of Compound (A), except that the amounts of substrate charged, Li, and THF used were changed to those shown in Table 6, the volume of the stainless steel solution was changed from 1.5 mL to 10 mL, the stainless steel ball with a diameter of 7 mm was changed to a stainless steel ball with a diameter of 9 mm, and the shaking stirring time was changed from 30 minutes to 1 hour. The results are shown in Table 6.

[0085] [Table 6]

[0086] As is clear from Table 6, in Synthesis Examples 1 to 4 (examination of the amount of lithium used), when the amount of lithium used was less than 4.5 equivalents, the yield decreased. Therefore, it is clear that 4.5 equivalents or more of lithium is preferable. Furthermore, from Synthesis Examples 1 and 5 (examination of the amount of THF used), it is clear that in order to synthesize compound (A), the reaction must be carried out in the presence of THF.

[0087] <Synthesis Examples 9 to 16: Examination of Solvent Types> [Synthesis Example 9] [ka] A 7 mm diameter stainless steel ball was placed in a 1.5 mL stainless steel container, and 82.6 mg (0.25 mmol, 1.00 eq) of compound (a) was weighed into it. Next, lithium wire (3.2 mm diameter, 99.9% purity) was washed with hexane in air to remove the mineral oil, cut with a knife, and weighed to a total of 10.4 mg (1.50 mmol, 6.0 eq) on an electronic balance and placed in the stainless steel container. 0.24 mL of dehydrated THF (specific gravity 0.889, 3.0 mmol, 12.0 eq) was weighed with a microsyringe as a solvent additive and similarly placed in the stainless steel container. An O-shaped polyethylene packing was placed between the container and the stainless steel lid was placed on top, and the container was then fixed to a mixer mill reactor (Retsch, MM400). A 7 mm diameter stainless steel ball was placed in a stainless steel container of the same weight, the lid was closed with a polyethylene gasket, and the container was fixed as a counterpart to the mixer mill reactor. The two reaction containers were shaken and stirred at a frequency of 30 Hz (equivalent to 1800 rpm) at room temperature for 30 minutes. The black, wet, clay-like reaction mixture and the 0.25 M iodine THF solution were then thoroughly mixed. Water and saturated aqueous sodium thiosulfate solution were added to the resulting mixed solution in air. The mixture was then extracted three times with chloroform, and the organic phase was dried over anhydrous sodium sulfate. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone was added to the organic layer and stirred at room temperature for 30 minutes. Saturated aqueous sodium thiosulfate solution was added to the solution, and the mixture was extracted three times with chloroform. The mixture was filtered, and the solvent was removed under reduced pressure using a rotary evaporator. The crude product obtained was analyzed using CH2Br2 as an internal standard. 1 The yield of compound (A) was calculated by HNMR analysis, and the results are shown in Table 7.

[0088] [Synthesis Examples 10-16] The yield of compound (A) was calculated in the same manner as in Synthesis Example 11, except that toluene, hexane, diethylene glycol dimethyl ether (diglyme), 1,2-dimethoxyethane (DME), diethyl ether (EtO), triethylamine (NEt), and ethylenediamine (EDA) were used instead of THF. The results are shown in Table 7.

[0089] [Table 7]

[0090] As is clear from Table 7, the yield decreased in Synthesis Examples 10 to 11 and 16, in which toluene, hexane, or EDA was used as the solvent. Therefore, it is clear that the solvent additive is preferably THF, diglyme, DME, Et2O, or NEt3.

[0091] <Synthesis Example 17: Synthesis of Compound (B) by Dehydrocyclization Using Mechanochemical Method> [Synthesis Example 17] [ka] A 7 mm diameter stainless steel ball was placed in a 5.0 mL stainless steel container, and 165.2 mg (0.50 mmol, 1.00 eq) of compound (a) was weighed into it. Next, lithium wire (3.2 mm diameter, 99.9% purity) was washed with hexane in air to remove the mineral oil, cut with a knife, and weighed to a total of 62.5 mg (9.0 mmol, 18.0 eq) on an electronic balance and placed in the stainless steel container. 0.24 mL (specific gravity 0.78, 3.27 mmol, 6.5 eq) of N,N,N',N'-tetramethylethylenediamine (TMEDA) was weighed with a microsyringe as a solvent additive and similarly placed in the stainless steel container. An O-shaped polyethylene gasket was placed between the wire and the stainless steel lid, and the container was then secured to a mixer mill reactor (Retsch MM400). A 7 mm diameter stainless steel ball was placed in a stainless steel container of the same weight, and the lid was closed with a polyethylene gasket. The container was then fixed as a mixer mill reactor counterpart. The two reaction containers were shaken at 30 Hz (equivalent to 1800 rpm) at room temperature for 1 hour. The black, wet, clay-like reaction mixture and 0.25 M iodine THF solution were then thoroughly mixed. Water and saturated aqueous sodium thiosulfate were added to the resulting mixture in air. The mixture was then extracted three times with chloroform, and the organic phase was dried over anhydrous sodium sulfate. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone was added to the organic layer and stirred at room temperature for 30 minutes. Saturated aqueous sodium thiosulfate was added to the solution, and the mixture was extracted three times with chloroform. The mixture was filtered, and the solvent was removed under reduced pressure using a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: chloroform:hexane = 1:9) to obtain compound (B) as a white solid in 86% yield.

