Photoelectric conversion element material, organic thin film, photoelectric conversion element, and fused ring compound

Abstract

This invention provides materials for photoelectric conversion elements, which facilitate the fabrication of photoelectric conversion elements with low dark current, high external quantum efficiency, and excellent responsiveness. This invention uses photoelectric conversion element materials containing a fused-ring compound represented by the following formula (1). In formula (1), ring A represents the structure represented by the following formula (2); R 1 ~R 8 Each of the following groups independently represents a hydrogen atom, an alkyl group with 1 to 18 carbon atoms (with or without substitution), an alkenyl group with 1 to 18 carbon atoms, a cycloalkyl group with 1 to 18 carbon atoms, a bicycloalkyl group with 1 to 18 carbon atoms, a tricycloalkyl group with 1 to 20 carbon atoms, an aromatic hydrocarbon group with 6 to 30 carbon atoms (with or without substitution), a heteroaryl group with 3 to 30 carbon atoms (with or without substitution), or -NR. 21 R 22 OR 23 .

Description

Technical Field

[0001] This invention relates to materials for photoelectric conversion elements, organic thin films, photoelectric conversion elements, and fused ring compounds. Background Technology

[0002] Photoelectric conversion elements for imaging are used in mobile phones, cameras, and other applications, and their development is actively underway.

[0003] In recent years, the market demand for photoelectric conversion elements used in camera components has been increasing, seeking materials that excel in any of the following areas: dark current, external quantum efficiency, and response speed. Under these circumstances, the possibility of using various polycyclic compounds as the core material for new materials continues to be explored and researched. As a polycyclic compound, Patent Document 1 discloses derivatives with benzothiophene and benzothiophene as the core material. In addition to benzothiophene and benzothiophene, Patent Document 2 discloses several other core materials. Patent Document 3 discloses unsubstituted dibenzo[g, p]π.

[0004] Existing technical documents Patent documents Patent Document 1: International Publication No. 2015 / 163349 Patent Document 2: International Publication No. 2020 / 022421 Patent Document 3: Japanese Patent Application Publication No. 2010-258438 Summary of the Invention

[0005] The problem that the invention aims to solve One objective of this invention is to propose a material for a photoelectric conversion element and a photoelectric conversion element using a compound having such a new core, while continuously exploring and researching the possibility of using various polycyclic compounds as the parent core of new materials.

[0006] Another objective of this invention is to provide a material for photoelectric conversion devices that facilitates the fabrication of photoelectric conversion devices with low dark current, high external quantum efficiency, and excellent responsiveness, and further to provide a compound that facilitates the fabrication of photoelectric conversion devices with low dark current, high external quantum efficiency, and excellent responsiveness.

[0007] Furthermore, Patent Document 3 describes the use of unsubstituted dibenzo[g,p]ₓ as a crystalline layer between the photoelectric conversion layer and the upper electrode. However, Patent Document 3 makes no mention of the molecular structure characteristics of dibenzo[g,p]ₓ or the amorphous film containing dibenzo[g,p]ₓ. Additionally, the dibenzo[g,p]ₓ described in Patent Document 3 does not provide any insights into improving the performance of photoelectric conversion elements for imaging sensors.

[0008] Technical solutions for solving the problem The inventors discovered that the above-mentioned problems could be solved by using specific fused-ring compounds, thus completing the present invention.

[0009] The present invention relates to materials for photoelectric conversion elements, organic thin films, photoelectric conversion elements, and fused ring compounds.

[0010] [1] A material for a photoelectric conversion element, comprising a fused-ring compound represented by the following formula (1), [Chemical Formula 1]

[0011] In equation (1), Ring A represents the structure represented by the following equation (2); R 1 ~R 8 Each of the following groups independently represents a hydrogen atom, an alkyl group with 1 to 18 carbon atoms (with or without substitution), an alkenyl group with 1 to 18 carbon atoms, a cycloalkyl group with 1 to 18 carbon atoms, a bicycloalkyl group with 1 to 18 carbon atoms, a tricycloalkyl group with 1 to 20 carbon atoms, an aromatic hydrocarbon group with 6 to 30 carbon atoms (with or without substitution), a heteroaryl group with 3 to 30 carbon atoms (with or without substitution), or -NR. 21 R 22 or -OR 23 ; R 21 ~R 23 Each can be independently represented as an alkyl group with 1 to 18 carbon atoms that are substituted or not, an aromatic hydrocarbon group with 6 to 30 carbon atoms that are substituted or not, or a heteroaryl group with 3 to 30 carbon atoms that are substituted or not. R 1 ~R 8 They can bond together to form a ring; Among them, R 1 ~R 4 At least one of them is an alkyl group having 1 to 18 carbon atoms (selected or unsubstituted), an aromatic hydrocarbon group having 6 to 30 carbon atoms (selected or unsubstituted), a heteroaryl group having 3 to 30 carbon atoms (selected or unsubstituted), and -NR. 21 R 22 The group of the donor substituent; [Chemical Formula 2]

[0012] In equation (2), X 1 ~X 4 The two adjacent atoms in the symbol represent carbon atoms shared with ring B, and the rest represent CR. 15 ; R 11 ~R15 Each of the following groups independently represents a hydrogen atom, an alkyl group with 1 to 18 carbon atoms (with or without substitution), an alkenyl group with 1 to 18 carbon atoms, a cycloalkyl group with 1 to 18 carbon atoms, a bicycloalkyl group with 1 to 18 carbon atoms, a tricycloalkyl group with 1 to 20 carbon atoms, an aromatic hydrocarbon group with 6 to 30 carbon atoms (with or without substitution), a heteroaryl group with 3 to 30 carbon atoms (with or without substitution), or -NR. 24 R 25 or -OR 26 ; R 24 ~R 26 Each can be independently represented as an alkyl group with 1 to 18 carbon atoms that are substituted or not, an aromatic hydrocarbon group with 6 to 30 carbon atoms that are substituted or not, or a heteroaryl group with 3 to 30 carbon atoms that are substituted or not. R A It represents an aromatic hydrocarbon group with 6 to 30 carbon atoms that are substituted or not, or a heteroaryl group with 3 to 30 carbon atoms that are substituted or not. L represents an alkylene group with 1 to 18 carbon atoms, a divalent aromatic hydrocarbon group with 6 to 30 carbon atoms (with or without substitution), a divalent heteroaryl group with 3 to 30 carbon atoms (with or without substitution), or a single bond.

[0013] [2] According to the material for photoelectric conversion elements described in [1], wherein R 1 ~R 8 Any two adjacent elements in the ring are bonded together to form a ring represented by the following equation (3). [Chemical Formula 3]

[0014] In equation (3), R 31 ~R 34 Each of the following groups independently represents a hydrogen atom, an alkyl group with 1 to 18 carbon atoms (with or without substitution), an alkenyl group with 1 to 18 carbon atoms, a cycloalkyl group with 1 to 18 carbon atoms, a bicycloalkyl group with 1 to 18 carbon atoms, a tricycloalkyl group with 1 to 20 carbon atoms, an aromatic hydrocarbon group with 6 to 30 carbon atoms (with or without substitution), a heteroaryl group with 3 to 30 carbon atoms (with or without substitution), or -NR. 21 R 22 or -OR 23 ; Adjacent R 31 ~R 34 They can bond together to form a ring; The carbon atom represents R 1 ~R 8 The carbon atoms in the 6-membered aromatic ring of the formula (1) that are bonded to any two adjacent carbon atoms.

[0015] [3] The material for photoelectric conversion elements according to [1] or [2], wherein the fused ring compound represented by formula (1) is a fused ring compound represented by formula (1A) or (1B) below. [Chemical Formula 4]

[0016] In equations (1A) and (1B), rings A and R 1 ~R 8 and R 31 ~R 34 Represents the rings A and R in equations (1) and (3). 1 ~R 8 and R 31 ~R 34 Same group.

[0017] [4] The material for photoelectric conversion element according to [1] or [2], wherein the fused ring compound represented by formula (1) is a fused ring compound represented by any of the following formulas (1C) to (1E). [Chemical Formula 5]

[0018] In equations (1C) to (1E), R 1 ~R 8 R 11 ~R 15 R A And L represents R in relation to equations (1) and (2). 1 ~R 8 R 11 ~R 15 R A and the same groups as L; Among them, it has an alkyl group selected from 1 to 18 carbon atoms (with or without substitution), an aromatic hydrocarbon group selected from 6 to 30 carbon atoms (with or without substitution), a heteroaryl group selected from 3 to 30 carbon atoms (with or without substitution), and -NR. 21 R 22 The donor substituent group in it is R. 1 ~R 4 At least one of them, or R 5 ~R 8 At least one of them.

[0019] [5] The material for the photoelectric conversion element according to any one of [2] to [4], wherein R 1 With R 2 R 3 With R 4 R5 With R 6 Or R 7 With R 8 Any one of the groups in the equation bonds to each other to form a ring represented by the equation (3).

[0020] [6] According to the photoelectric conversion element material described in [3], wherein ring A in the fused ring compound represented by formula (1) represents a structure represented by formula (2A) or (2B) below. [Chemical Formula 6]

[0021] In equations (2A) and (2B), X 1 ~X 3 This indicates the carbon atom shared with ring B. R 11 ~R 15 R A And L represents R in equation (2). 11 ~R 15 R A And the same group as L.

[0022] [7] The photoelectric conversion element material according to [2], [3], [5] or [6], wherein the fused ring compound represented by formula (1) is a fused ring compound represented by the following formula (1F), [Chemical Formula 7]

[0023] In equation (1F), R 35 ~R 38 Each of the following groups independently represents a hydrogen atom, an alkyl group with 1 to 18 carbon atoms (with or without substitution), an alkenyl group with 1 to 18 carbon atoms, a cycloalkyl group with 1 to 18 carbon atoms, a bicycloalkyl group with 1 to 18 carbon atoms, a tricycloalkyl group with 1 to 20 carbon atoms, an aromatic hydrocarbon group with 6 to 30 carbon atoms (with or without substitution), a heteroaryl group with 3 to 30 carbon atoms (with or without substitution), or -NR. 21 R 22 or -OR 23 ; Adjacent R 35 ~R 38 They can bond together to form a ring; R 1 ~R 4 R 11 ~R 15 R 31 ~R 34 R AAnd L represents R in relation to equations (1) and (3). 1 ~R 4 R 11 ~R 15 R 31 ~R 34 R A And the same group as L.

[0024] [8] According to the material for photoelectric conversion elements described in [7], wherein adjacent R 1 ~R 4 and R 31 ~R 38 They do not bond with each other to form rings.

[0025] [9] The material for photoelectric conversion element according to [7] or [8], wherein L is a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted terphenylene, a substituted or unsubstituted naphthylene, or a single bond.

[0026]

[10] The material for the photoelectric conversion element according to any one of [7] to [9], wherein R 1 ~R 4 R 11 ~R 15 R 31 ~R 38 and R A Each of the following is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, n-octyl, n-decyl, n-dodecyl, n-octadecyl, adamantyl, dimadamantyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirodifluorenyl, substituted or unsubstituted benzo[a]fluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluoranyl, substituted or unsubstituted triphenylene, substituted or unsubstituted anthrayl, substituted or unsubstituted pyrene, substituted or unsubstituted carbazole, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophene, -NR 21 R 22 or -OR 23 The groups that make up the group; R 21 ~R 23Each group is independently selected from the group consisting of hydrogen atom, adamantyl, diadamantyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirodifluorenyl, substituted or unsubstituted benzo[a]fluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluoranyl, substituted or unsubstituted triphenylene, substituted or unsubstituted anthracene, substituted or unsubstituted pyrene, substituted or unsubstituted carbazole, substituted or unsubstituted dibenzofuranyl, and substituted or unsubstituted dibenzothiophene.

[0027]

[11] The material for the photoelectric conversion element according to any one of [7] to

[10] , wherein R 31 ~R 38 It is a hydrogen atom.

[0028]

[12] An organic thin film comprising any one of the photoelectric conversion element materials described in [1] to

[11] .

[0029]

[13] A photoelectric conversion element comprising the material for photoelectric conversion element described in any one of [1] to

[11] .

[0030]

[14] A photoelectric conversion element comprising, in the photoelectric conversion layer, any one of [1] to

[11] as the material for photoelectric conversion element.

[0031]

[15] A photoelectric conversion element comprising, in a hole transport layer or an electron blocking layer, any one of the photoelectric conversion element materials described in [1] to

[11] .

[0032]

[16] The photoelectric conversion element material according to any one of [1] to

[11] is used in a photoelectric conversion element for a camera element.

