Materials for photovoltaic devices, organic thin films, photovoltaic devices, and condensed ring compounds

Abstract

The present invention provides a material for a photoelectric conversion device that contributes to the fabrication of a photoelectric conversion device having low dark current, high external quantum efficiency, and excellent responsiveness. The material for a photoelectric conversion device containing a condensed ring compound represented by the following formula (1) is used. In formula (1), ring A represents a structure represented by the following formula (2); R1 to R8 each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkeneyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, -NR21R22 or -OR23.

Description

Technology Field

[0001] The present invention relates to a material for a photoelectric conversion device, an organic thin film, a photoelectric conversion device, and a condensed ring compound. Background Technology

[0002] Photoelectric conversion devices for imaging elements are used for purposes such as mobile phones and cameras, and their development is being actively carried out.

[0003] Recently, market demand for photoelectric conversion devices for imaging devices has been increasing, and materials that are excellent in terms of dark current, external quantum efficiency, and response speed are required. Under these circumstances, the potential of various polycyclic compounds as cores for new materials is being explored and examined. As for polycyclic compounds, Patent Document 1 discloses a derivative based on benzothienobenzothiophene as a core. In addition, Patent Document 2 discloses various cores in addition to benzothienobenzothiophene. Patent Document 3 discloses unsubstituted dibenzo[g, p]chrysene. Prior art literature

[0004] (Patent Document 0001) WO 2015-163349 A (Patent Document 0002) WO 2020-022421 A (Patent Document 0003) JP 2010-258438 A The problem to be solved

[0005] The objective of one aspect of the present invention is to propose a material for a photoelectric conversion device and a photoelectric conversion device using a compound having a new core, while the possibility of various polycyclic compounds as cores of new materials is still being explored and examined.

[0006] The objective of another aspect of the present invention is to provide a material for a photovoltaic device that contributes to the fabrication of a photovoltaic device having low dark current, high external quantum efficiency, and excellent responsiveness, and furthermore, a compound that contributes to the fabrication of a photovoltaic device having low dark current, high external quantum efficiency, and excellent responsiveness.

[0007] However, Patent Document 3 describes the use of unsubstituted dibenzo[g, p]chrysene as a crystal layer between the photoelectric conversion layer and the upper electrode. However, Patent Document 3 does not mention at all the characteristics of the molecular structure of dibenzo[g, p]chrysene or the amorphous film containing dibenzo[g, p]chrysene. Furthermore, the dibenzo[g, p]chrysene described in Patent Document 3 does not provide any knowledge for improving the performance of a photoelectric conversion device for an imaging device. means of solving the problem

[0008] The inventors have discovered that the above problem can be solved by using a specific condensed ring compound, and have completed the present invention.

[0009] The aspects of the present disclosure relate to the following materials for photoelectric conversion devices, organic thin films, photoelectric conversion devices, and condensed ring compounds.

[0010] [1] A material for photoelectric conversion devices containing a condensed ring compound represented by the following formula (1):

[0011]

[0012] Among the formula (1),

[0013] Ring A represents a structure indicated by the following formula (2);

[0014] R 1 to R 8 Each independently comprises a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR 21 R 22 or -OR 23 Representing;

[0015] R 21 to R 23 Each represents an alkyl group having 1 to 18 carbon atoms that may be independently substituted, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, or a heteroaromatic group having 3 to 30 carbon atoms that may be substituted;

[0016] R 1 to R 8 They may combine with each other to form rings;

[0017] However, R 1 to R 4 At least one of the following is an alkyl group having 1 to 18 carbon atoms that may be substituted, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR 21 R 22 It is a group having a donor substituent selected from;

[0018]

[0019] Among the (2) formulas,

[0020] X 1 To X 4 Of these, the two adjacent atoms represent carbon atoms shared with ring B, and the rest are CR 15 Representing;

[0021] R 11 to R 15 Each independently comprises a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR 24 R 25 or -OR 26Representing;

[0022] R 24 to R 26 Each represents an alkyl group having 1 to 18 carbon atoms that may be independently substituted, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, or a heteroaromatic group having 3 to 30 carbon atoms that may be substituted;

[0023] R A represents an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, or a heteroaromatic group having 3 to 30 carbon atoms that may be substituted;

[0024] L represents an alkylene group having 1 to 18 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a divalent heteroaromatic group having 3 to 30 carbon atoms that may be substituted, or a single bond.

[0025] [2] R 1 to R 8 A photoelectric conversion element material described in [1], wherein any two adjacent ones are combined with each other to form a ring represented by the following formula (3):

[0026]

[0027] Among the (3) formulas,

[0028] R 31 to R 34 Each independently comprises a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR 21 R 22 or -OR 23 Representing;

[0029] Adjacent R 31 to R 34 They may combine with each other to form a ring;

[0030] The carbon atom of * is R 1 to R 8 It represents a carbon atom in the six-membered aromatic ring of the above formula (1), in which two adjacent atoms of either one are bonded.