[0092] <Comparative Synthesis Example 1: Synthesis of Compound (A) by Dehydrocyclization Using a Solution Method> [Comparative Synthesis Example 1] 66.1 mg (0.20 mmol, 1.0 eq) of compound (a) and 3.89 mL of dehydrated THF (specific gravity 0.889, 48.0 mmol, 240 eq) were weighed into a pressure vessel equipped with a magnetic stirrer. The pressure vessel was then degassed for 15 minutes. Next, lithium wire (3.2 mm diameter, 99.9% purity) was washed with hexane in air to remove the mineral oil, cut with a knife, and weighed on an electronic balance to a total of 41.6 mg (6.0 mmol, 30 eq) and added to the reaction mixture. The pressure vessel was sealed and the reaction was allowed to proceed at 25°C for 2 hours. The reaction mixture was then cannulated to obtain a solution with the lithium removed. The reaction solution and 4.0 mL of 0.25 M iodine in THF were thoroughly mixed. Water and saturated aqueous sodium thiosulfate solution were added to the resulting mixture in air. Subsequently, the mixture was subjected to liquid separation and extraction three times with chloroform, and the organic phase was dried with anhydrous sodium sulfate, filtered, and the solvent was distilled off under reduced pressure with a rotary evaporator. An attempt was made to calculate the yield of the obtained crude product in the same manner as in Synthesis Example 11, but the yield was too low to calculate.

[0093] <Synthesis Examples of Various Fused Ring Compounds> [Synthesis example I-1] [ka] A 7 mm diameter stainless steel ball was placed in a 1.5 mL stainless steel container, and 132.2 mg (0.400 mmol, 1.00 eq) of compound (a) was weighed into it. Next, lithium wire (3.2 mm diameter, 99.9% purity) was washed with hexane in air to remove the mineral oil, cut with a knife, and weighed to a total of 16.7 mg (2.4 mmol, 6.0 eq) on an electronic balance and placed in the stainless steel container. 0.39 mL of dehydrated THF (specific gravity 0.889, 12 eq) was weighed with a microsyringe and similarly placed in the stainless steel container. An O-shaped polyethylene packing was placed between the wire and the container, and the container was sealed with a stainless steel lid and attached to a mixer mill reactor (Retsch, MM400). A 7 mm diameter stainless steel ball was placed in a stainless steel vessel of equal weight, the lid was closed with a polyethylene gasket, and the vessel was fixed as a mixer mill reactor counterpart. The two vessels were shaken and stirred at 30 Hz for 30 minutes. The lid of the vessel was then opened, and the black, wet, clay-like reaction mixture and the 0.25 M iodine THF solution were thoroughly mixed. Water (5 mL) and saturated aqueous sodium thiosulfate (5 mL) were added to the resulting mixture in air. The mixture was then extracted three times with chloroform (30 mL). The organic phase containing compound (A) was dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure using a rotary evaporator. The resulting crude product was purified by silica gel column chromatography (eluent: chloroform:hexane = 1:9) to obtain 97.5 mg (0.296 mmol, 74% yield) of compound (A) as a white solid. 1 HNMR (400MHz, CDCl3): δ9.34(s,1H),9.16(s,1H),9.07(d,J=8.3Hz,1H)8.85-8.82(m,1H),8.60- 8.57(m,2H),8.15(d,J=6.7Hz,1H),8.08(d,J=7.1Hz,1H),8.04-8.01(m,2H),7.72-7.60(m,6H).

[0094] [Synthesis example I-2] [ka] A 7 mm diameter stainless steel ball was placed in a 5.0 mL stainless steel container, and 165.2 mg (0.500 mmol, 1.00 eq) of compound (a) was weighed into it. Next, lithium wire (3.2 mm diameter, 99.9% purity) was washed with hexane in air to remove the mineral oil, cut with a knife, and weighed to a total of 62.5 mg (9.0 mmol, 18.0 eq) on an electronic balance and placed in the stainless steel container. 0.24 mL of TMEDA (specific gravity 0.78, 6.5 eq) was weighed with a microsyringe and similarly placed in the stainless steel container. An O-shaped polyethylene packing was placed between the wire and the container, and the container was sealed with a stainless steel lid and attached to a mixer mill reactor (Retsch, MM400). A 7 mm diameter stainless steel ball was placed in a stainless steel container of the same weight, and the lid was closed with a polyethylene gasket. The container was then fixed as a mixer mill reactor counterpart. The two containers were shaken at 30 Hz at room temperature for 1 hour. The lid of the container was then opened, and the black, wet, clay-like reaction mixture and the 0.25 M iodine THF solution were thoroughly mixed. To the resulting mixture, water (5 mL) and saturated aqueous sodium thiosulfate (5 mL) were added in air. The mixture was then extracted three times with chloroform (30 mL), and the organic phase containing compound (B) was dried over anhydrous sodium sulfate. 681 mg (3.0 mmol) of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone was added to the organic layer and stirred at room temperature for 30 minutes. Saturated aqueous sodium thiosulfate was added to the solution, which was then extracted three times with chloroform. The mixture was then filtered, and the solvent was removed under reduced pressure using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (eluent: chloroform:hexane=1:9) to obtain 140.7 mg (0.428 mmol, 86% yield) of Compound (B) as a white solid. 1 HNMR (600MHz, CDCl3): δ9.18(s,2H),8.99(s,2H),8.70(dd,J=6.0Hz,3.6Hz,2H),8.11(dd,J=5.9 Hz,1.8Hz,2H),8.06(dd,J=6.0Hz,3.6Hz,2H),7.65(dd,J=6.0Hz,3.0Hz,2H),7.59-7.56(m,4H).