[0033]

[17] A fused-ring compound, represented by the following formula (4), [Chemical Formula 8]

[0034] In equation (4), Ring A represents the structure represented by the following equation (5); R a1 ~R a8 Each of the following groups independently represents a hydrogen atom, an alkyl group with 1 to 18 carbon atoms (with or without substitution), an alkenyl group with 1 to 18 carbon atoms, a cycloalkyl group with 1 to 18 carbon atoms, a bicycloalkyl group with 1 to 18 carbon atoms, a tricycloalkyl group with 1 to 20 carbon atoms, an aromatic hydrocarbon group with 6 to 30 carbon atoms (with or without substitution), a heteroaryl group with 3 to 30 carbon atoms (with or without substitution), or -NR. a21 Ra22 or -OR a23 ; R a21 ~R a23 Each of the following can be independently represented: an alkyl group with 1 to 18 carbon atoms that are substituted or not; an aromatic hydrocarbon group with 6 to 30 carbon atoms that are substituted or not; or a heteroaryl group with 3 to 30 carbon atoms that are substituted or not. R a1 ~R a8 They can bond together to form a ring; Among them, R a1 ~R a4 At least one of them is an alkyl group having 1 to 18 carbon atoms (selected or unsubstituted), an aromatic hydrocarbon group having 6 to 30 carbon atoms (selected or unsubstituted), a heteroaryl group having 3 to 30 carbon atoms (selected or unsubstituted), and -NR. a21 R a22 The group of the donor substituent; R a1 ~R a8 Any two adjacent elements in the middle bond together to form a ring represented by the following equation (6); [Chemical Formula 9]

[0035] In equation (5), X a1 ~X a4 The two adjacent atoms in the symbol represent carbon atoms shared with ring B, and the rest represent CR. a15 ; R a11 ~R a15 Each of the following groups independently represents a hydrogen atom, an alkyl group with 1 to 18 carbon atoms (with or without substitution), an alkenyl group with 1 to 18 carbon atoms, a cycloalkyl group with 1 to 18 carbon atoms, a bicycloalkyl group with 1 to 18 carbon atoms, a tricycloalkyl group with 1 to 20 carbon atoms, an aromatic hydrocarbon group with 6 to 30 carbon atoms (with or without substitution), a heteroaryl group with 3 to 30 carbon atoms (with or without substitution), or -NR. a24 R a25 or -OR a26 ; R a24 ~R a26 Each of the following can be independently represented: an alkyl group with 1 to 18 carbon atoms that are substituted or not; an aromatic hydrocarbon group with 6 to 30 carbon atoms that are substituted or not; or a heteroaryl group with 3 to 30 carbon atoms that are substituted or not. R aA It represents an aromatic hydrocarbon group with 6 to 30 carbon atoms that are substituted or not, or a heteroaryl group with 3 to 30 carbon atoms that are substituted or not. La It represents an alkylene group with 1 to 18 carbon atoms, a divalent aromatic hydrocarbon group with 6 to 30 carbon atoms (with or without substitution), a divalent heteroaryl group with 3 to 30 carbon atoms (with or without substitution), or a single bond; [Chemical Formula 10]

[0036] In equation (6), R a31 ~R a34 Each of the following groups independently represents a hydrogen atom, an alkyl group with 1 to 18 carbon atoms (with or without substitution), an alkenyl group with 1 to 18 carbon atoms, a cycloalkyl group with 1 to 18 carbon atoms, a bicycloalkyl group with 1 to 18 carbon atoms, a tricycloalkyl group with 1 to 20 carbon atoms, an aromatic hydrocarbon group with 6 to 30 carbon atoms (with or without substitution), a heteroaryl group with 3 to 30 carbon atoms (with or without substitution), or -NR. a21 R a22 or -OR a23 ; Adjacent R a31 ~R a34 They can bond together to form a ring; The carbon atom represents R a1 ~R a8 The carbon atoms in the 6-membered aromatic ring of the formula (4) that are bonded to any two adjacent carbon atoms.

[0037]

[18] According to

[17] , the fused-ring compound represented by formula (4) is represented by formula (4A) or (4B) below. [Chemical Formula 11]

[0038] In equations (4A) and (4B), rings A and R a1 ~R a8 and R a31 ~R a34 Represents the rings A and R in equations (4) and (6). a1 ~R a8 and R a31 ~R a34 Same group.

[0039]

[19] According to

[17] or

[18] , the fused ring compound, wherein ring A represents a structure represented by the following formula (5A) or (5B), [Chemical Formula 12]

[0040] In equations (5A) and (5B), X a1 ~X a3 This indicates the carbon atom shared with ring B. R a11 ~R a15 R aA and L a R represents the expression in equation (5). a11 ~R a15 R aA and L a Same group.

[0041]

[20] According to

[18] or

[19] , the fused-ring compound represented by the formula (4A) or (4B) is represented by the following formula (4C). [Chemical Formula 13]

[0042] In equation (4C), R a35 ~R a38 Each of the following groups independently represents a hydrogen atom, an alkyl group with 1 to 18 carbon atoms (with or without substitution), an alkenyl group with 1 to 18 carbon atoms, a cycloalkyl group with 1 to 18 carbon atoms, a bicycloalkyl group with 1 to 18 carbon atoms, a tricycloalkyl group with 1 to 20 carbon atoms, an aromatic hydrocarbon group with 6 to 30 carbon atoms (with or without substitution), a heteroaryl group with 3 to 30 carbon atoms (with or without substitution), or -NR. a21 R a22 or -OR a23 ; Adjacent R a35 ~R a38 They can bond together to form a ring; R a1 ~R a4 R a11 ~R a15 R a31 ~R a34 R aA and L a R represents the expression in equations (4) and (6). a1 ~R a4 R a11 ~R a15 R a31 ~R a34 R aA and L a Same group.

[0043]

[21] According to the fused ring compound of

[20] , wherein, in the fused ring compound represented by the formula (4C), adjacent R a1 ~Ra4 and R a31 ~R a38 They do not bond with each other to form rings.

[0044]

[22] According to the fused ring compound of

[20] or

[21] , wherein L a It can be a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted terphenylene, a substituted or unsubstituted naphthylene, or a single bond.

[0045]

[23] The fused-ring compound according to any one of

[20] to

[22] , wherein R a1 ~R a4 R a11 ~R a15 R a31 ~R a38 and R aA Each of the following is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, n-octyl, n-decyl, n-dodecyl, n-octadecyl, adamantyl, dimadamantyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirodifluorenyl, substituted or unsubstituted benzo[a]fluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluoranyl, substituted or unsubstituted triphenylene, substituted or unsubstituted anthrayl, substituted or unsubstituted pyrene, substituted or unsubstituted carbazole, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophene, -NR a21 R a22 or -OR a23 The groups that make up the group; R a21 ~R a23 Each group is independently selected from the group consisting of hydrogen atom, adamantyl, diadamantyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirodifluorenyl, substituted or unsubstituted benzo[a]fluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluoranyl, substituted or unsubstituted triphenylene, substituted or unsubstituted anthracene, substituted or unsubstituted pyrene, substituted or unsubstituted carbazole, substituted or unsubstituted dibenzofuranyl, and substituted or unsubstituted dibenzothiophene.

[0046]

[24] The fused ring compound according to any one of

[20] to

[23] , wherein R a31 ~R a38 It is a hydrogen atom.

[0047] Invention Effects According to one aspect of the present invention, a material for photoelectric conversion elements that facilitates the fabrication of photoelectric conversion elements with low dark current, high external quantum efficiency, and excellent responsiveness can be provided, and a compound that facilitates the fabrication of photoelectric conversion elements with low dark current, high external quantum efficiency, and excellent responsiveness can also be provided. Attached Figure Description

[0048] Figure 1 This is a schematic cross-sectional view showing an example of a stacked structure of a camera element photoelectric conversion element incorporating materials for a camera element photoelectric conversion element according to one aspect of the present invention. Detailed Implementation

[0049] The following describes in detail the materials used in the photoelectric conversion element according to one aspect of the present invention.

[0050] Materials for photoelectric conversion elements Fused ring compounds represented by the following formula (1) are suitable for use as materials for photoelectric conversion elements.

[0051] That is, the material for the photoelectric conversion element according to one aspect of this disclosure comprises a fused ring compound represented by the following formula (1), [Chemical Formula 14]

[0052] In equation (1), Ring A represents the structure represented by the following equation (2); R 1 ~R 8 Each of the following can be independently represented: hydrogen atom, alkyl group with 1-18 substituted carbon atoms, alkenyl group with 1-18 carbon atoms, cycloalkyl group with 1-18 carbon atoms, bicycloalkyl group with 1-18 carbon atoms, tricycloalkyl group with 1-20 carbon atoms, aromatic hydrocarbon group with 6-30 substituted carbon atoms, heteroaryl group with 3-30 substituted carbon atoms, -NR 21 R 22 or -OR 23 ; R 21 ~R 23 Each can be independently represented as an alkyl group with 1 to 18 carbon atoms that can be substituted, an aromatic hydrocarbon group with 6 to 30 carbon atoms that can be substituted, or a heteroaryl group with 3 to 30 carbon atoms that can be substituted; R 1 ~R 8 They can bond together to form a ring; Among them, R 1 ~R 4At least one of them is an alkyl group having 1 to 18 substituted carbon atoms, an aromatic hydrocarbon group having 6 to 30 substituted carbon atoms, a heteroaryl group having 3 to 30 substituted carbon atoms, and -NR. 21 R 22 The group of the donor substituent; [Chemical Formula 15]

[0053] In equation (2), X 1 ~X 4 The two adjacent atoms in the symbol represent carbon atoms shared with ring B, and the rest represent CR. 15 ; R 11 ~R 15 Each of the following can be independently represented: hydrogen atom, alkyl group with 1-18 substituted carbon atoms, alkenyl group with 1-18 carbon atoms, cycloalkyl group with 1-18 carbon atoms, bicycloalkyl group with 1-18 carbon atoms, tricycloalkyl group with 1-20 carbon atoms, aromatic hydrocarbon group with 6-30 substituted carbon atoms, heteroaryl group with 3-30 substituted carbon atoms, -NR 24 R 25 or -OR 26 ; R 24 ~R 26 Each can be independently represented as an alkyl group with 1 to 18 carbon atoms that can be substituted, an aromatic hydrocarbon group with 6 to 30 carbon atoms that can be substituted, or a heteroaryl group with 3 to 30 carbon atoms that can be substituted; R A It represents an aromatic hydrocarbon group with 6 to 30 carbon atoms that can be substituted, or a heteroaryl group with 3 to 30 carbon atoms that can be substituted; L represents an alkylene group with 1 to 18 carbon atoms, a divalent aromatic hydrocarbon group with 6 to 30 carbon atoms that can be substituted, a divalent heteroaryl group with 3 to 30 carbon atoms that can be substituted, or a single bond.

[0054] In the above formula (1), the structure represented by the above formula (2) is ring A, and a group having the above-mentioned donor substituent is provided. Thus, the photoelectric conversion element material containing the compound represented by the above formula (1) can provide a photoelectric conversion element with low dark current, high external quantum efficiency and excellent responsiveness. Therefore, the compound represented by the above formula (1) is suitable for use as a material for photoelectric conversion elements.

[0055] Specific examples and preferred methods of the definitions in equations (1) and (2) above are shown below.

[0056] <R 1 ~R8 > As R 1 ~R 8 Alkyl groups having 1 to 18 carbon atoms that can be substituted include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-nonyl, cyclohexyl, octyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, n-tridecyl, n-tetradecyl, 2-ethylhexyl, 3-ethylheptyl, 3-ethyldecyl, 2-hexyldecyl, cyclopentyl, cyclohexyl, cycloheptyl, etc.

[0057] As R 1 ~R 8 Examples of alkenyl groups with 1 to 18 carbon atoms include: vinyl, propenyl, butenyl, 2-methylpropenyl, n-pentenyl, 2-methylbutenyl, n-hexenyl, 2-methylpentenyl, n-heptenyl, n-octenyl, 2-ethylhexenyl, n-nonenyl, 2-ethylheptenyl, n-decenyl, n-dodecenyl, cyclopenten-1-yl, cyclohexen-1-yl, cyclohepten-1-yl, etc.

[0058] As R 1 ~R 8 Examples of cycloalkyl groups having 1 to 18 carbon atoms include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, and cyclododecyl. This cycloalkyl group can be substituted with an alkyl group having 1 to 4 carbon atoms. Examples of alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, cyclopropylmethyl, 2-methylpropyl, 2,2-dimethylpropyl, cyclopropyl, tert-butyl, and cyclobutyl.

[0059] As R 1 ~R 8 Examples of bicyclic alkyl groups having 1 to 18 carbon atoms include, for example, norbornyl, 3-pinel, bicyclo[3.1.0]hexyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl-2-yl, etc.

[0060] As R 1 ~R 8 Examples of tricyclic alkyl groups with 1 to 20 carbon atoms include, for example, adamantyl, noradamantyl, and diadamantyl.

[0061] As R 1 ~R 8Examples of substituted aromatic hydrocarbon groups with 6 to 30 carbon atoms include: substituted phenyl, substituted biphenyl, substituted terphenyl, substituted naphthyl, substituted anthracene, substituted phenanthryl, substituted pyrene, substituted phenyl, substituted benzo[g, p] ...

[0062] As R 1 ~R 8 Examples of substituted heteroaryl groups with 3 to 30 carbon atoms include: substituted dibenzofuranyl, substituted dibenzothiophenyl, substituted carbazoyl, substituted dibenzofuranylphenyl, substituted dibenzothiophenylphenyl, substituted carbazoylphenyl, substituted pyrroleyl, substituted thiophenyl, substituted furanyl, substituted imidazoyl, substituted pyrazolyl, substituted thiazoyl, substituted isothiazolyl, substituted oxazolyl, substituted isoxazolyl, substituted pyridyl, substituted phenylpyridyl, substituted pyridylphenyl, substituted pyrimidinyl, substituted pyrazinyl, substituted 1,3,5-triazinyl, substituted 1,3,5-triazinylphenyl, substituted 1,3,5-triazinylbiphenyl, and substituted 4,6-diphenyl-1,3,5-triazinyl. 5-Triazinyl, substituted indolyl, substituted benzothiopheneyl, substituted benzofuranyl, substituted benzimidazolyl, substituted indazoleyl, substituted benzothiazolyl, substituted benzoisothiazolyl, substituted 2,1,3-benzothiadiazolyl, substituted benzoxazolyl, substituted benzoisothiazolyl, substituted 2,1,3-benzoxadiazolyl, substituted quinolinyl, substituted isoquinolinyl, substituted quinoxolinyl, substituted quinazolinyl, substituted carbazolyl, substituted 9-phenylcarbazolyl, substituted 9-(4-biphenyl)carbazolyl, substituted dibenzothiopheneyl, substituted dibenzofuranyl, substituted phenoxazinyl, substituted phenthiazinyl, substituted phenazinyl, substituted thiaanthrayl, etc.

[0063] As R 21 ~R 23Alkyl groups having 1 to 18 carbon atoms that can be substituted include: those that are R as mentioned above. 1 ~R 8 It can be replaced by alkyl groups with 1 to 18 carbon atoms.