[0031] [3] A material for a photoelectric conversion device described in [1] or [2], wherein the condensed ring compound represented by the above formula (1) is a condensed ring compound represented by the following formula (1A) or (1B):

[0032]

[0033] [In formulas (1A) and (1B), ring A, R 1 to R 8 and R 31 to R 34 is the ring A, R of the above equations (1) and (3). 1 to R 8 and R 31 to R 34 [It represents a similar energy].

[0034] [4] A material for a photoelectric conversion device described in [1] or [2], wherein the condensed ring compound represented by the above formula (1) is a condensed ring compound represented by any of the following formulas (1C) to (1E):

[0035]

[0036] [In formulas (1C) to (1E), R 1 to R 8 , R 11 to R 15 , R A and L is R of the above equations (1) and (2). 1 to R 8 , R 11 to R 15 , R A and represents groups such as L;

[0037] However, an alkyl group having 1 to 18 carbon atoms that may be substituted, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR 21 R 22 A group having a donor substituent selected from is R 1 to R 4 It may be at least one of them, and R 5 to R 8 [At least one of them may be used].

[0038] [5] R 1 and R 2 , R 3 and R 4 , R 5 and R 6 or R 7 and R 8 A photoelectric conversion element material described in any one of [2] to [4], wherein one of them is combined with another to form a ring represented by the above formula (3).

[0039] [6] A photoelectric conversion material described in [3] in which ring A of the condensed ring compound represented by the above formula (1) has a structure represented by the following formula (2A) or (2B):

[0040]

[0041] [Among Equations (2A) and (2B),

[0042] X 1 To X 3 represents a carbon atom shared with ring B, and

[0043] R 11 to R 15 , R A and L is R of the above equation (2). 11 to R 15 , R A [and represents groups such as L].

[0044] [7] A material for a photoelectric conversion device described in [2], [3], [5] or [6], wherein the condensed ring compound represented by the above formula (1) is a condensed ring compound represented by the following formula (1F):

[0045]

[0046] [Essence (1F),

[0047] R 35 to R 38 Each independently comprises a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR 21 R 22 or -OR 23 Representing;

[0048] Adjacent R 35 to R 38 They may combine with each other to form rings;

[0049] R 1 to R 4 , R 11 to R 15 , R 31 to R 34 , R A and L is R of the above equations (1) and (3). 1 to R 4 , R 11 to R 15 , R 31 to R 34 , R A [and represents groups such as L].

[0050] [8] Adjacent R 1 to R 4 and R 31 to R 38The photoelectric conversion device material described in [7], which does not form rings by being bonded together.

[0051] [9] A photoelectric conversion material described in [7] or [8] in which L is a phenylene group that may be substituted, a biphenylene group that may be substituted, a terphenylene group that may be substituted, a naphthylene group that may be substituted, or a single bond.

[0052]

[10] R 1 to R 4 , R 11 to R 15 , R 31 to R 38 and R A Each independently a hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-octadecyl group, adamantyl group, diamantyl group, a substituted phenyl group, a substituted biphenylyl group, a substituted terphenylyl group, a substituted naphthyl group, a substituted fluorenyl group, a substituted spirobifluorenyl group, a substituted benzoflurenyl group, a substituted phenanthyl group, a substituted fluoranthenyl group, a substituted triphenylenyl group, a substituted anthryl group, a substituted pyrenyl group, a substituted carbazolyl group, a substituted dibenzofuranyl group, Dibenzotien diary that may be substituted, -NR 21 R 22 and -OR 23 It is a group selected from the group consisting of;

[0053] R 21 to R 23A material for a photoelectric conversion device described in any one of [7] to [9], each independently selected from the group consisting of a hydrogen atom, an adamantyl group, adamantyl group, a phenyl group that may be substituted, a biphenylyl group that may be substituted, a terphenylyl group that may be substituted, a naphthyl group that may be substituted, a fluorenyl group that may be substituted, a spirobifluorenyl group that may be substituted, a benzofluorenyl group that may be substituted, a phenanthyl group that may be substituted, a fluoranthenyl group that may be substituted, a triphenylenyl group that may be substituted, an anthryl group that may be substituted, a pyrenyl group that may be substituted, a carbazolyl group that may be substituted, a dibenzofuranyl group that may be substituted, and a dibenzothienyl group that may be substituted.

[0054]

[11] R 31 to R 38 This hydrogen atom is a material for photoelectric conversion devices described in any of [7] to

[10] .

[0055]

[12] An organic thin film comprising a material for a photoelectric conversion device as described in any of [1] to

[11] .

[0056]

[13] A photoelectric conversion device comprising a material for a photoelectric conversion device described in any of [1] to

[11] .

[0057]

[14] A photoelectric conversion device comprising a photoelectric conversion material described in any one of [1] to

[11] in a photoelectric conversion layer.

[0058]

[15] A photoelectric conversion device comprising a material for a photoelectric conversion device described in any one of [1] to

[11] in a hole transport layer or an electron blocking layer.