[0095] [Synthesis example I-3] [ka] A 7 mm diameter stainless steel ball was placed in a 1.5 mL stainless steel container, and 165.2 mg (0.500 mmol, 1.00 eq) of compound (c) was weighed into it. Next, lithium wire (3.2 mm diameter, 99.9% purity) was washed with hexane in air to remove the mineral oil, cut with a knife, and weighed to a total of 41.7 mg (6.0 mmol, 12.0 eq) on an electronic balance and placed in the stainless steel container. 0.49 mL of dehydrated THF (specific gravity 0.889, 12 eq) was weighed with a microsyringe and similarly placed in the stainless steel container. An O-shaped polyethylene packing was placed between the wire and the container, and the container was sealed with a stainless steel lid and attached to a mixer mill reactor (Retsch, MM400). A 7 mm diameter stainless steel ball was placed in a stainless steel container of the same weight, and the lid was closed with a polyethylene gasket. The container was then fixed as a mixer mill reactor counterpart. The two containers were shaken and stirred at 30 Hz for 1 hour. The lid of the container was then opened, and the black, wet, clay-like reaction mixture and the 0.25 M iodine THF solution were thoroughly mixed. To the resulting mixture, water (5 mL) and saturated aqueous sodium thiosulfate (5 mL) were added in air. The mixture was then extracted three times with chloroform (30 mL), and the organic phase containing compound (C) was dried over anhydrous sodium sulfate. 227 mg (1.0 mmol) of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone was added to the organic layer and stirred at room temperature for 30 minutes. Saturated aqueous sodium thiosulfate was added to the solution, which was then extracted three times with chloroform. The mixture was then filtered, and the solvent was removed under reduced pressure using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (eluent: chloroform:hexane=1:9) to obtain 82.7 mg (0.252 mmol, 50% yield) of Compound (C) as a white solid. 1HNMR (600MHz, CDCl3): δ9.15(s,1H),9.09(s,1H),8.91(d,J=8.4Hz,1H),8.84(d,J=8.4Hz,1H),8.81(d,J=7.8Hz,1H),8.7 6(d,J=9.0Hz,1H),8.14-8.12(m,2H),8.04(d,J=9.0Hz,1H),8.02(d,J=7.2Hz,1H),7.70(t,7.2Hz,1H),7.76-7.56(m,5H).

[0096] [Synthesis Example I-4]

change

[0097] [Synthesis Example I-5]

change

[0098] [Synthesis example I-6] [ka] Under atmospheric pressure, 391 mg (1.14 mmol, 1.00 eq) of compound (AB-11) and 15 mL of dichloromethane were added to a 50 mL two-neck flask, followed by 0.375 mL (4.65 mmol, 4.1 eq) of pyridine and 0.290 mL (1.69 mmol, 1.5 eq) of trifluoromethanesulfonic anhydride, and the mixture was stirred at room temperature for 15 minutes. After adding 1 M hydrochloric acid and stirring, the aqueous and organic layers were separated. The resulting organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate was stirred in methanol at 65 °C and then filtered to obtain 508 mg (1.07 mmol, 94% yield) of compound (AB-19) as a white solid. 1 HNMR (400MHz, CDCl3): δ9.32(s,1H),9.09(s,1H),9.04(d,J=8.3Hz,1H),8.87(d,J=9.1 Hz,1H),8.41-8.39(m,2H),8.15(d,J=7.9Hz,1H),8.10-8.04(m,3H),7.72-7.57(m,5H), 19 FNMR (400MHz, CDCl3): δ-72.5.

[0099] [Synthesis example I-7] [ka] Under a nitrogen atmosphere, 453 mg (0.950 mmol, 1.00 eq) of compound (AB-19), 324 mg (1.13 mmol, 1.20 eq) of 9-phenylcarbazole-3-boronic acid, 21.0 mg (0.094 mmol, 0.10 eq) of palladium(II) acetate, 51.0 mg (0.19 mmol, 0.20 eq) of triphenylphosphine, 524 mg (3.77 mmol, 4.00 eq) of potassium carbonate, 9 mL of toluene, and 1 mL of water were added to a 50 mL two-necked flask and stirred at 100°C for 21.5 hours. After cooling to room temperature, the reaction solution was added dropwise to hexane, and the solid was collected by filtration. The mixture was stirred in toluene at 110° C., cooled to room temperature, and then the solid was collected by filtration to obtain 368 mg (0.65 mmol, 68% yield) of compound (AB-54) as a pale yellow solid. 1 HNMR (400MHz, CDCl3): δ9.35(s,1H),9.20(s,1H),9.10(d,J=7.9Hz,1H),8.92(d,J=8.3Hz,1H),8.89(s,1H),8.74(d,J=9.1Hz,1H),8.58(d,J=1. 2Hz,1H), 8.30(d,J=7.5Hz,1H),8.17(d,J=7.9Hz,1H),8.11-8.05(m,4H),7.88(dd,J=8.3Hz,1.6Hz,1H),7.71-7.47(m,12H),7.38-7.34(m,1H).