[0064] As R 21 ~R 23 Aromatic hydrocarbon groups with 6 to 30 carbon atoms that can be substituted include: those that are R as mentioned above. 1 ~R 8 It can be replaced by aromatic hydrocarbon groups with 6 to 30 carbon atoms that are identical to the substituted group.

[0065] As R 21 ~R 23 Examples of heteroaryl groups with 3 to 30 carbon atoms that can be substituted include: those that are R as mentioned above. 1 ~R 8 It can be replaced by heteroaryl groups with 3 to 30 carbon atoms.

[0066] <R 11 ~R 15 > As R 11 ~R 15 Alkyl groups having 1 to 18 carbon atoms that can be substituted include: those that are R as mentioned above. 1 ~R 8 It can be replaced by alkyl groups with 1 to 18 carbon atoms.

[0067] As R 11 ~R 15 Alkenes with 1 to 18 carbon atoms can be exemplified by: those that are R as mentioned above. 1 ~R 8 A group with the same alkenyl group having 1 to 18 carbon atoms.

[0068] As R 11 ~R 15 Cycloalkyl groups having 1 to 18 carbon atoms can be exemplified by: those that are R as mentioned above. 1 ~R 8 The same group as the cycloalkyl group with 1 to 18 carbon atoms.

[0069] As R 11 ~R 15 Bicyclic alkyl groups having 1 to 18 carbon atoms can be exemplified by: those that are R as mentioned above. 1 ~R 8 It consists of bicyclic alkyl groups with 1 to 18 carbon atoms.

[0070] As R 11 ~R 15Tricyclic alkyl groups having 1 to 20 carbon atoms can be exemplified by: those that are R as mentioned above. 1 ~R 8 It consists of tricyclic alkyl groups with 1 to 20 carbon atoms.

[0071] As R 11 ~R 15 Aromatic hydrocarbon groups with 6 to 30 carbon atoms that can be substituted include: those that are R as mentioned above. 1 ~R 8 It can be replaced by aromatic hydrocarbon groups with 6 to 30 carbon atoms that are identical to the substituted group.

[0072] As R 11 ~R 15 Examples of heteroaryl groups with 3 to 30 carbon atoms that can be substituted include: those that are R as mentioned above. 1 ~R 8 It can be replaced by heteroaryl groups with 3 to 30 carbon atoms.

[0073] As R 24 ~R 26 Alkyl groups having 1 to 18 carbon atoms that can be substituted include: those that are R as mentioned above. 1 ~R 8 It can be replaced by alkyl groups with 1 to 18 carbon atoms.

[0074] As R 24 ~R 26 Aromatic hydrocarbon groups with 6 to 30 carbon atoms that can be substituted include: those that are R as mentioned above. 1 ~R 8 It can be replaced by aromatic hydrocarbon groups with 6 to 30 carbon atoms that are identical to the substituted group.

[0075] As R 24 ~R 26 Examples of heteroaryl groups with 3 to 30 carbon atoms that can be substituted include: those that are R as mentioned above. 1 ~R 8 It can be replaced by heteroaryl groups with 3 to 30 carbon atoms.

[0076] <R A > As R A Aromatic hydrocarbon groups with 6 to 30 carbon atoms that can be substituted include: those that are R as mentioned above. 1 ~R 8 It can be replaced by aromatic hydrocarbon groups with 6 to 30 carbon atoms that are identical to the substituted group.

[0077] As R AExamples of heteroaryl groups with 3 to 30 carbon atoms that can be substituted include: those that are R as mentioned above. 1 ~R 8 It can be replaced by heteroaryl groups with 3 to 30 carbon atoms.

[0078] <l> Examples of alkylene groups with 1 to 18 carbon atoms in the L group include, for example, methylene, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, etc.

[0079] Examples of divalent aromatic hydrocarbon groups with 6 to 30 carbon atoms that can be substituted as L include: phenylene, biphenylene, terphenylene, naphthylene, phenylnaphthyl-diyl, binaphthyl, fluorene-diyl, benzo[a]fluorene-diyl, dibenzo[a]fluorene-diyl, phenanthrene-diyl, fluoranthene-diyl, anthracene-diyl, β-diyl, pyrene-diyl, triphenylene-diyl, perylene-diyl, etc.

[0080] Examples of divalent heteroaryl groups with 3 to 30 carbon atoms that can be substituted as L include, for example, pyrrole-diyl, thiophene-diyl, furan-diyl, imidazole-diyl, thiazole-diyl, isothiazole-diyl, oxazole-diyl, isoxazole-diyl, pyridine-diyl, pyrazin-diyl, triazine-diyl, indole-diyl, benzothiophene-diyl, benzofuran-diyl, benzimidazole-diyl, benzothiazole-diyl, benzoisothiazole-diyl, 2,1,3-benzothiadiazole-diyl, benzooxazole-diyl, benzoisothiazole-diyl, 2,1 ,3-benzoxadiazole-diyl, thienothiophene-diyl, dithienothiophene-diyl, benzodithiophene-diyl, quinoline-diyl, isoquinoline-diyl, quinoxaline-diyl, phenanthroline-diyl, dibenzothiophene-diyl, benzothiophene-diyl, dibenzofuran-diyl, carbazole-diyl, phenoxazine-diyl, phenthiazine-diyl, thiathane-diyl, phenylthiophene-diyl, diphenylthiophene-diyl, phenylfuran-diyl, diphenylfuran-diyl, bithiophene-diyl, trithiophene-diyl, phenylpyridine-diyl, bipyridine-diyl, etc.

[0081] In the above formula (1), preferably, R 1 ~R 8 Any two adjacent elements are bonded together to form a ring represented by the following equation (3).

[0082] [Chemical Formula 16]

[0083] In equation (3), R 31 ~R 34 Each of the following can be independently represented: hydrogen atom, alkyl group with 1-18 substituted carbon atoms, alkenyl group with 1-18 carbon atoms, cycloalkyl group with 1-18 carbon atoms, bicycloalkyl group with 1-18 carbon atoms, tricycloalkyl group with 1-20 carbon atoms, aromatic hydrocarbon group with 6-30 substituted carbon atoms, heteroaryl group with 3-30 substituted carbon atoms, -NR 21 R 22 or -OR 23 ; Adjacent R 31 ~R 34 They can bond together to form a ring; The carbon atom represents R 1 ~R 8 The carbon atoms in the 6-membered aromatic ring of the formula (1) that are bonded to any two adjacent carbon atoms.

[0084] The preferred method of the definition in the above formula (3) is shown below.

[0085] <R 31 ~R 34 > As R 31 ~R 34 Alkyl groups having 1 to 18 carbon atoms that can be substituted include: those that are R as mentioned above. 1 ~R 8 It can be replaced by alkyl groups with 1 to 18 carbon atoms.

[0086] As R 31 ~R 34 Alkenes with 1 to 18 carbon atoms can be exemplified by: those that are R as mentioned above. 1 ~R 8 A group with the same alkenyl group having 1 to 18 carbon atoms.

[0087] As R 31 ~R 34 Cycloalkyl groups having 1 to 18 carbon atoms can be exemplified by: those that are R as mentioned above. 1 ~R 8 The same group as the cycloalkyl group with 1 to 18 carbon atoms.

[0088] As R 31 ~R 34 Bicyclic alkyl groups having 1 to 18 carbon atoms can be exemplified by: those that are R as mentioned above. 1 ~R 8 It consists of bicyclic alkyl groups with 1 to 18 carbon atoms.

[0089] As R 31 ~R 34 Tricyclic alkyl groups having 1 to 20 carbon atoms can be exemplified by: those that are R as mentioned above. 1 ~R 8 It consists of tricyclic alkyl groups with 1 to 20 carbon atoms.

[0090] As R 31 ~R 34 Aromatic hydrocarbon groups with 6 to 30 carbon atoms that can be substituted include: those that are R as mentioned above. 1 ~R 8 It can be replaced by aromatic hydrocarbon groups with 6 to 30 carbon atoms that are identical to the substituted group.

[0091] As R 31 ~R 34 Examples of heteroaryl groups with 3 to 30 carbon atoms that can be substituted include: those that are R as mentioned above. 1 ~R 8 It can be replaced by heteroaryl groups with 3 to 30 carbon atoms.

[0092] Preferably, the fused-ring compound represented by formula (1) is a fused-ring compound represented by formula (1A) or (1B) below.

[0093] [Chemical Formula 17]

[0094] In equations (1A) and (1B), rings A and R 1 ~R 8 and R 31 ~R 34 Represents the rings A and R in equations (1) and (3). 1 ~R 8 and R 31 ~R 34 Same group.

[0095] Preferably, the fused ring compound represented by formula (1) is a fused ring compound represented by any of the following formulas (1C) to (1E).

[0096] [Chemical Formula 18]

[0097] In equations (1C) to (1E), R 1 ~R 8 R 11 ~R 15 R A And L represents R in relation to equations (1) and (2). 1 ~R 8 R 11 ~R 15 R A and the same groups as L; It comprises an alkyl group selected from 1 to 18 substituted carbon atoms, an aromatic hydrocarbon group selected from 6 to 30 substituted carbon atoms, a heteroaryl group selected from 3 to 30 substituted carbon atoms, and -NR. 21 R 22 The donor substituent group in it is R. 1 ~R 4 At least one of them, or R 5 ~R 8 At least one of them.

[0098] In the fused-ring compounds represented by formulas (1C) to (1E) above, preferably, R 1 With R 2 R 3 With R 4 R 5 With R 6 Or R 7 With R 8 Any one of the groups in the equation bonds to each other to form a ring represented by the equation (3).

[0099] In the fused-ring compounds represented by formulas (1), (1A), and (1B) above, preferably, ring A represents a structure represented by formula (2A) or (2B) below. [Chemical Formula 19]

[0100] In equations (2A) and (2B), X 1 ~X 3 This indicates the carbon atom shared with ring B. R 11 ~R 15 R A And L represents R in equation (2). 11 ~R 15 R A And the same group as L.

[0101] Preferably, the fused-ring compound represented by formula (1) is a fused-ring compound represented by the following formula (1F).

[0102] [Chemical Formula 20]

[0103] In equation (1F), R 35 ~R 38 Each of the following can be independently represented: hydrogen atom, alkyl group with 1-18 substituted carbon atoms, alkenyl group with 1-18 carbon atoms, cycloalkyl group with 1-18 carbon atoms, bicycloalkyl group with 1-18 carbon atoms, tricycloalkyl group with 1-20 carbon atoms, aromatic hydrocarbon group with 6-30 substituted carbon atoms, heteroaryl group with 3-30 substituted carbon atoms, -NR 21 R 22 or -OR 23 ; Adjacent R 35 ~R 38 They can bond together to form a ring; R 1 ~R 4 R 11 ~R 15 R 31 ~R 34 R A And L represents R in relation to equations (1) and (3). 1 ~R 4 R 11 ~R 15 R 31 ~R 34 R A And the same group as L.

[0104] In the fused-ring compound represented by the above formula (1F), preferably, adjacent R 1 ~R 4 and R 31 ~R 38 They do not bond with each other to form rings.

[0105] In the fused-ring compound represented by the above formula (1F), preferably, L is a substituted phenylene, a substituted biphenylene, a substituted terphenylene, a substituted naphthylene, or a single bond.

[0106] In the fused-ring compound represented by the above formula (1F), preferably, R 1 ~R 4 R 11 ~R 15 R 31 ~R 38 and R A Each of the following can be independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, n-octyl, n-decyl, n-dodecyl, n-octadecyl, adamantyl, dimadamantyl, substituted phenyl, substituted biphenyl, substituted terphenyl, substituted naphthyl, substituted fluorenyl, substituted spirodifluorenyl, substituted benzo[a]fluorenyl, substituted phenanthryl, substituted fluoranyl, substituted triphenylene, substituted anthraquinone, substituted pyrene, substituted carbazole, substituted dibenzofuranyl, substituted dibenzothiophene, -NR 21 R 22 or -OR 23 The groups that make up the group; R 21 ~R 23 Each of the following groups is independently selected from the group consisting of hydrogen atom, adamantyl, diadamantyl, substituted phenyl, substituted biphenyl, substituted terphenyl, substituted naphthyl, substituted fluorenyl, substituted spirodifluorenyl, substituted benzofluorenyl, substituted phenanthryl, substituted fluoranyl, substituted triphenylene, substituted anthracene, substituted pyrene, substituted carbazolyl, substituted dibenzofuranyl, and substituted dibenzothiophene.

[0107] In the fused-ring compound represented by the above formula (1F), preferably, R 31 ~R 38 It is a hydrogen atom.

[0108] <Physical Properties of Fused-Ring Compounds> The preferred physical properties of the fused ring compound represented by formula (1) will be described below.

[0109] (HOMO value) The HOMO value of the fused ring compound represented by formula (1) is not particularly limited, but from the perspective of suitability for photoelectric conversion elements, it is preferably 5.0 to 6.5 eV. It should be noted that this HOMO value is obtained by measuring the vapor-deposited film using an atmospheric photoelectron yield spectrometer.

[0110] (band gap) The band gap of the fused ring compound represented by formula (1) is not particularly limited, but from the perspective of suitability for photoelectric conversion elements, it is preferably 2.5 to 4.0 eV. It should be noted that this band gap is a value obtained from the wavelength end of the absorption spectrum of the vapor-deposited film.

[0111] (LUMO value) The LUMO value of the fused ring compound represented by formula (1) is not particularly limited, but from the perspective of suitability for photoelectric conversion devices, it is preferably 2.0 to 3.5 eV. It should be noted that this LUMO value is obtained from the above-mentioned HOMO value and band gap.

[0112] (Glass transition temperature) The glass transition temperature of the fused ring compound represented by formula (1) is not particularly limited, but from the perspective of suitability for photoelectric conversion elements, it is preferably 130°C or higher. It should be noted that this glass transition temperature is a value obtained by differential scanning calorimetry.