[0100] [Synthesis example I-8] [ka] Under a nitrogen atmosphere, 300 mg (0.630 mmol, 1.00 eq) of compound (AB-19), 150 mg (0.76 mmol, 1.20 eq) of 2-biphenylboronic acid, 14.4 mg (0.064 mmol, 0.10 eq) of palladium(II) acetate, 33.5 mg (0.13 mmol, 0.20 eq) of triphenylphosphine, 351 mg (2.52 mmol, 4.00 eq) of potassium carbonate, 9 mL of toluene, and 1 mL of water were added to a 50 mL two-necked flask and stirred at 100 °C for 24 hours. After cooling to room temperature, the mixture was separated and extracted with ethyl acetate. The organic phase containing compound (AB-35) was dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (eluent: chloroform:hexane=1:9) to obtain 216 mg (0.45 mmol, 71% yield) of compound (AB-35) as a pale yellow solid. 1 HNMR(600MHz,DMSO-d6):δ9.39(s,1H),9.30(s,1H),9.00(d,J=8.9Hz,1H),8.80(d,J =8.9Hz,1H),8.53(s,1H),8.47(d,J=8.9Hz,1H),8.21(t,J=8.2Hz,2H),8.13(d,J=8. 2Hz,1H),8.08(d,J=8.9Hz,1H),7.75-7.61(m,5H),7.58-7.53(m,2H),7.51(dd,J=7. 2,1.7Hz,1H),7.43(dd,J=8.6,1.7Hz,1H),7.25-7.22(m,4H),7.17(t,J=3.4Hz,1H).

[0101] [Synthesis example I-9] [ka] Under a nitrogen atmosphere, 690 mg (1.45 mmol, 1.00 eq) of compound (AB-19), 434 mg (1.74 mmol, 1.20 eq) of 4-[(t-butoxycarbonyl)amino]phenylboronic acid, 32.6 mg (0.145 mmol, 0.10 eq) of palladium(II) acetate, 77.6 mg (0.29 mmol, 0.20 eq) of triphenylphosphine, 806 mg (5.80 mmol, 4.00 eq) of potassium carbonate, 18 mL of toluene, and 2 mL of water were placed in a 50 mL two-necked flask and stirred at 100°C for 1 hour. After cooling to room temperature, the solids in the solution were filtered off, and the solvent was removed under reduced pressure using a rotary evaporator. The obtained crude product was stirred in water, and then the solid was collected by filtration to obtain 748 mg (1.44 mmol, 99% yield) of compound (AB-31) as a gray solid. 1 HNMR(400MHz, CDCl3): δ9.34(s,1H),9.16(s,1H),9.08(d,J=8.3Hz,1H),8.87 (d,J=8.7Hz,1H),8.74(s,1H),8.66(d,J=8.7Hz,1H),8.16(d,J=7.1Hz,1H),8. 09(d,J=7.9Hz,1H),8.04(d,J=8.7Hz,2H),7.92(d,J=7.9Hz,1H),7.77(d,J=8 .7Hz, 2H), 7.68 (t, J=7.5Hz, 1H), 7.65-7.54 (m, 5H), 6.59 (s, 1H), 1.57 (s, 9H).

[0102] [Synthesis example I-10] [ka] Under a nitrogen atmosphere, 720 mg (1.39 mmol, 1.00 eq) of compound (AB-31), 12 mL of concentrated hydrochloric acid, and 23 mL of 1,4-dioxane were added to a Schlenk tube and stirred at 50°C for 3 hours. After cooling to room temperature, the precipitate was collected by filtration. The resulting crude material was stirred in 50 mL of THF, and 100 mL of aqueous sodium bicarbonate solution was added. After adding ethyl acetate and stirring, the aqueous and organic layers were separated. The resulting organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain 357 mg (0.85 mmol, 61% yield) of compound (AB-30) as a brown solid. 1 HNMR (400MHz, CDCl3): δ9.32(s,1H),9.15(s,1H),9.08(d,J=7.9Hz,1H),8.84(d,J=8.3Hz,1H),8.72(s,1H),8.66(d,J=9.1Hz,1H) ,8.15(d,J=7.5Hz,1H),8.08(d,J=7.5Hz,1H),8.04-8.02(m,2H),7.90(d,J=9.1Hz,1H),7.69-7.56(m,6H),6.87(d,J=7.9Hz,2H).

[0103] [Synthesis example I-11] [ka] Under a nitrogen atmosphere, 338 mg (0.806 mmol, 1.00 eq) of compound (AB-30), 459 mg (1.93 mmol, 2.40 eq) of 4-bromobiphenyl, 18.0 mg (0.081 mmol, 0.10 eq) of palladium(II) acetate, 33.1 mg (0.16 mmol, 0.20 eq) of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 185 mg (1.93 mmol, 2.40 eq) of sodium t-butoxide, and 10 mL of xylene were added to a 50 mL two-necked flask and stirred at 140°C for 7 hours. After cooling to room temperature, the reaction solution was added dropwise to hexane, and the solid was collected by filtration. After stirring in dichlorobenzene at 140°C, the mixture was passed through a small amount of silica gel, and the resulting solution was concentrated under reduced pressure to obtain 519 mg (0.72 mmol, 89% yield) of compound (AB-115) as a pale yellow solid. 1 HNMR(600MHz, CDCl3): δ9.34(s,1H),9.17(s,1H),9.08(d,J=9.0Hz,1H),8.8 8(d,J=9.0Hz,1H),8.78(s,1H),8.67(d,J=8.4Hz,1H),8.16(d,J=8.4Hz,1H) ,8.09(d,J=7.8Hz,1H),8.04(d,J=8.4Hz,2H),7.95(d,J=8.4Hz,1H),7.76(d ,J=8.4Hz,2H),8.76-8.56(m,12H),7.45(t,J=6.6Hz,4H),7.36-7.29(m,8H).