[0113] (Molecular weight) The molecular weight of the fused ring compound represented by formula (1) is not particularly limited, but from the perspective of heat resistance stability during sublimation, it is preferably 600 or more and less than 1000.

[0114] <Specific examples of fused-ring compounds> Hereinafter, preferred compounds are given for fused-ring compounds represented by formula (1), but the fused-ring compounds are not limited to these compounds.

[0115] <Specific Examples of Preferred Fused-Ring Compounds> Hereinafter, preferred compounds are given for the fused-ring compounds represented by formula (1), but the fused-ring compounds are not limited to these compounds.

[0116] Compounds whose substituent R in the skeletons (Aa) to (Ej) shown in Tables 1 to 3 is a group n selected from the groups shown in Tables 4 to 6 are defined as (Lm-n).

[0117] Here, Lm represents any symbol from Aa to Ej, and n represents any integer from 1 to 115. For example, the compound (Ab-2) represents a skeleton having (Ab) and the substituent R of the skeleton being methyl.

[0118] [Table 1]

[0119] [Table 2]

[0120] [Table 3]

[0121] [Table 4]

[0122] [Table 5]

[0123] [Table 6]

[0124] Applications of materials used in photoelectric conversion elements The aforementioned materials for photoelectric conversion elements are suitable, for example, for use as materials for photoelectric conversion elements in imaging elements. Preferably, these are charge transport materials or charge blocking materials for photoelectric conversion elements in imaging elements. Preferably, these are hole transport materials for photoelectric conversion elements in imaging elements. Preferably, these are electron blocking materials for photoelectric conversion elements in imaging elements.

[0125] The aforementioned materials for photoelectric conversion elements are also suitable for use as materials for organic electronic components. Examples of organic electronic components include organic electroluminescent elements and organic photoelectric conversion elements. Examples of materials for organic electronic components include materials for organic electroluminescent elements and materials for organic photoelectric conversion elements. The aforementioned materials for organic electronic components are preferably used as organic thin films.

[0126] Preferred embodiments of a photoelectric conversion element material comprising the aforementioned fused ring compound include: an organic thin film comprising the photoelectric conversion element material, a photoelectric conversion element comprising the photoelectric conversion element material, a photoelectric conversion element comprising the photoelectric conversion element material in a photoelectric conversion layer, and a photoelectric conversion element comprising the photoelectric conversion element material in a hole transport layer or an electron blocking layer.

[0127] The following description, as an example, illustrates the photoelectric conversion element used in this embodiment for imaging.

[0128] <Photoelectric conversion element for camera components> The photoelectric conversion element for the camera element in this embodiment includes the aforementioned charge transport material for the photoelectric conversion element for the camera element.

[0129] There are no particular limitations on the structure of the photoelectric conversion element used in the camera element, and examples include the following (i) to (v).

[0130] (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 It should be noted that the buffer layer can be replaced with a layer with other names or functions as needed. Examples of layers with other names or functions include: hole injection layer, work function adjustment layer, etc.

[0131] Preferred layer structures for photoelectric conversion elements used in imaging devices include, for example, an upper electrode, a lower electrode, a photoelectric conversion layer, and a hole transport layer, wherein 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.

[0132] Other preferred layer structures for photoelectric conversion elements used in imaging elements include, for example, an upper electrode, a lower electrode, a photoelectric conversion layer, a hole transport layer, and a buffer layer, wherein 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 is adjacent to the hole transport layer.

[0133] The photoelectric conversion element for an image sensor preferably includes the aforementioned photoelectric conversion element material in at least one layer selected from the group consisting of an electron transport layer (hole blocking layer), a photoelectric conversion layer, a hole transport layer (electron blocking layer), and a buffer layer. Furthermore, the photoelectric conversion element for an image sensor preferably includes the aforementioned photoelectric conversion element material in the photoelectric conversion layer and / or the hole transport layer (electron blocking layer), and more preferably, it includes the aforementioned photoelectric conversion element material in the hole transport layer (electron blocking layer). It should be noted that the photoelectric conversion element material for an image sensor may be included in multiple layers of the photoelectric conversion element for an image sensor.

[0134] The following will use the structure (v) above as an example, referring to... Figure 1 The photoelectric conversion element for the camera element involved in this embodiment will be described in more detail. Figure 1 This is a schematic cross-sectional view showing an example of a stacked structure of a camera element photoelectric conversion element including a hole transport material or an electron blocking material for a camera element photoelectric conversion element as described in this embodiment.

[0135] Figure 1 The photoelectric conversion element 100 for the camera element sequentially comprises 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. It should be noted that in this embodiment, some of these layers may be omitted, or other layers may be added.

[0136] In the photoelectric conversion element 100 for an imaging element, light enters from below the transparent lower electrode 2. Furthermore, a voltage is applied to the photoelectric conversion element 100, causing electrons in the charges (holes and electrons) generated in the photoelectric conversion layer 4 to move to the lower electrode 2, and holes to move to the upper electrode 7. That is, the photoelectric conversion element 100 uses the lower electrode 2 as an electron collecting electrode and the upper electrode 7 as a hole collecting electrode.

[0137] [Layer containing charge transport material for photoelectric conversion elements of camera components] The photoelectric conversion element 100 for an imaging element includes a photoelectric conversion element material 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. Preferably, the photoelectric conversion element 100 includes a charge transport material or a charge blocking material in the photoelectric conversion layer 4 and / or the hole transport layer (electron blocking layer) 5; more preferably, it includes a charge transport material or a charge blocking material in the hole transport layer (electron blocking layer) 5. It should be noted that the charge transport material or the charge blocking material may be included in multiple layers of the photoelectric conversion element 100.

[0138] The following describes a camera element photoelectric conversion element 100, which includes a hole transport layer (electron blocking layer) 5 containing a hole transport material for a camera element photoelectric conversion element or an electron blocking material for a camera element photoelectric conversion element.

[0139] [Substrate 1] There are no particular limitations on the substrate, and examples include glass plates, quartz plates, and plastic plates. In the case where light is incident from the side of substrate 1, substrate 1 preferably has high transmittance for the wavelength of light (e.g., transmittance of 80% or more, preferably 90% or more).

[0140] [Lower Electrode 2] A lower electrode 2 is provided on the substrate 1.

[0141] In the case of a photoelectric conversion element for an imaging element with a structure in which light passes through the lower electrode 2 and is incident on the photoelectric conversion layer, the lower electrode 2 preferably has high transmittance to the wavelength of the incident light (for example, transmittance of 80% or more, preferably 90% or more).

[0142] 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 can 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.

[0143] It should be noted that in the case of a photoelectric conversion element for an imaging device with a structure in which light is incident only from the upper electrode 7 side to the photoelectric conversion layer, the transmission characteristics of the lower electrode 2 are not important. Therefore, an example of the material used for the lower electrode 2 in this case could be gold, iridium, molybdenum, palladium, platinum, etc.

[0144] [Electron transport layer (hole blocking layer) 3] An electron transport layer (hole blocking layer) 3 is provided between the lower electrode 2 and the photoelectric conversion layer 4.

[0145] The electron transport layer (hole blocking layer) 3 has the function of transporting electrons generated in the photoelectric conversion layer 4 to the lower electrode 2, and blocking holes generated in the photoelectric conversion layer 4 from moving to the lower electrode 2.

[0146] The electron transport layer (hole blocking layer) 3 can be a single-layer structure made of one or more materials, or a stacked structure made of multiple layers with the same or different compositions. For example, the electron transport layer (hole blocking layer) 3 can be a two-layer structure comprising a layer adjacent to a photoelectric conversion layer 4 made of a material specific to hole blocking properties, and a layer adjacent to a lower electrode 2 made of a material specific to electron transport properties.

[0147] The electron transport layer (hole blocking layer) 3 can be a layer containing a known electron transport material. Examples of known electron transport materials include, for instance, bis(8-hydroxyquinoline)manganese, tris(8-hydroxyquinoline)aluminum, tris(2-methyl-8-hydroxyquinoline)aluminum, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis(2-methyl-8-quinoline)-4-(phenylphenol)aluminum), 4,6-bis(3,5-bis(pyridin-4-yl)phenyl)-2-methylpyrimidine, N,N'-diphenyl-1,4,5,8-naphthalenetetracarboxylic acid diimide, N,N'-bis(4-pyridyl)-1,4,5,8-naphthalenetetracarboxylic acid diimide, etc.

[0148] [Photoelectric conversion layer 4] A photoelectric conversion layer 4 is disposed between the electron transport layer (hole blocking layer) 3 and the hole transport layer (electron blocking layer) 5 (described later). The photoelectric conversion layer 4 contains a material with photoelectric conversion function.

[0149] The photoelectric conversion layer 4 can be made of organic or inorganic materials, as long as it can generate signal charges corresponding to the amount of light received. When the photoelectric conversion layer 4 is made of organic materials, it can be a single-layer structure made of one or more materials, or a stacked structure made of multiple layers with the same or different compositions.

[0150] Materials used for photoelectric conversion layer 4 include n-type semiconductors and p-type semiconductors. n-type semiconductors are acceptor organic semiconductors, using compounds that readily accept electrons and have high electron transport properties. p-type semiconductors are donor organic semiconductors, using compounds that readily donate electrons and have high hole transport properties.

[0151] When multiple materials are used in the photoelectric conversion layer 4, examples of combinations include: n-type semiconductors and p-type semiconductors, n-type semiconductors and compounds with lower acceptor properties than the aforementioned n-type semiconductors, p-type semiconductors and compounds with lower donor properties than the aforementioned p-type semiconductors, etc. One or more of each material may be used.

[0152] The photoelectric conversion layer 4 may contain a pigment compound that exhibits excellent absorption of specific light. The pigment compound may be a compound with lower acceptor activity than the n-type semiconductor, or a compound with lower donor activity than the p-type semiconductor. From the viewpoint of improving photoelectric conversion efficiency, the photoelectric conversion layer 4 preferably contains a pigment compound in addition to the n-type and p-type semiconductors.

[0153] Examples of compounds included in the photoelectric conversion layer 4 include: coumarin and its derivatives, quinacridone and its derivatives, phthalocyanine and its derivatives, fullerene and its derivatives, azole derivatives such as imidazole, thiazole, thiadiazole, oxazole, oxadiazole, and triazole, naphthalenetetracarboxylic acid diimide, hole transport materials, etc.

[0154] The photoelectric conversion layer 4, which is composed of these materials, can be formed, for example, by vapor deposition using a mixed powder obtained by mixing powders of the various materials, or by co-depositing the various materials in any proportion.

[0155] 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 chloroboronide phthalocyanine, chloroboronide phthalocyanine (SubNC), F6-SubPC-OC6F5, and Cl6-SubPC-OC6.

[0156] Specific examples of fullerenes and their derivatives include:

[60] fullerene,

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

[60] PCBM), etc.

[0157] Hole transport materials can be any known hole transport materials. Examples of hole transport materials include, for instance, aromatic tertiary amine compounds, naphthalene compounds, anthracene compounds, tetraphenylene compounds, pentaphenylene compounds, phenanthrene compounds, pyrene compounds, perylene compounds, fluorene compounds, carbazole compounds, indole compounds, pyrrole compounds, styrene compounds, thiophene compounds, benzotrifuran compounds, benzotrithiophene compounds, naphthodithiophene compounds, naphthothiophene compounds, benzodifuran compounds, benzodithiophene compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, benzodithiophene compounds, benzothiophene compounds, indole-carbazole compounds, etc. Among them, preferred compounds are fluorene compounds, naphthodithiophene compounds, naphthothiophene compounds, benzodifuran compounds, benzothiophene compounds, naphthobisbenzothiophene compounds, denominated dithiophene compounds, benzothiophene compounds, and indole-carbazole compounds; more preferred compounds are fluorene compounds, denominated dithiophene compounds, benzothiophene compounds, and indole-carbazole compounds.

[0158] Specific examples of hole transport materials include: 9,9'-(9,9'-spirobis[9H-fluorene]-2,7'-diyl)bis[9H-carbazole], 2,7-diphenyl[1]benzothiophene[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]thiopheno[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, benzo[1,2-b:8,7-b']dithiophene, [1]benzothiophene[3,2-b][1]benzothiophene, compounds represented by the following formula (ic-1), compounds represented by the following formula (ic-2), etc.

[0159] [Chemical Formula 21]

[0160] It should be noted that the aforementioned material with photoelectric conversion function may be contained only in the photoelectric conversion layer 4, or it may be contained in layers other than the photoelectric conversion layer 4. For example, the layers adjacent to the photoelectric conversion layer 4 (electron transport layer (hole blocking layer) 3, hole transport layer (electron blocking layer) 5) may contain material with photoelectric conversion function.

[0161] [Hole transport layer (electron blocking layer) 5] A hole transport layer (electron blocking layer) 5 is disposed between the photoelectric conversion layer 4 and the buffer layer 6 described later.

[0162] The hole transport layer (electron blocking layer) 5 serves to transport holes generated in the photoelectric conversion layer 4 to the upper electrode 7 and to block electrons generated in the photoelectric conversion layer 4 from moving to the upper electrode 7. The hole transport layer (electron blocking layer) 5 preferably comprises the aforementioned charge transport material for photoelectric conversion elements of an imaging element or charge blocking material for photoelectric conversion elements of an imaging element.

[0163] The hole transport layer (electron blocking layer) 5 can be a single-layer structure made of one or more materials, or a stacked structure made of multiple layers with the same or different compositions. For example, the hole transport layer (electron blocking layer) 5 can be a two-layer structure comprising a layer adjacent to a photoelectric conversion layer 4 made of a material specific to electron blocking properties, and a layer adjacent to a buffer layer 6 made of a material specific to hole transport properties.

[0164] In addition to the materials used in the photoelectric conversion element for the imaging element described above, the hole transport layer (electron blocking layer) 5 may also contain a known hole transport material. Preferred compounds and specific examples of known hole transport materials include compounds identical to those described in the photoelectric conversion layer 4.

[0165] [Buffer Layer 6] A buffer layer 6 is disposed between the hole transport layer (electron blocking layer) 5 and the upper electrode 7 described later. When the upper electrode 7 is formed by sputtering, the buffer layer 6 serves to reduce damage to the organic layer (e.g., the hole transport layer (electron blocking layer) 5) during sputtering. Furthermore, by adjusting the work function of the buffer layer 6, it also has the function of efficiently accepting holes from the hole transport layer (electron blocking layer) 5, and is also referred to as a hole injection layer or work function adjustment layer.

[0166] The material constituting the buffer layer 6 can be a known material, such as naphthalene-1,4,5,8-tetracarboxylic acid dianhydride (NTCDA), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (HATCN), etc.

[0167] [Upper Electrode 7] An upper electrode 7 is provided on the buffer layer 6.

[0168] The material of the upper electrode 7 is not particularly limited, and can be, for example, sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, silver, magnesium / silver mixture, aluminum, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / alumina (Al2O3) mixture, indium, lithium / aluminum mixture, rare earth metals, etc.

[0169] [Methods of forming each layer] The materials of each layer (and, as needed, adhesive resins, solvents, etc.) can be made into thin films by known methods such as vacuum evaporation, spin coating, casting, and LB (Langmuir-Blodgett) to form the layers other than the lower electrode 2 and the upper electrode 7.

[0170] The thickness of the layers other than the lower electrode 2 and the upper electrode 7 is not particularly limited and can be selected appropriately according to the situation. The thickness of the layers other than the lower electrode 2 and the upper electrode 7 is usually in the range of 5 nm or more and 5 μm or less.

[0171] The lower electrode 2 and the upper electrode 7 can be formed by depositing electrode materials into thin films through methods such as vapor deposition and sputtering.

[0172] When the lower electrode 2 and the upper electrode 7 have patterns, the patterns can be formed, for example, through a mask of the desired shape. Alternatively, after forming a thin film by evaporation, sputtering, or the like, the pattern of the desired shape can be formed by photolithography.

[0173] The film thickness of the lower electrode 2 and the upper electrode 7 can be less than 1 μm, preferably more than 10 nm and less than 200 nm.

[0174] The materials constituting the lower electrode 2 and the upper electrode 7 can be replaced as needed (also known as an inversion structure). In this case, it is a photoelectric conversion element for an imaging element, in which light passes through the upper electrode 7 and is incident on the photoelectric conversion layer 4.

[0175] The camera element having the photoelectric conversion element involved in this embodiment can be applied to camera elements such as digital cameras and digital video cameras, as well as camera elements built into mobile phones.

[0176] The preferred embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments.

[0177] The following provides a detailed description of one aspect of the fused-ring compounds involved in this disclosure.

[0178] <Fused-ring compounds> One aspect of this disclosure relates to a fused-ring compound represented by the following formula (4), [Chemical Formula 22]

[0179] In equation (4), Ring A represents the structure represented by the following equation (5); R a1 ~R a8 Each of the following can be independently represented: hydrogen atom, alkyl group with 1-18 substituted carbon atoms, alkenyl group with 1-18 carbon atoms, cycloalkyl group with 1-18 carbon atoms, bicycloalkyl group with 1-18 carbon atoms, tricycloalkyl group with 1-20 carbon atoms, aromatic hydrocarbon group with 6-30 substituted carbon atoms, heteroaryl group with 3-30 substituted carbon atoms, -NR a21 R a22 or -OR a23 ; R a21 ~R a23 Each can be independently represented as an alkyl group with 1 to 18 carbon atoms that can be substituted, an aromatic hydrocarbon group with 6 to 30 carbon atoms that can be substituted, or a heteroaryl group with 3 to 30 carbon atoms that can be substituted; R a1 ~R a8 They can bond together to form a ring; Among them, R a1 ~R a4 At least one of them is an alkyl group having 1 to 18 substituted carbon atoms, an aromatic hydrocarbon group having 6 to 30 substituted carbon atoms, a heteroaryl group having 3 to 30 substituted carbon atoms, and -NR. a21 R a22 The group of the donor substituent; R a1 ~R a8 Any two adjacent elements are bonded together to form a ring as represented by the following equation (6).

[0180] [Chemical Formula 23]

[0181] In equation (5), X a1 ~X a4 The two adjacent atoms in the symbol represent carbon atoms shared with ring B, and the rest represent CR. a15 ; R a11 ~R a15 Each of the following can be independently represented: hydrogen atom, alkyl group with 1-18 substituted carbon atoms, alkenyl group with 1-18 carbon atoms, cycloalkyl group with 1-18 carbon atoms, bicycloalkyl group with 1-18 carbon atoms, tricycloalkyl group with 1-20 carbon atoms, aromatic hydrocarbon group with 6-30 substituted carbon atoms, heteroaryl group with 3-30 substituted carbon atoms, -NR a24 R a25 or -OR a26 ; R a24 ~R a26 Each can be independently represented as an alkyl group with 1 to 18 carbon atoms that can be substituted, an aromatic hydrocarbon group with 6 to 30 carbon atoms that can be substituted, or a heteroaryl group with 3 to 30 carbon atoms that can be substituted; R aA It represents an aromatic hydrocarbon group with 6 to 30 carbon atoms that can be substituted, or a heteroaryl group with 3 to 30 carbon atoms that can be substituted; L a It can refer to an alkylene group with 1 to 18 carbon atoms, a divalent aromatic hydrocarbon group with 6 to 30 carbon atoms that can be substituted, a divalent heteroaryl group with 3 to 30 carbon atoms that can be substituted, or a single bond.

[0182] [Chemical Formula 24]

[0183] In equation (6), R a31 ~R a34 Each of the following can be independently represented: hydrogen atom, alkyl group with 1-18 substituted carbon atoms, alkenyl group with 1-18 carbon atoms, cycloalkyl group with 1-18 carbon atoms, bicycloalkyl group with 1-18 carbon atoms, tricycloalkyl group with 1-20 carbon atoms, aromatic hydrocarbon group with 6-30 substituted carbon atoms, heteroaryl group with 3-30 substituted carbon atoms, -NR a21 R a22 or -OR a23 ; Adjacent R a31 ~R a34 They can bond together to form a ring; The carbon atom represents R a1 ~R a8 The carbon atoms in the 6-membered aromatic ring of the formula (4) that are bonded to any two adjacent carbon atoms.

[0184] In the above formula (4), the structure represented by the above formula (5) is ring A, and a group having the above-mentioned donor substituent is included. Thus, the compound represented by the above formula (4) is suitable for preparing photoelectric conversion elements with low dark current, high external quantum efficiency, and excellent responsiveness. Therefore, the compound represented by the above formula (4) is suitable for use as a material for photoelectric conversion elements.

[0185] Specific examples and preferred methods of the definitions in equations (4) to (6) above are shown below.

[0186] <R a1 ~R a8 > As R a1 ~R a8 Alkyl groups having 1 to 18 carbon atoms that can be substituted include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-nonyl, cyclohexyl, octyl, n-decyl, n-undecyl, n-dodecyl, n-octadecyl, n-tridecyl, n-tetradecyl, 2-ethylhexyl, 3-ethylheptyl, 3-ethyldecyl, 2-hexyldecyl, cyclopentyl, cyclohexyl, cycloheptyl, etc.

[0187] As R a1 ~R a8 Examples of alkenyl groups with 1 to 18 carbon atoms include: vinyl, propenyl, butenyl, 2-methylpropenyl, n-pentenyl, 2-methylbutenyl, n-hexenyl, 2-methylpentenyl, n-heptenyl, n-octenyl, 2-ethylhexenyl, n-nonenyl, 2-ethylheptenyl, n-decenyl, n-dodecenyl, cyclopenten-1-yl, cyclohexen-1-yl, cyclohepten-1-yl, etc.

[0188] As R a1 ~R a8 Examples of cycloalkyl groups having 1 to 18 carbon atoms include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, and cyclododecyl. This cycloalkyl group can be substituted with an alkyl group having 1 to 4 carbon atoms. Examples of alkyl groups having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, cyclopropylmethyl, 2-methylpropyl, 2,2-dimethylpropyl, cyclopropyl, tert-butyl, and cyclobutyl.

[0189] As R a1 ~R a8 Examples of bicyclic alkyl groups having 1 to 18 carbon atoms include, for example, norbornyl, 3-pinel, bicyclo[3.1.0]hexyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl-2-yl, etc.

[0190] As R a1 ~R a8 Examples of tricyclic alkyl groups with 1 to 20 carbon atoms include, for example, adamantyl, noradamantyl, and diadamantyl.

[0191] As R a1 ~R a8 Examples of substituted aromatic hydrocarbon groups with 6 to 30 carbon atoms include: substituted phenyl, substituted biphenyl, substituted terphenyl, substituted naphthyl, substituted anthracene, substituted phenanthryl, substituted pyrene, substituted phenyl, substituted benzo[g, p] ...

[0192] As R a1 ~R a8 Examples of substituted heteroaryl groups with 3 to 30 carbon atoms include: substituted dibenzofuranyl, substituted dibenzothiophenyl, substituted carbazoyl, substituted dibenzofuranylphenyl, substituted dibenzothiophenylphenyl, substituted carbazoylphenyl, substituted pyrroleyl, substituted thiophenyl, substituted furanyl, substituted imidazoyl, substituted pyrazolyl, substituted thiazoyl, substituted isothiazolyl, substituted oxazolyl, substituted isoxazolyl, substituted pyridyl, substituted phenylpyridyl, substituted pyridylphenyl, substituted pyrimidinyl, substituted pyrazinyl, substituted 1,3,5-triazinyl, substituted 1,3,5-triazinylphenyl, substituted 1,3,5-triazinylbiphenyl, and substituted 4... 6-Diphenyl-1,3,5-triazinyl, substituted indolyl, substituted benzothiopheneyl, substituted benzofuranyl, substituted benzimidazolyl, substituted indazoleyl, substituted benzothiazolyl, substituted benzoisothiazolyl, substituted 2,1,3-benzothiadiazolyl, substituted benzoxazolyl, substituted benzoisothiazolyl, substituted 2,1,3-benzoxadiazolyl, substituted quinolinyl, substituted isoquinolinyl, substituted quinoxolinyl, substituted quinazolinyl, substituted carbazolyl, substituted 9-phenylcarbazolyl, substituted 9-(4-biphenyl)carbazolyl, substituted dibenzothiopheneyl, substituted dibenzofuranyl, substituted phenoxazinyl, substituted phenthiazinyl, substituted phenazinyl, substituted thiaanthrayl, etc.

[0193] As R a21 ~R a23 Alkyl groups having 1 to 18 carbon atoms that can be substituted include: those that are R as mentioned above. a1 ~R a8 It can be replaced by alkyl groups with 1 to 18 carbon atoms.

[0194] As R a21 ~R a23 Aromatic hydrocarbon groups with 6 to 30 carbon atoms that can be substituted include: those that are R as mentioned above. a1 ~R a8 It can be replaced by aromatic hydrocarbon groups with 6 to 30 carbon atoms that are identical to the substituted group.

[0195] As R a21 ~R a23 Examples of heteroaryl groups with 3 to 30 carbon atoms that can be substituted include: those that are R as mentioned above. a1 ~R a8 It can be replaced by heteroaryl groups with 3 to 30 carbon atoms.

[0196] <R a11 ~R a15 > As R a11 ~R a15 Alkyl groups having 1 to 18 carbon atoms that can be substituted include: those that are R as mentioned above. a1 ~R a8 It can be replaced by alkyl groups with 1 to 18 carbon atoms.

[0197] As R a11 ~R a15 Alkenes with 1 to 18 carbon atoms can be exemplified by: those that are R as mentioned above. a1 ~R a8 A group with the same alkenyl group having 1 to 18 carbon atoms.

[0198] As R a11 ~R a15 Cycloalkyl groups having 1 to 18 carbon atoms can be exemplified by: those that are R as mentioned above. a1 ~R a8 The same group as the cycloalkyl group with 1 to 18 carbon atoms.

[0199] As R a11 ~R a15 Bicyclic alkyl groups having 1 to 18 carbon atoms can be exemplified by: those that are R as mentioned above. a1 ~R a8 It consists of bicyclic alkyl groups with 1 to 18 carbon atoms.

[0200] As R a11 ~R a15 Tricyclic alkyl groups having 1 to 20 carbon atoms can be exemplified by: those that are R as mentioned above. a1 ~R a8 It consists of tricyclic alkyl groups with 1 to 20 carbon atoms.

[0201] As R a11 ~R a15 Aromatic hydrocarbon groups with 6 to 30 carbon atoms that can be substituted include: those that are R as mentioned above. a1 ~R a8 It can be replaced by aromatic hydrocarbon groups with 6 to 30 carbon atoms that are identical to the substituted group.

[0202] As R a11 ~R a15 Examples of heteroaryl groups with 3 to 30 carbon atoms that can be substituted include: those that are R as mentioned above. a1 ~R a8 It can be replaced by heteroaryl groups with 3 to 30 carbon atoms.

[0203] As R a24 ~R a26 Alkyl groups having 1 to 18 carbon atoms that can be substituted include: those that are R as mentioned above. a1 ~R a8 It can be replaced by alkyl groups with 1 to 18 carbon atoms.

[0204] As R a24 ~R a26 Aromatic hydrocarbon groups with 6 to 30 carbon atoms that can be substituted include: those that are R as mentioned above. a1 ~R a8 It can be replaced by aromatic hydrocarbon groups with 6 to 30 carbon atoms that are identical to the substituted group.

[0205] As R a24 ~R a26 Examples of heteroaryl groups with 3 to 30 carbon atoms that can be substituted include: those that are R as mentioned above. a1 ~R a8 It can be replaced by heteroaryl groups with 3 to 30 carbon atoms.

[0206] <R aA > As R aA Aromatic hydrocarbon groups with 6 to 30 carbon atoms that can be substituted include: those that are R as mentioned above. a1 ~R a8 It can be replaced by aromatic hydrocarbon groups with 6 to 30 carbon atoms that are identical to the substituted group.