[0104] [Synthesis example I-12] [ka] Under a nitrogen atmosphere, 966 mg (2.03 mmol, 1.00 eq) of compound (AB-19), 2.4 mL (2.4 mmol, 1.18 eq) of lithium hexamethyldisilazide, 13.4 mg (0.060 mmol, 0.029 eq) of palladium(II) acetate, 24.1 mg (0.083 mmol, 0.041 eq) of tri-t-butylphosphonium tetrafluoroborate, and 10 mL of xylene were added to a 50 mL two-necked flask and stirred at 140 °C for 20 hours. After cooling to room temperature, 20 mL of 1 M hydrochloric acid was added and stirred at room temperature for 1 hour. The precipitated solid was filtered. The resulting solid was stirred in 40 mL of THF, and 40 mL of aqueous sodium bicarbonate solution was added. Ethyl acetate was added and stirred, and the aqueous and organic layers were separated. The resulting organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (eluent: chloroform:methanol=95:5) to obtain 327 mg (0.95 mmol, 47% yield) of compound (AB-75) as a brown solid. 1HNMR(600MHz,CDCl3):9.27(s,1H),9.06(d,J=8.9Hz,1H),8.98(s,1H),8.63(d,J=8.2Hz,1 H),8.45(d,J=8.2Hz,1H),8.09(d,J=8.2Hz,1H),8.04(d,J=8.2Hz,1H),8.01(d,J=7.6Hz,1 H),7.98(d,J=8.2Hz,1H),7.81(d,J=2.1Hz,1H),7.66(t,J=7.6Hz,1H),7.60(t,J=7.2Hz,1 H),7.57(t,J=6.9Hz,1H),7.52(t,J=7.6Hz,1H),7.10(dd,J=8.6,2.4Hz,1H),4.03(s,2H).

[0105] [Synthesis example I-13] [ka] Under a nitrogen atmosphere, 153 mg (0.444 mmol, 1.00 eq) of compound (AB-75), 255 mg (1.07 mmol, 2.40 eq) of 4-bromobiphenyl, 10.0 mg (0.045 mmol, 0.10 eq) of palladium(II) acetate, 36.3 mg (0.089 mmol, 0.20 eq) of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 105 mg (1.09 mmol, 2.40 eq) of sodium t-butoxide, and 5 mL of xylene were added to a Schlenk tube and stirred at 140 °C for 4 hours. After cooling to room temperature, the mixture was separated and extracted with ethyl acetate. The organic phase containing compound (AB-84) was dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography (eluent: ethyl acetate:hexane=1:9) to obtain 182 mg (0.28 mmol, 63% yield) of compound (AB-84) as a yellow solid. 1HNMR (600MHz, CDCl3): δ9.30(s,1H),9.07(d,J=8.9Hz,1H),9.04(s,1H),8. 70(d,J=8.2Hz,1H),8.37(s,1H),8.25(d,J=8.9Hz,1H),8.11(d,J=8.2Hz,1 H),8.07(d,J=8.2Hz,1H),7.98(d,J=8.2Hz,1H),7.90(d,J=8.2Hz,1H),7.6 8-7.56(m,12H),7.51(d,J=8.9Hz,1H),7.46(t,J=7.2Hz,4H),7.34(m,6H).

[0106] [Synthesis example I-14] [ka] Under a nitrogen atmosphere, 316 mg (0.921 mmol, 1.00 eq) of compound (AB-75), 694 mg (2.24 mmol, 2.40 eq) of 4-bromo-p-terphenyl, 10.6 mg (0.047 mmol, 0.050 eq) of palladium(II) acetate, 38.1 mg (0.093 mmol, 0.10 eq) of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 216 mg (2.25 mmol, 2.40 eq) of sodium t-butoxide, and 10 mL of xylene were added to a 50 mL two-necked flask and stirred at 140°C for 12 hours. After cooling to room temperature, the reaction solution was added dropwise to hexane, and the solid was collected by filtration. The obtained solid was stirred in chlorobenzene at 140° C., then cooled to room temperature, and filtered to obtain 493 mg (0.62 mmol, 67% yield) of compound (AB-90) as a yellow solid. 1HNMR(600MHz,CDCl3):δ9.32(s,1H),9.29(s,1H),9.05(d,J=8.2Hz,1H),8.94(d,J=8.2Hz,1 H),8.39(s,1H),8.34(d,J=8.9Hz,1H),8.23(d,J=8.2Hz,1H),8.18(d,J=8.2Hz,1H),8.08(d ,J=8.2Hz,1H),8.05(d,J=8.2Hz,1H),7.80-7.74(m,13H),7.71(d,J=7.6Hz,4H),7.64(m,3H ),7.55(d,J=8.9Hz,1H),7.48(t,J=7.9Hz,4H),7.37(t,J=7.9Hz,2H),7.34(d,J=8.9Hz,4H).