[0207] As R aA Examples of heteroaryl groups with 3 to 30 carbon atoms that can be substituted include: those that are R as mentioned above. a1 ~R a8 It can be replaced by heteroaryl groups with 3 to 30 carbon atoms.

[0208] <L a > As L a Alkylenes having 1 to 18 carbon atoms include, for example, methylene, ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, etc.

[0209] As L a Examples of substituted divalent aromatic hydrocarbon groups with 6 to 30 carbon atoms include: phenylene, biphenylene, terphenylene, naphthylene, phenylnaphthyl-diyl, binaphthyl, fluorene-diyl, benzo[a]fluorene-diyl, dibenzo[a]fluorene-diyl, phenanthrene-diyl, fluoranthene-diyl, anthracene-diyl, β-diyl, pyrene-diyl, triphenylene-diyl, perylene-diyl, etc.

[0210] As L a Examples of divalent heteroaryl groups with 3 to 30 substituted carbon atoms include, for example, pyrrole-diyl, thiophene-diyl, furan-diyl, imidazole-diyl, thiazole-diyl, isothiazole-diyl, oxazole-diyl, isoxazole-diyl, pyridine-diyl, pyrazin-diyl, triazine-diyl, indole-diyl, benzothiophene-diyl, benzofuran-diyl, benzimidazole-diyl, benzothiazole-diyl, benzoisothiazole-diyl, 2,1,3-benzothiadiazole-diyl, benzoox ...benzothiadiazole-diyl, benzothiadiazole-diyl, benzothiadiazole-diyl, benzothiadiazole-diyl, benzothiadiazole-diyl, benzothiadiazole-diyl, benzothiadiazole-diyl, benzothiadiazole-diyl, benzothiadiazole-diyl, benzothiadiazole-diyl, benzothiadiazole-diyl, benzothiadiazole-diyl, benzothiadiazole-diyl, benzothiadiazole-diyl, benzothiadiazole- -Benzoxadiazole-diyl, thienothiophene-diyl, dithienothiophene-diyl, benzodithiophene-diyl, quinoline-diyl, isoquinoline-diyl, quinoxaline-diyl, phenanthroline-diyl, dibenzothiophene-diyl, benzothiophene-diyl, dibenzofuran-diyl, carbazole-diyl, phenoxazine-diyl, phenthiazine-diyl, thiazoline-diyl, phenylthiophene-diyl, diphenylthiophene-diyl, phenylfuran-diyl, diphenylfuran-diyl, bithiophene-diyl, trithiophene-diyl, phenylpyridine-diyl, bipyridine-diyl, etc.

[0211] <R a31 ~R a34 > As R a31 ~R a34 Alkyl groups having 1 to 18 carbon atoms that can be substituted include: those that are R as mentioned above. a1 ~R a8 It can be replaced by alkyl groups with 1 to 18 carbon atoms.

[0212] As R a31 ~R a34 Alkenes with 1 to 18 carbon atoms can be exemplified by: those that are R as mentioned above. a1 ~R a8 A group with the same alkenyl group having 1 to 18 carbon atoms.

[0213] As R a31 ~R a34 Cycloalkyl groups having 1 to 18 carbon atoms can be exemplified by: those that are R as mentioned above. a1 ~R a8 The same group as the cycloalkyl group with 1 to 18 carbon atoms.

[0214] As R a31 ~R a34 Bicyclic alkyl groups having 1 to 18 carbon atoms can be exemplified by: those that are R as mentioned above. a1 ~R a8 It consists of bicyclic alkyl groups with 1 to 18 carbon atoms.

[0215] As R a31 ~R a34 Tricyclic alkyl groups having 1 to 20 carbon atoms can be exemplified by: those that are R as mentioned above. a1 ~R a8 It consists of tricyclic alkyl groups with 1 to 20 carbon atoms.

[0216] As R a31 ~R a34 Aromatic hydrocarbon groups with 6 to 30 carbon atoms that can be substituted include: those that are R as mentioned above. a1 ~R a8 It can be replaced by aromatic hydrocarbon groups with 6 to 30 carbon atoms that are identical to the substituted group.

[0217] As R a31 ~R a34 Examples of heteroaryl groups with 3 to 30 carbon atoms that can be substituted include: those that are R as mentioned above. a1 ~R a8 It can be replaced by heteroaryl groups with 3 to 30 carbon atoms.

[0218] The fused-ring compound represented by formula (4) above is preferably a fused-ring compound represented by formula (4A) or (4B) below. [Chemical Formula 25]

[0219] In equations (4A) and (4B), rings A and R a1 ~R a8 and R a31 ~R a34 Represents the rings A and R in equations (4) and (6) above. a1 ~R a8 and R a31 ~R a34 Same group.

[0220] In the fused-ring compounds represented by the above formulas (4), (4A) and (4B), preferably, R a1 With R a2 R a3 With R a4 R a5 With R a6 Or R a7 With R a8 Any pair of elements in the equation can bond together to form a ring as represented by the above equation (6).

[0221] In the fused ring compounds represented by the above formulas (4A) and (4B), preferably, ring A represents the structure represented by the following formula (5A) or (5B).

[0222] [Chemical Formula 26]

[0223] In equations (5A) and (5B), X a1 ~X a3 This indicates the carbon atom shared with ring B. R a11 ~R a15 R aA and L a R represents the expression in equation (5) above. a11 ~R a15 R aA and L a Same group.

[0224] The fused-ring compound represented by formula (4A) or (4B) above is preferably a fused-ring compound represented by formula (4C) below.

[0225] [Chemical Formula 27]

[0226] In equation (4C), R a35 ~R a38 Each of the following can be independently represented: hydrogen atom, alkyl group with 1-18 substituted carbon atoms, alkenyl group with 1-18 carbon atoms, cycloalkyl group with 1-18 carbon atoms, bicycloalkyl group with 1-18 carbon atoms, tricycloalkyl group with 1-20 carbon atoms, aromatic hydrocarbon group with 6-30 substituted carbon atoms, heteroaryl group with 3-30 substituted carbon atoms, -NR a21 R a22 or -OR a23 ; Adjacent R a35 ~R a38 They can bond together to form a ring; R a1 ~R a4 R a11 ~R a15 R a31 ~R a34 R aA and L a R represents the expression in equations (4) and (6) above. a1 ~R a4 R a11 ~R a15 R a31 ~R a34 R aA and L a Same group.

[0227] In the fused-ring compound represented by the above formula (4C), preferably, adjacent R a1 ~R a4 and R a31 ~R a38 They do not bond with each other to form rings.

[0228] In the fused-ring compound represented by the above formula (4C), preferably, L a It can be a substituted phenylene, a substituted biphenylene, a substituted terphenylene, a substituted naphthylene, or a single bond.

[0229] In the fused-ring compound represented by the above formula (4C), preferably, R a1 ~R a4 R a11 ~R a15 R a31 ~R a38 and R aA Each of the following can be independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, n-octyl, n-decyl, n-dodecyl, n-octadecyl, adamantyl, dimadamantyl, substituted phenyl, substituted biphenyl, substituted terphenyl, substituted naphthyl, substituted fluorenyl, substituted spirodifluorenyl, substituted benzo[a]fluorenyl, substituted phenanthryl, substituted fluoranyl, substituted triphenylene, substituted anthraquinone, substituted pyrene, substituted carbazole, substituted dibenzofuranyl, substituted dibenzothiophene, -NR a21 R a22 or -OR a23 The groups that make up the group; R a21 ~R a23 Each of the following groups is independently selected from the group consisting of hydrogen atom, adamantyl, diadamantyl, substituted phenyl, substituted biphenyl, substituted terphenyl, substituted naphthyl, substituted fluorenyl, substituted spirodifluorenyl, substituted benzofluorenyl, substituted phenanthryl, substituted fluoranyl, substituted triphenylene, substituted anthracene, substituted pyrene, substituted carbazolyl, substituted dibenzofuranyl, and substituted dibenzothiophene.

[0230] In the fused-ring compound represented by the above formula (4C), preferably, R a31 ~R a38 It is a hydrogen atom.

[0231] <Physical Properties of Fused-Ring Compounds> The preferred HOMO value, band gap, LUMO value, glass transition temperature and molecular weight of the fused ring compound represented by formula (4) are the same as those of the preferred HOMO value, band gap, LUMO value, glass transition temperature and molecular weight of the fused ring compound represented by formula (1) in the aforementioned <Materials for Photoelectric Conversion Elements>.

[0232] <Specific Examples of Preferred Fused-Ring Compounds> The preferred specific example of the fused ring compound represented by formula (4) is the same as the preferred specific example of the fused ring compound represented by formula (1) in the aforementioned <Materials for Photoelectric Conversion Elements>.

[0233] <Uses of Fused Ring Compounds> The uses of the fused ring compound represented by formula (4) are the same as those described in the "Uses of Materials for Photoelectric Conversion Elements" section of the aforementioned "Materials for Photoelectric Conversion Elements".

[0234] Example The present invention will now be described in more detail based on embodiments, but the present invention is not limited to these embodiments in any way.

[0235] [Synthesis Example 1: Synthesis of Compound (Bn-77)] [Chemical Formula 28]

[0236] (Synthesis of compound (P-1)) Compound (P-1) was synthesized by the method described in Japanese Patent No. 7127418.

[0237] (Synthesis of compound (P-2)) Under a nitrogen stream, 1.8 g (5.0 mmol) of compound (P-1), 1.3 g (6.0 mmol) of dibenzothiophene-2-boric acid, 22 mg (0.1 mmol) of palladium acetate, 111 mg (0.2 mmol) of 1,1'-bis(diphenylphosphine)ferrocene, 50 mL of tetrahydrofuran, and 5 mL of 2M potassium carbonate aqueous solution were added to a 200 mL glass container. The mixture was stirred at 75 °C for 12 hours. After cooling to room temperature, 50 mL of pure water was added and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol, thereby separating 2.0 g (85% yield) of colorless powder of compound (P-2).

[0238] (Synthesis of compound (P-3)) Under a nitrogen stream, 2.0 g (4.3 mmol) of compound (P-2), 45 mL of dichloromethane, and 5 mL of nitromethane were added to a 200 mL glass container. The solution was cooled to 0 °C while stirring, and 5.2 g (32 mmol) of ferric chloride (FeCl3) was added. The mixture was stirred at 0 °C for 20 minutes. Next, 100 mL of methanol was added to the reaction mixture and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol, thus separating 1.6 g (81% yield) of a pale yellow powder of compound (P-3).

[0239] (Synthesis of compound (P-4)) Under a nitrogen atmosphere, 1.6 g (3.4 mmol) of compound (P-3), 1.2 g (6.8 mmol) of m-chloroperoxybenzoic acid, and 68 mL of dichloromethane were added to a 200 mL glass container, and the mixture was stirred at room temperature for 12 hours. Then, 50 mL of a saturated sodium thiosulfate aqueous solution was added to the reaction mixture for separation. The organic layer obtained by separation was concentrated, and the precipitated solid was washed with methanol, thereby separating 1.5 g (88% yield) of a pale yellow powder of compound (P-4).

[0240] (Synthesis of compound (P-5)) Under a nitrogen atmosphere, 1.5 g (3.0 mmol) of compound (P-4), 0.88 g (3.6 mmol) of N-phenyl-4-benzidine, 26 mg (0.06 mmol) of palladium acetate, 24 mg (0.12 mmol) of tri-tert-butylphosphine, 0.43 g (4.5 mmol) of sodium tert-butoxide, and 30 mL of o-xylene were added to a 100 mL glass container, and the mixture was stirred at 140 °C for 24 hours. Then, 40 mL of methanol was added to the reaction mixture and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol, thereby separating 1.6 g (75% yield) of a pale yellow powder of compound (P-5).

[0241] (Synthesis of compound (Bn-77)) Under a nitrogen stream, 1.6 g (2.3 mmol) of compound (P-5), 0.43 g (4.6 mmol) of aniline, 14 mL (6.9 mmol) of a 0.5 M toluene solution of bis(trimethylsilyl)aminopotassium, and 25 mL of dioxane were added to a 200 mL glass container, and the mixture was stirred at 120 °C for 12 hours. Then, 50 mL of pure water was added to the reaction mixture and stirred. The precipitated solid was collected by filtration and recrystallized from toluene to separate 0.88 g (52% yield) of a pale yellow powder of compound (Bn-77). The obtained compound (Bn-77) was identified as... 1 H-NMR was performed.

[0242] 1 H-NMR (CDCl3) δ (ppm): 9.37 (s, 1H), 8.81 (d, J=8.8Hz, 1H), 8.77 (dd, J=8.0, 0.8Hz, 1H), 8.63 (dd, J=8.0, 0.8Hz, 1H), 8.62 (s, 1H), 8.58 (dd, J=8.8,0.8Hz, 1H), 8.41 (ddd, J=8.0, 0.8, 0.8Hz, 1H), 8.28-8.24 (m, 2H), 7.71-7.26 (m, 26H), 7.13-7.07 (m, 1H) [Synthesis Example 2: Synthesis of Compound (Cg-79)] [Chemical Formula 29]

[0243] (Synthesis of compound (Q-1)) Under a nitrogen stream, 7.6 g (32 mmol) of 1-bromo-2-methoxynaphthalene, 10 g (35 mmol) of 9-phenylcarbazole-2-boric acid, 144 mg (0.64 mmol) of palladium acetate, 610 mg (1.3 mmol) of 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (Xphos), 160 mL of 1,4-dioxane, and 24 mL of a 2M potassium phosphate aqueous solution were added to a 500 mL glass container. The mixture was stirred at 100 °C for 18 hours. After cooling to room temperature, the organic layer was concentrated by separation with toluene. The precipitated solid was dissolved in acetone, and methanol was added and stirred. The precipitated solid was collected by filtration and washed with methanol, thereby separating 12.2 g (95% yield) of compound (Q-1).

[0244] (Synthesis of compound (Q-2)) Under a nitrogen stream, 39 mL of a 1 M boron tribromide solution in dichloromethane was added to a 100 mL glass container containing 12 g (30 mmol) of compound (Q-1) and 30 mL of chloroform. The mixture was stirred at room temperature for 16 hours. After adding pure water, the reaction mixture was separated from the liquid using toluene, and the resulting organic layer was concentrated. The precipitated solid was dissolved in acetone, and methanol was added and stirred. The precipitated solid was collected by filtration and washed with methanol, thereby separating 7.7 g of compound (Q-2) (67% yield).

[0245] (Synthesis of compound (Q-3)) Under a nitrogen stream, 5.6 mL of triethylamine was added dropwise to a 300 mL glass container containing 7.7 g (20 mmol) of compound (Q-2) and 100 mL of chloroform, and the mixture was stirred at 0 °C for 1 hour. Next, 4.9 mL of trifluoromethanesulfonic anhydride was added dropwise to the solution at 0 °C, and the mixture was stirred at room temperature for 24 hours. After adding an aqueous sodium bicarbonate solution, the reaction mixture was separated from the solvent using toluene, and the resulting organic layer was concentrated. The precipitated solid was dissolved in toluene, and methanol was added and stirred. The precipitated solid was collected by filtration and washed with methanol, thereby separating 8.6 g of compound (Q-3) (yield 82%).

[0246] (Synthesis of compound (Q-4)) Under a nitrogen stream, 6.2 g (12 mmol) of compound (Q-3), 3.7 g (14 mmol) of 4-chloro-[2-(pyrrolidine-1-yldiazeninyl)phenyl]boronic acid, 0.20 g (0.24 mmol) of dichloro[1,1'-bis(diphenylphosphine)ferrocene]palladium·dichloromethane (PdCl2(dppf)·CH2Cl2), 4.5 mL of 4M sodium hydroxide aqueous solution, and 60 mL of 1,4-dioxane were added to a 200 mL glass container. The mixture was stirred at 100 °C for 12 hours. After cooling to room temperature, the organic layer was concentrated by separation with toluene. The precipitated solid was dissolved in acetone, and methanol was added and stirred. The precipitated solid was collected by filtration and washed with methanol, thereby separating 2.9 g (46% yield) of compound (Q-4).

[0247] (Synthesis of compound (Q-5)) Under a nitrogen stream, 2.9 g (5.0 mmol) of compound (Q-3) and 50 mL of chlorobenzene were added to a 200 mL glass container. The solution was cooled to 0 °C while stirring. 1.9 g (6.5 mmol) of ferric bromide was added, and the mixture was stirred at room temperature for 1 hour. Pure water was added to the reaction solution, and the precipitated solid was filtered off. The resulting organic layer was concentrated using chloroform. The solid was dissolved in toluene and passed through an alumina column to concentrate the organic solvent, thereby separating 1.3 g (54% yield) of compound (Q-5).

[0248] (Synthesis of compound (Cg-79)) Under a nitrogen stream, 1.3 g (2.8 mmol) of compound (Q-5), 1.2 g (3.6 mmol) of N,N-bisphenylamine, 12 mg (0.06 mmol) of palladium acetate, 23 mg (0.11 mmol) of tri-tert-butylphosphine, 0.40 g (4.2 mmol) of sodium tert-butoxide, and 28 mL of o-xylene were added to a 100 mL glass container. The mixture was stirred at 140 °C for 12 hours. After cooling to room temperature, hexane was added to the reaction solution, and the precipitated solid was filtered off. The solid was washed with a 1:1 mixture of ethyl acetate and hexane, and the solid was collected by filtration, thus separating 1.3 g (60% yield) of a yellow powder of compound (Cg-79). The obtained compound (Cg-79) was identified as... 1 H-NMR was performed.

[0249] 1 H-NMR (CDCl3) δ (ppm): 9.03 (d, J=8.4Hz, 1H), 8.81 (d, J=8.0Hz, 1H), 8.56 (d, J=8.8Hz, 1H), 8.43 (d, J=7.6Hz, 1H), 8.36 (d, J=9.6Hz, 1H), 8.26 (d, J=8.8Hz, 1H), 8.24 (d, J=1.6Hz, 1H), 8.11 (d, J=8.0Hz, 1H), 8.04 (d, J=8.8Hz, 1H), 7.76 (t, J=8.4Hz, 1H), 7.72-7.67 (m, 10H), 7.53(t, J=9.2Hz, 1H), 7.48 (t, J=7.6Hz, 5H), 7.43-7.40 (m, 3H), 7.36 (t, J=7.2Hz, 2H), 7.32-7.25 (m, 2H), 7.10 (d, J=8.4Hz, 4H), 6.82 (d, J=9.6Hz, 1H) (Comparative Example 1) As a comparative example 1, compound (X1) represented by the following formula was used. It should be noted that compound (X1) was synthesized according to the method disclosed in Japanese Patent Application Publication No. 2019-034939.

[0250] [Chemical Formula 30]

[0251] (Comparative Example 2) As a comparative example 2, a compound (Y1) represented by the following formula was used.

[0252] [Chemical Formula 31]

[0253] [Synthetic Example 3: Synthesis of Comparative Compound (Y1)] [Chemical Formula 32]

[0254] (Synthesis of compound (y-1)) Compound (y-1) was synthesized according to the method described in Japanese Patent Application Publication No. 2016-147846.

[0255] (Synthesis of compound (y-2)) Under a nitrogen stream, 1.4 g (2.9 mmol) of compound (y-1) and 90 mL of chloroform were added to a 200 mL glass container. The solution was cooled to 0 °C while stirring. 4.7 g (29 mmol) of ferric chloride and 20 mL of nitromethane were then added, and the mixture was stirred for 90 minutes. After adding pure water to the reaction solution, the mixture was separated using chloroform, and the resulting organic layer was concentrated. The crude product was purified by silica gel column chromatography (elution: ethyl acetate: hexane = 1:9) to give 0.87 g (63% yield) of compound (y-2).

[0256] (Synthesis of compound (Y1)) Under a nitrogen stream, 0.87 g (1.8 mmol) of compound (y-2), 0.38 g (2.2 mmol) of diphenylamine, 21 mg (0.09 mmol) of palladium acetate, 150 mg (0.18 mmol) of tri-tert-butylphosphine, 0.27 g (2.8 mmol) of sodium tert-butoxide, and 10 mL of o-xylene were added to a 100 mL glass container, and the mixture was stirred at 140 °C for 4 hours. After adding an aqueous solution of ammonium chloride to the reaction mixture, the mixture was separated by toluene, and the resulting organic layer was concentrated. The crude product was purified by silica gel column chromatography (elution: ethyl acetate: hexane = 1:9), yielding 0.79 g (76% yield) of a yellow powder of compound (Y1). The obtained compound (Y1) was identified as... 1 H-NMR was performed.

[0257] 1 H-NMR (DMSO-d6) δ (ppm): 8.85-8.68 (m, 5H), 8.34 (s, 1H), 7.78-7.73 (m, 4H), 7.71 (t, J=8.0Hz, 1H), 7.68-7.56 (m, 4H), 7.42 (d, J=9.2Hz, 1H), 7.32 (t, J=7.2Hz, 4H), 7.26 (d, J=9.2Hz, 1H), 7.10-6.97 (m, 7H) (Glass transition temperature) The measurements were performed using a DSC7020 manufactured by Hitachi High Tech Co., Ltd. The results are shown in Table 1.

[0258] (HOMO value) As the HOMO value of the compound obtained from the synthesis example, the HOMO value of the vapor-deposited film of the compound (100 nm film formed on a quartz substrate at a rate of 0.10 nm / s) was determined using an atmospheric photoelectron spectrometer (AC-3) manufactured by Riken Keiki Co., Ltd. The results are shown in Table 7.

[0259] [Table 7]

[0260] Component Example 1 (Refer to) Figure 1 )> like Figure 1 As shown, a photoelectric conversion element having a stacked structure consisting of a substrate 1, a first electrode 2, a hole blocking layer 3, a photoelectric conversion layer 4, an electron blocking layer 5, a hole transport layer 6, and a second electrode 7 is fabricated as an imaging element 100, and the dark current, external quantum efficiency, and responsivity of the imaging element are evaluated.

[0261] (Preparation of substrate 1 and first electrode 2) As a substrate having a first electrode on its surface, a glass substrate with a transparent ITO electrode is prepared, in which a 2 mm wide indium tin oxide (ITO) film (110 nm thick) is patterned into stripes. Next, the substrate is cleaned with isopropanol and then surface-treated by ozone ultraviolet cleaning.

[0262] (Preparation for vacuum evaporation) On a cleaned and surface-treated substrate, vacuum evaporation is performed on each layer to form the layers.

[0263] First, the glass substrate is introduced into a vacuum evaporation bath, and the pressure is reduced to 7.0 × 10⁻⁶. -5Pa Then, the films were prepared separately according to the film-forming conditions of each layer, following the order below.

[0264] (Preparation of hole blocking layer 3) Hole blocking layer 3 was prepared by forming a 10 nm film of 4,6-bis(3,5-di(pyridin-4-yl)phenyl)-2-methylpyrimidine purified by sublimation at a speed of 0.03 nm / s.

[0265] (Preparation of photoelectric conversion layer (light-receiving layer) 4) A photoelectric conversion layer 4 was prepared by forming a 120 nm film of N,N-dimethylquinacridone and C60 at a mass ratio of 4:1. The film formation rate was 0.15 nm / s.

[0266] (Preparation of electron blocking layer 5) An electron blocking layer 5 was prepared by depositing a 10 nm film of compound (Bn-77) at a speed of 0.10 nm / s.

[0267] (Preparation of hole transport layer 6) Hole transport layer 6 was prepared by forming a 10 nm film of compound 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (HATCN) at a speed of 0.10 nm / s.

[0268] (Preparation of the second electrode 7) Finally, a metal mask is configured orthogonally to the ITO stripes on the substrate to form the second electrode 7, which serves as the upper electrode. Specifically, the second electrode 7 is fabricated by depositing an 80 nm silver film at a rate of 0.1 nm / s.

[0269] Based on the above, the following was prepared: Figure 1 The area shown is 4mm. 2 The photoelectric conversion element 100 for imaging. It should be noted that the film thickness was measured using a stylus-type film thickness gauge (DEKTAK, manufactured by Bruker).

[0270] The component is then sealed in a glove box under a nitrogen atmosphere with an oxygen and moisture concentration of less than 1 ppm. The sealing is performed using a glass sealing cap and a film-forming substrate (component) made of bisphenol F epoxy resin (manufactured by Nagase Chemical Co., Ltd.).

[0271] A voltage of 2.6V was applied to the imaging element prepared above, and the dark current, external quantum efficiency, and response time were evaluated. The dark current was measured using a current source 2636B manufactured by Keysley Instruments. The external quantum efficiency was measured using a solar cell spectrophotometer (manufactured by Soma Kogyo). The illumination wavelength was 560 nm, and the intensity was 50 μW / cm². 2 The measurement was performed below. The response time is the time required for the measured current value to recover to its pre-irradiation value after the light pulse is applied.

[0272] It should be noted that the dark current, external quantum efficiency, and response time are relative values ​​with the results in Comparative Example 1 as the baseline (1.00). A lower dark current value indicates better performance, a higher external quantum efficiency value indicates better performance, and a lower response time value indicates better performance. The measured results are shown in Table 2.

[0273] <Component Example 2, Component Comparative Examples 1-2> In the preparation of the electron blocking layer 5 of Element Example 1, compound (Cg-79), comparative compound (X1), and comparative compound (Y1) were used in place of compound (Bn-77) in turn. Otherwise, the photoelectric conversion elements for imaging of Element Example 2, Element Comparative Example 1, and Element Comparative Example 2 were prepared and evaluated in the same manner as Element Example 1. The measurement results are shown in Table 8.

[0274] [Table 8]

[0275] As shown in Table 8, compared with the components of the comparative examples, the components of the embodiments using materials for photoelectric conversion elements of specific camera elements have suppressed dark current, achieved high external quantum efficiency, and exhibit excellent responsiveness.

[0276] Explanation of reference numerals in the attached figures 1 substrate 2 First electrode 3. Cavity blocking layer 4. Photoelectric conversion layer (light-receiving layer) 5 Electron blocking layer 6. Hole transport layer 7 Second electrode 100 Camera element (photoelectric conversion element).< / l>

Claims

1. A material for a photoelectric conversion element, characterized in that, Contains fused-ring compounds represented by the following formula (1), In equation (1), Ring A represents the structure represented by the following equation (2); R 1 ~R 8 respectively independently represent a hydrogen atom, a substituted or unsubstituted 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, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, -NR 21 R 22 or -OR 23 ; R 21 ~R 23 Each can be independently represented as an alkyl group with 1 to 18 carbon atoms that are substituted or not, an aromatic hydrocarbon group with 6 to 30 carbon atoms that are substituted or not, or a heteroaryl group with 3 to 30 carbon atoms that are substituted or not. R 1 ~R 8 They can bond together to form a ring; Among them, R 1 ~R 4 At least one of them is an alkyl group having 1 to 18 carbon atoms (selected or unsubstituted), an aromatic hydrocarbon group having 6 to 30 carbon atoms (selected or unsubstituted), a heteroaryl group having 3 to 30 carbon atoms (selected or unsubstituted), and -NR. 21 R 22 The group of the donor substituent; In equation (2), X 1 ~X 4 The two adjacent atoms in the symbol represent carbon atoms shared with ring B, and the rest represent CR. 15 ; R 11 ~R 15 Each of the following groups independently represents a hydrogen atom, an alkyl group with 1 to 18 carbon atoms (with or without substitution), an alkenyl group with 1 to 18 carbon atoms, a cycloalkyl group with 1 to 18 carbon atoms, a bicycloalkyl group with 1 to 18 carbon atoms, a tricycloalkyl group with 1 to 20 carbon atoms, an aromatic hydrocarbon group with 6 to 30 carbon atoms (with or without substitution), a heteroaryl group with 3 to 30 carbon atoms (with or without substitution), or -NR. 24 R 25 or -OR 26 ; R 24 ~R 26 Each can be independently represented as an alkyl group with 1 to 18 carbon atoms that are substituted or not, an aromatic hydrocarbon group with 6 to 30 carbon atoms that are substituted or not, or a heteroaryl group with 3 to 30 carbon atoms that are substituted or not. R A It represents an aromatic hydrocarbon group with 6 to 30 carbon atoms that are substituted or not, or a heteroaryl group with 3 to 30 carbon atoms that are substituted or not. L represents an alkylene group with 1 to 18 carbon atoms, a divalent aromatic hydrocarbon group with 6 to 30 carbon atoms (with or without substitution), a divalent heteroaryl group with 3 to 30 carbon atoms (with or without substitution), or a single bond.