[0107] [Comparative Example 1] Compound (X1) represented by the following formula was used as Comparative Example 1. Compound (X1) was synthesized according to the method disclosed in JP 2019-034939 A. [ka]

[0108] <Element Examples> [Element Example 1: Preparation of a photoelectric conversion element for an imaging element using compound (AB-54)] As shown in FIG. 1, a photoelectric conversion element 100 for an imaging device was fabricated, having a layered structure consisting of a substrate 1, a lower 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 an upper electrode 7, and the external quantum efficiency and responsiveness of the photoelectric conversion element were evaluated.

[0109] (Preparing substrate 1 and bottom electrode 2) A glass substrate with an indium-tin oxide (ITO) transparent electrode, patterned with a 2 mm wide stripe of ITO (110 nm thick), was prepared as a substrate with a lower electrode on its surface. The substrate was then cleaned with isopropyl alcohol and then subjected to surface treatment using ozone and ultraviolet light.

[0110] (Preparation for vacuum deposition) After cleaning, each layer was deposited on the surface-treated substrate by vacuum deposition using a vacuum deposition method, and each layer was laminated. First, the glass substrate was placed in a vacuum deposition chamber. -5 The pressure was reduced to 100 Pa. Then, each layer was formed in the following order according to the film formation conditions.

[0111] (Preparation of Electron Transport Layer (Hole Blocking Layer) 3) The sublimation-purified compound 4,6-bis(3,5-di(pyridin-4-yl)phenyl)-2-methylpyrimidine was deposited at a rate of 0.10 nm / sec to form a 10 nm film, thereby forming an electron transport layer (hole blocking layer) 3 .

[0112] (Fabrication of Photoelectric Conversion Layer 4) A 120 nm film was formed by mixing N,N-dimethylquinacridone and C60 in a mass ratio of 4:1 to produce photoelectric conversion layer 4. The film formation rate was 0.15 nm / second.

[0113] (Fabrication of Hole Transport Layer (Electron Blocking Layer) 5) The sublimation-purified compound (PA-4) was formed into a film of 10 nm at a rate of 0.10 nm / second to form a hole transport layer 5.

[0114] (Fabrication of Buffer Layer 6) A buffer layer 6 was prepared by depositing a 10 nm film of the sublimation-purified compound 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN) at a rate of 0.10 nm / sec.

[0115] (Fabrication of upper electrode 7) Finally, a metal mask was placed perpendicular to the ITO stripes on the substrate, and the upper electrode 7 was formed. Specifically, a silver film was formed to a thickness of 80 nm at a rate of 0.1 nm / sec to form the upper electrode 7.

[0116] As a result, the area of ​​4mm shown in Figure 1 2 The photoelectric conversion element 100 for an imaging device was fabricated. The film thickness of each film was measured using a stylus film thickness measuring instrument (DEKTAK, manufactured by Bruker).

[0117] The device was then sealed in a nitrogen atmosphere glove box with an oxygen and moisture concentration of 1 ppm or less by sealing the glass sealing cap and the film-formed substrate (device) with bisphenol F epoxy resin (manufactured by Nagase ChemteX Corporation).

[0118] The external quantum efficiency and response time (responsivity) were evaluated when a voltage of 2.6 V was applied to the image sensor fabricated as described above. The external quantum efficiency was measured using a solar cell spectral response measurement device (manufactured by Soma Optical Co., Ltd.). The wavelength of the irradiated light was 560 nm, and the intensity was 50 μW / cm. 2 The response time was measured by irradiating a light pulse and measuring the time it took for the current value to return to the value before irradiation.

[0119] [Element Example 2, Element Comparative Example 1] Photoelectric conversion elements for imaging devices of Device Example 2 and Device Comparative Example 1 were prepared in the same manner as Device Example 1, except that compound (AB-115) and comparative compound (X), respectively, were used instead of compound (AB-54) in the preparation of hole transport layer (electron blocking layer) 5 of Device Example 1. The external quantum efficiency and response time were measured in the same manner as Device Example 1. The results are shown in Table 8. In Table 8, the external quantum efficiency and response time of element examples 1 to 3 are relative values ​​when the external quantum efficiency and response time of element comparative example 1 are set to a reference value (1.0). A higher external quantum efficiency value indicates better performance, and a lower response time value indicates better performance.

[0120] [Table 8]

[0121] As can be seen from Table 8, the photoelectric conversion element material for an imaging device containing the Example compound of the present application according to one embodiment of the present invention had a higher external quantum efficiency and was superior in responsiveness than the photoelectric conversion element material containing the Comparative Example compound. As with Device Example 2, the compound (AB-90) synthesized in Synthesis Example also showed suppression of dark current and improvement of external quantum efficiency. [Explanation of symbols]

[0122] 1 board 2 Lower electrode 3 Electron transport layer (hole blocking layer) 4 Photoelectric conversion layer 5. Hole transport layer (electron blocking layer) 6 Buffer layer 7 Upper electrode 100 Photoelectric conversion element