2. The material for the photoelectric conversion element according to claim 1, wherein, R 1 ~R 8 Any two adjacent elements in the chain are bonded together to form a ring as represented by the following equation (3). In equation (3), R 31 ~R 34 Each of the following groups independently represents a hydrogen atom, an alkyl group with 1 to 18 carbon atoms (with or without substitution), an alkenyl group with 1 to 18 carbon atoms, a cycloalkyl group with 1 to 18 carbon atoms, a bicycloalkyl group with 1 to 18 carbon atoms, a tricycloalkyl group with 1 to 20 carbon atoms, an aromatic hydrocarbon group with 6 to 30 carbon atoms (with or without substitution), a heteroaryl group with 3 to 30 carbon atoms (with or without substitution), or -NR. 21 R 22 or -OR 23 ; Adjacent R 31 ~R 34 They can bond together to form a ring; The carbon atom represents R 1 ~R 8 The carbon atoms in the 6-membered aromatic ring of the formula (1) that are bonded to any two adjacent carbon atoms.

3. The material for the photoelectric conversion element according to claim 1 or 2, wherein, The fused-ring compound represented by formula (1) is a fused-ring compound represented by formula (1A) or (1B) below. In equations (1A) and (1B), rings A and R 1 ~R 8 and R 31 ~R 34 Represents the rings A and R in equations (1) and (3). 1 ~R 8 and R 31 ~R 34 Same group.

4. The material for the photoelectric conversion element according to claim 1, wherein, The fused-ring compound represented by formula (1) is a fused-ring compound represented by any of the following formulas (1C) to (1E). In equations (1C) to (1E), R 1 ~R 8 R 11 ~R 15 R A And L represents R in equations (1) and (2). 1 ~R 8 R 11 ~R 15 R A and groups with the same as L; Among them, it has an alkyl group selected from 1 to 18 carbon atoms (with or without substitution), an aromatic hydrocarbon group selected from 6 to 30 carbon atoms (with or without substitution), a heteroaryl group selected from 3 to 30 carbon atoms (with or without substitution), and -NR. 21 R 22 The donor substituent group in it is R. 1 ~R 4 At least one of them, or R 5 ~R 8 At least one of them.

5. The material for a photoelectric conversion element according to claim 2 or 4, wherein, R 1 With R 2 R 3 With R 4 R 5 With R 6 Or R 7 With R 8 Any one of the groups in the equation bonds to each other to form a ring represented by the equation (3).

6. The material for photoelectric conversion elements according to claim 3, wherein, In the fused-ring compound represented by formula (1), ring A represents a structure represented by formula (2A) or formula (2B) below. In equations (2A) and (2B), X 1 ~X 3 This indicates the carbon atom shared with ring B. R 11 ~R 15 R A And L represents R in equation (2). 11 ~R 15 R A And the same group as L.

7. The material for a photoelectric conversion element according to claim 2 or 6, wherein, The fused-ring compound represented by formula (1) is a fused-ring compound represented by formula (1F) below. In equation (1F), R 35 ~R 38 Each of the following groups independently represents a hydrogen atom, an alkyl group with 1 to 18 carbon atoms (with or without substitution), an alkenyl group with 1 to 18 carbon atoms, a cycloalkyl group with 1 to 18 carbon atoms, a bicycloalkyl group with 1 to 18 carbon atoms, a tricycloalkyl group with 1 to 20 carbon atoms, an aromatic hydrocarbon group with 6 to 30 carbon atoms (with or without substitution), a heteroaryl group with 3 to 30 carbon atoms (with or without substitution), or -NR. 21 R 22 or -OR 23 ; Adjacent R 35 ~R 38 They can bond together to form a ring; R 1 ~R 4 R 11 ~R 15 R 31 ~R 34 R A And L represents R in equations (1) and (3). 1 ~R 4 R 11 ~R 15 R 31 ~R 34 R A And the same group as L.

8. The material for a photoelectric conversion element according to claim 7, wherein, Adjacent R 1 ~R 4 and R 31 ~R 38 They do not bond with each other to form rings.

9. The material for a photoelectric conversion element according to claim 8, wherein, L can be a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted terphenylene, a substituted or unsubstituted naphthylene, or a single bond.

10. The material for a photoelectric conversion element according to claim 9, wherein, R 1 ~R 4 R 11 ~R 15 R 31 ~R 38 and R A Each of the following is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, n-octyl, n-decyl, n-dodecyl, n-octadecyl, adamantyl, dimadamantyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirodifluorenyl, substituted or unsubstituted benzo[a]fluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluoranyl, substituted or unsubstituted triphenylene, substituted or unsubstituted anthrayl, substituted or unsubstituted pyrene, substituted or unsubstituted carbazole, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophene, -NR 21 R 22 or -OR 23 The groups that make up the group; R 21 ~R 23 Each group is independently selected from the group consisting of hydrogen atom, adamantyl, diadamantyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirodifluorenyl, substituted or unsubstituted benzo[a]fluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluoranyl, substituted or unsubstituted triphenylene, substituted or unsubstituted anthracene, substituted or unsubstituted pyrene, substituted or unsubstituted carbazole, substituted or unsubstituted dibenzofuranyl, and substituted or unsubstituted dibenzothiophene.

11. The material for a photoelectric conversion element according to claim 10, wherein, R 31 ~R 38 It is a hydrogen atom.

12. An organic thin film, characterized in that, The material for photoelectric conversion elements comprising any one of claims 1 to 11.

13. A photoelectric conversion element, characterized in that, The material for photoelectric conversion elements comprising any one of claims 1 to 11.

14. A photoelectric conversion element, characterized in that, The photoelectric conversion layer contains the material for a photoelectric conversion element as described in any one of claims 1 to 11.

15. A photoelectric conversion element, characterized in that, The hole transport layer or electron blocking layer contains the material for the photoelectric conversion element as described in any one of claims 1 to 11.

16. The material for a photoelectric conversion element according to any one of claims 1 to 11, wherein, The aforementioned material for photoelectric conversion elements is used in photoelectric conversion elements for camera elements.

17. A fused-ring compound, characterized in that, It is represented by the following formula (4), In equation (4), Ring A represents the structure represented by the following equation (5); R a1 ~R a8 Each of the following groups independently represents a hydrogen atom, an alkyl group with 1 to 18 carbon atoms (with or without substitution), an alkenyl group with 1 to 18 carbon atoms, a cycloalkyl group with 1 to 18 carbon atoms, a bicycloalkyl group with 1 to 18 carbon atoms, a tricycloalkyl group with 1 to 20 carbon atoms, an aromatic hydrocarbon group with 6 to 30 carbon atoms (with or without substitution), a heteroaryl group with 3 to 30 carbon atoms (with or without substitution), or -NR. a21 R a22 or -OR a23 ; R a21 ~R a23 Each can be independently represented as an alkyl group with 1 to 18 carbon atoms that are substituted or not, an aromatic hydrocarbon group with 6 to 30 carbon atoms that are substituted or not, or a heteroaryl group with 3 to 30 carbon atoms that are substituted or not. R a1 ~R a8 They can bond together to form a ring; Among them, R a1 ~R a4 At least one of them is an alkyl group having 1 to 18 carbon atoms (selected or unsubstituted), an aromatic hydrocarbon group having 6 to 30 carbon atoms (selected or unsubstituted), a heteroaryl group having 3 to 30 carbon atoms (selected or unsubstituted), and -NR. a21 R a22 The group of the donor substituent; R a1 ~R a8 Any two adjacent elements in the ring are bonded together to form a ring represented by the following equation (6); In equation (5), X a1 ~X a4 The two adjacent atoms in the symbol represent carbon atoms shared with ring B, and the rest represent CR. a15 ; R a11 ~R a15 Each of the following groups independently represents a hydrogen atom, an alkyl group with 1 to 18 carbon atoms (with or without substitution), an alkenyl group with 1 to 18 carbon atoms, a cycloalkyl group with 1 to 18 carbon atoms, a bicycloalkyl group with 1 to 18 carbon atoms, a tricycloalkyl group with 1 to 20 carbon atoms, an aromatic hydrocarbon group with 6 to 30 carbon atoms (with or without substitution), a heteroaryl group with 3 to 30 carbon atoms (with or without substitution), or -NR. a24 R a25 or -OR a26 ; R a24 ~R a26 Each can be independently represented as an alkyl group with 1 to 18 carbon atoms that are substituted or not, an aromatic hydrocarbon group with 6 to 30 carbon atoms that are substituted or not, or a heteroaryl group with 3 to 30 carbon atoms that are substituted or not. R aA It represents an aromatic hydrocarbon group with 6 to 30 carbon atoms that are substituted or not, or a heteroaryl group with 3 to 30 carbon atoms that are substituted or not. L a It represents an alkylene group with 1 to 18 carbon atoms, a divalent aromatic hydrocarbon group with 6 to 30 carbon atoms (with or without substitution), a divalent heteroaryl group with 3 to 30 carbon atoms (with or without substitution), or a single bond; In equation (6), R a31 ~R a34 Each of the following groups independently represents a hydrogen atom, an alkyl group with 1 to 18 carbon atoms (with or without substitution), an alkenyl group with 1 to 18 carbon atoms, a cycloalkyl group with 1 to 18 carbon atoms, a bicycloalkyl group with 1 to 18 carbon atoms, a tricycloalkyl group with 1 to 20 carbon atoms, an aromatic hydrocarbon group with 6 to 30 carbon atoms (with or without substitution), a heteroaryl group with 3 to 30 carbon atoms (with or without substitution), or -NR. a21 R a22 or -OR a23 ; Adjacent R a31 ~R a34 They can bond together to form a ring; The carbon atom represents R a1 ~R a8 The carbon atoms in the 6-membered aromatic ring of the formula (4) that are bonded to any two adjacent carbon atoms in the ring are respectively bonded.

18. The fused-ring compound according to claim 17, wherein, The fused-ring compound represented by formula (4) is represented by formula (4A) or formula (4B) below. In equations (4A) and (4B), rings A and R a1 ~R a8 and R a31 ~R a34 Represents the rings A and R in equations (4) and (6). a1 ~R a8 and R a31 ~R a34 Same group.

19. The fused-ring compound according to claim 18, wherein, Ring A represents the structure represented by the following equation (5A) or equation (5B). In equations (5A) and (5B), X a1 ~X a3 This indicates the carbon atom shared with ring B. R a11 ~R a15 R aA and L a R represents the expression in equation (5). a11 ~R a15 R aA and L a Same group.

20. The fused-ring compound according to claim 19, wherein, Fused ring compounds represented by formula (4A) or (4B) are represented by formula (4C). In equation (4C), R a35 ~R a38 Each of the following groups independently represents a hydrogen atom, an alkyl group with 1 to 18 carbon atoms (with or without substitution), an alkenyl group with 1 to 18 carbon atoms, a cycloalkyl group with 1 to 18 carbon atoms, a bicycloalkyl group with 1 to 18 carbon atoms, a tricycloalkyl group with 1 to 20 carbon atoms, an aromatic hydrocarbon group with 6 to 30 carbon atoms (with or without substitution), a heteroaryl group with 3 to 30 carbon atoms (with or without substitution), or -NR. a21 R a22 or -OR a23 ; Adjacent R a35 ~R a38 They can bond together to form a ring; R a1 ~R a4 R a11 ~R a15 R a31 ~R a34 R aA and L a R represents the expression in equations (4) and (6). a1 ~R a4 R a11 ~R a15 R a31 ~R a34 R aA and L a Same group.

21. The fused-ring compound according to claim 20, wherein, In the fused-ring compound represented by formula (4C), adjacent R a1 ~R a4 and R a31 ~R a38 They do not bond with each other to form rings.

22. The fused-ring compound according to claim 21, wherein, L a It can be a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted terphenylene, a substituted or unsubstituted naphthylene, or a single bond.

23. The fused-ring compound according to claim 22, wherein, R a1 ~R a4 R a11 ~R a15 R a31 ~R a38 and R aA Each of the following is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, n-octyl, n-decyl, n-dodecyl, n-octadecyl, adamantyl, dimadamantyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirodifluorenyl, substituted or unsubstituted benzo[a]fluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluoranyl, substituted or unsubstituted triphenylene, substituted or unsubstituted anthrayl, substituted or unsubstituted pyrene, substituted or unsubstituted carbazole, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophene, -NR a21 R a22 or -OR a23 The groups that make up the group; R a21 ~R a23 Each group is independently selected from the group consisting of hydrogen atom, adamantyl, diadamantyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted spirodifluorenyl, substituted or unsubstituted benzo[a]fluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluoranyl, substituted or unsubstituted triphenylene, substituted or unsubstituted anthracene, substituted or unsubstituted pyrene, substituted or unsubstituted carbazole, substituted or unsubstituted dibenzofuranyl, and substituted or unsubstituted dibenzothiophene.

24. The fused-ring compound according to claim 23, wherein, R a31 ~R a38 It is a hydrogen atom.

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