Claims

1. A material for a photoelectric conversion element, comprising a fused ring compound represented by the following formula (1): 【Chemical 1】 In the above formula (1), R １ ~R １０ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR ２１ R ２２ , or -OR ２３ represents R ２１ ~R ２３ each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, an optionally substituted silyl group having 1 to 18 carbon atoms, an optionally substituted acyl group having 1 to 18 carbon atoms, or an optionally substituted methanesulfonyl group having 1 to 18 carbon atoms, Adjacent R １ ~R １０ may be bonded to each other to form a ring, X １ ~X ４ Among these, adjacent two represent carbon atoms bonded to a group represented by the following formula (2), and the remaining are each independently C—R １１ represents R １１ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR ２４ R ２５ , or -OR ２６ represents R ２４ ~R ２６ each independently represents an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, an optionally substituted silyl group having 1 to 18 carbon atoms, an optionally substituted acyl group having 1 to 18 carbon atoms, or an optionally substituted methanesulfonyl group having 1 to 18 carbon atoms. However, in the above formula (1), R １ ~R １０ at least one of the above alkyl group having 1 to 18 carbon atoms which may be substituted, the above aromatic hydrocarbon group having 6 to 30 carbon atoms which may be substituted, the above heteroaromatic group having 3 to 30 carbon atoms which may be substituted, and the above —NR ２１ R ２２ represents a group having at least one substituent selected from the group consisting of: 【Chemistry 2】 In the above formula (2), R １２ ~R １５ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR ２１ R ２２ , or -OR ２３ represents Adjacent R １２ ~R １５ may be bonded to each other to form a ring, The carbon atom at the position * is X in the above formula (1). １ ~X ４ Two adjacent ones of these represent the carbon atoms to which they are bonded.

2. In the above formula (1), adjacent R １ ~R １５ The material for a photoelectric conversion element according to claim 1 , wherein are not bonded to each other to form a ring.

3. In the above formula (1), R １ ~R １５ each independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, an n-octadecyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, -NR ２１ R ２２ , and -OR ２３ is at least one group selected from the group consisting of R ２１ ~R ２３ are each independently at least one group selected from the group consisting of a hydrogen atom, a benzyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, an optionally substituted trimethylsilyl group, an optionally substituted phenyldimethylsilyl group, an optionally substituted diphenylmethylsilyl group, an optionally substituted acetyl group, an optionally substituted benzoyl group, and an optionally substituted methanesulfonyl group.

4. In the above formula (1), R ５ ~R １５ The material for a photoelectric conversion element according to claim 1 , wherein all of are hydrogen atoms.

5. The material for a photoelectric conversion element according to claim 1 , which is a material for a photoelectric conversion element for an imaging element.

6. The material for a photoelectric conversion element according to claim 1 , which is a hole transport material for a photoelectric conversion element for an imaging element or an electron blocking material for a photoelectric conversion element for an imaging element.

7. A fused ring compound represented by the following formula (5): 【Chemistry 3】 In the above formula (5), R ｂ１ ~R ｂ１０ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR ｂ２１ R ｂ２２ , or -OR ｂ２３ represents R ｂ２１ ~R ｂ２３ each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, an optionally substituted silyl group having 1 to 18 carbon atoms, an optionally substituted acyl group having 1 to 18 carbon atoms, or an optionally substituted methanesulfonyl group having 1 to 18 carbon atoms, Adjacent R ｂ１ ~R ｂ１０ may be bonded to each other to form a ring, X ｂ１ ~X ｂ４ Among these, adjacent two represent carbon atoms bonded to a group represented by the following formula (6), and the remaining are each independently C—R ｂ１１ represents R ｂ１１ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR ｂ２４ R ｂ２５ , or -OR ｂ２６ represents R ｂ２４ ~R ｂ２６ each independently represents an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, an optionally substituted silyl group having 1 to 18 carbon atoms, an optionally substituted acyl group having 1 to 18 carbon atoms, or an optionally substituted methanesulfonyl group having 1 to 18 carbon atoms. However, in the above formula (5), R ｂ１ ~R ｂ１０ at least one of the above alkyl group having 1 to 18 carbon atoms which may be substituted, the above aromatic hydrocarbon group having 6 to 30 carbon atoms which may be substituted, the above heteroaromatic group having 3 to 30 carbon atoms which may be substituted, and the above —NR ｂ２１ R ｂ２２ is a group having at least one substituent selected from the following: 【Chemistry 4】 In the above formula (6), R ｂ１２ ~R ｂ１５ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR ｂ２１ R ｂ２２ , or -OR ｂ２３ represents Adjacent R ｂ１２ ~R ｂ１５ may be bonded to each other to form a ring, The carbon atom at the position * is X in the above formula (5). ｂ１ ~X ｂ４ Two adjacent ones of these represent the carbon atoms to which they are bonded.

8. The fused ring compound according to claim 7, wherein the fused ring compound represented by the formula (5) is represented by the following formula (7A) or formula (7B): 【Chemistry 5】 In the above formula (7A) and formula (7B), R ｂ１ ~R ｂ１０ is R in the above formula (5). ｂ１ ~Rb １０ has the same definition as R ｂ１１ are each independently R in the above formula (5). ａ１１ has the same definition as R ｂ１２ ~R ｂ１５ is R in the above formula (6) ａ１２ ~R ａ１５ is the same definition as

9. The fused ring compound represented by the above formula (7A) or (7B) is ｂ１ ~R ｂ１５ The fused ring compound according to claim 8 , wherein are not bonded to each other to form a ring.

10. In the above formulas (7A) and (7B), R ｂ１ ~R ｂ１５ each independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, an n-octadecyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, -NR ｂ２１ R ｂ２２ , and -OR ｂ２３ is at least one group selected from the group consisting of R ｂ２１ ~R ｂ２３ are each independently at least one group selected from the group consisting of a hydrogen atom, a benzyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, an optionally substituted trimethylsilyl group, an optionally substituted phenyldimethylsilyl group, an optionally substituted diphenylmethylsilyl group, an optionally substituted acetyl group, an optionally substituted benzoyl group, and an optionally substituted methanesulfonyl group.

11. In the above formula (7A) and formula (7B), R ｂ５ ~R ｂ１５ The fused ring compound according to claim 8 , wherein all of are hydrogen atoms.

12. An organic thin film comprising the material for photoelectric conversion devices according to any one of claims 1 to 6, or the material for photoelectric conversion devices containing the fused ring compound according to any one of claims 7 to 11.

13. A photoelectric conversion device comprising the material for photoelectric conversion devices according to any one of claims 1 to 6, or the material for photoelectric conversion devices containing the fused ring compound according to any one of claims 7 to 11.

14. A photoelectric conversion element for an imaging device, comprising the material for a photoelectric conversion element according to any one of claims 1 to 6, or the material for a photoelectric conversion element containing the fused ring compound according to any one of claims 7 to 11.

15. A method for producing a fused ring compound represented by the following formula (3), comprising mixing a compound represented by the following formula (A) with an alkali metal using a grinder in the presence of a solvent, and carrying out intramolecular cyclization by a mechanochemical reaction. 【Chemistry 6】 In the above formula (A), R ａ１ ~R ａ１０ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR ａ２１ R ａ２２ , or -OR ａ２３ represents R ａ２１ ~R ａ２３ each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, an optionally substituted silyl group having 1 to 18 carbon atoms, an optionally substituted acyl group having 1 to 18 carbon atoms, or an optionally substituted methanesulfonyl group having 1 to 18 carbon atoms, Adjacent R ａ１ ~R ａ１０ may be bonded to each other to form a ring, X ａ１ ~X ａ４ Among these, adjacent two represent carbon atoms bonded to a group represented by the following formula (4), and the remaining are each independently C—R ａ１１ represents R ａ１１ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR ａ２４ R ａ２５ , or -OR ａ２６ represents R ａ２４ ~R ａ２６ each independently represents an optionally substituted alkyl group having 1 to 18 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, an optionally substituted silyl group having 1 to 18 carbon atoms, an optionally substituted acyl group having 1 to 18 carbon atoms, or an optionally substituted methanesulfonyl group having 1 to 18 carbon atoms. 【Chemistry 7】 In the above formula (4), R ａ１２ ~R ａ１５ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 30 carbon atoms, an optionally substituted heteroaromatic group having 3 to 30 carbon atoms, -NR ａ２１ R ａ２２ , or -OR ａ２３ represents Adjacent R ａ１２ ~R ａ１５ may be bonded to each other to form a ring, The carbon atom at the position * is X in the above formula (a). ａ１ ~X ａ４ Two adjacent ones of these represent the carbon atoms to which they are bonded. 【Chemistry 8】 In the above formula (3), R ａ１ ~R ａ１０ , and X ａ１ ~X ａ４ is R in the above formula (A). ａ１ ~R ａ１０ , and X ａ１ ~X ａ４ is the same definition as

16. The compound represented by the formula (A) has adjacent R ａ１ ~R ａ１５ The method for producing a fused ring compound according to claim 15 , wherein are not bonded to each other to form a ring.

17. In the above formula (A), R ａ１ ~R ａ１５ each independently represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, an n-octadecyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, -NR ａ２１ R ａ２２ and —ORa23, and at least one group selected from the group consisting of —ORa23, R ａ２１ ~R ａ２３ are each independently at least one group selected from the group consisting of a hydrogen atom, a benzyl group, an adamantyl group, a diamantyl group, an optionally substituted phenyl group, an optionally substituted biphenylyl group, an optionally substituted terphenylyl group, an optionally substituted naphthyl group, an optionally substituted fluorenyl group, an optionally substituted spirobifluorenyl group, an optionally substituted benzofluorenyl group, an optionally substituted phenanthryl group, an optionally substituted fluoranthenyl group, an optionally substituted triphenylenyl group, an optionally substituted anthryl group, an optionally substituted pyrenyl group, an optionally substituted carbazolyl group, an optionally substituted dibenzofuranyl group, an optionally substituted dibenzothienyl group, an optionally substituted trimethylsilyl group, an optionally substituted phenyldimethylsilyl group, an optionally substituted diphenylmethylsilyl group, an optionally substituted acetyl group, an optionally substituted benzoyl group, and an optionally substituted methanesulfonyl group.

18. In the above formula (A), R ａ５ ~R ａ１５ The method for producing a fused ring compound according to claim 15, wherein all of are hydrogen atoms.

19. The method for producing a fused ring compound according to claim 15, wherein the pulverizer is at least one selected from the group consisting of a ball mill, a bead mill, a rod mill, a jet mill, and a rocking mill.

20. The method for producing a fused ring compound according to claim 15, wherein the alkali metal is at least one selected from the group consisting of lithium, sodium, and potassium.

21. The method according to claim 15 or 16, wherein the solvent is at least one selected from the group consisting of tetrahydrofuran, diethylene glycol dimethyl ether, 1,2-dimethoxyethane, diethyl ether, triethylamine, and N,N,N',N'-tetramethylethylenediamine.

Images