[0059]

[16] A photoelectric conversion element material described in any one of [1] to

[11] , used in a photoelectric conversion element for an imaging element.

[0060]

[17] Condensed ring compounds represented by the following formula (4):

[0061]

[0062] Among the formulas (4),

[0063] Ring A represents a structure indicated by the following formula (5);

[0064] R a1 to R a8 Each independently comprises a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR a21 R a22 or -OR a23 Representing;

[0065] R a21 to R a23 Each represents an alkyl group having 1 to 18 carbon atoms that may be independently substituted, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, or a heteroaromatic group having 3 to 30 carbon atoms that may be substituted;

[0066] R a1 to R a8 They may combine with each other to form rings;

[0067] However, R a1 to R a4 At least one of the following is an alkyl group having 1 to 18 carbon atoms that may be substituted, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR a21 R a22 A group having a donor substituent selected from;

[0068] R a1 to Ra8 Any two adjacent ones combine with each other, and a ring is formed as shown in the following formula (6);

[0069]

[0070] Among the (5) formulas,

[0071] X a1 To X a4 Of these, the two adjacent atoms represent carbon atoms shared with ring B, and the rest are CR a15 Representing;

[0072] R a11 to R a15 Each independently comprises a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR a24 R a25 or -OR a26 Representing;

[0073] R a24 to R a26 Each represents an alkyl group having 1 to 18 carbon atoms that may be independently substituted, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, or a heteroaromatic group having 3 to 30 carbon atoms that may be substituted;

[0074] R aA ...represents an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, or a heteroaromatic group having 3 to 30 carbon atoms that may be substituted;

[0075] L a...represents an alkylene group having 1 to 18 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a divalent heteroaromatic group having 3 to 30 carbon atoms that may be substituted, or a single bond;

[0076]

[0077] Among the formulas (6),

[0078] R a31 to R a34 Each independently comprises a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR a21 R a22 or -OR a23 Representing;

[0079] Adjacent R a31 to R a34 They may combine with each other to form a ring;

[0080] The carbon atom of * is R a1 to R a8 It represents a carbon atom in the six-membered aromatic ring of the above formula (4), in which two adjacent atoms of either one are bonded.

[0081]

[18] A condensed ring compound represented by the above formula (4) is a condensed ring compound described in

[17] , represented by the following formula (4A) or (4B):

[0082]

[0083] [Among formulas (4A) and (4B), ring A, R a1 to R a8 and R a31 to R a34is the ring A, R of the above equations (4) and (6). a1 to R a8 and R a31 to R a34 [Represents a similar energy].

[0084]

[19] Condensed ring compounds described in

[17] or

[18] , wherein ring A has a structure represented by the following formula (5A) or (5B):

[0085]

[0086] [Among formulas (5A) and (5B),

[0087] X a1 To X a3 represents a carbon atom shared with ring B, and

[0088] R a11 to R a15 , R aA and L a is R of the above equation (5). a11 to R a15 , R aA and L a [Represents a similar energy].

[0089]

[20] A condensed ring compound represented by the above formula (4A) or (4B) is a condensed ring compound represented by the following formula (4C), as described in

[18] or

[19] :

[0090]

[0091] [Among the formula (4C),

[0092] R a35 to R a38 Each independently comprises a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NRa21 R a22 or -OR a23 Representing;

[0093] Adjacent R a35 to R a38 They may combine with each other to form rings;

[0094] R a1 to R a4 , R a11 to R a15 , R a31 to R a34 , R aA and L a is R of the above equations (4) and (6). a1 to R a4 , R a11 to R a15 , R a31 to R a34 , R aA and L a [Represents a similar energy].

[0095]

[21] The condensation ring compound represented by the above formula (4C) is adjacent to R a1 to R a4 and R a31 to R a38 These are condensed ring compounds described in

[20] that do not combine to form rings.

[0096]

[22] L a A condensed ring compound described in

[20] or

[21] , which may be substituted with a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, or a single bond.

[0097]

[23] R a1 to R a4 , R a11 to R a15 , R a31 to R a38 and R aAEach independently a hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-octadecyl group, adamantyl group, diamantyl group, a substituted phenyl group, a substituted biphenylyl group, a substituted terphenylyl group, a substituted naphthyl group, a substituted fluorenyl group, a substituted spirobifluorenyl group, a substituted benzoflurenyl group, a substituted phenanthyl group, a substituted fluoranthenyl group, a substituted triphenylenyl group, a substituted anthryl group, a substituted pyrenyl group, a substituted carbazolyl group, a substituted dibenzofuranyl group, Dibenzotien diary that may be substituted, -NR a21 R a22 and -OR a23 It is a group selected from the group consisting of;

[0098] R a21 to R a23 A condensed ring compound described in any one of

[20] to

[22] , each independently selected from the group consisting of a hydrogen atom, an adamantyl group, adamantyl group, a phenyl group that may be substituted, a biphenylyl group that may be substituted, a terphenylyl group that may be substituted, a naphthyl group that may be substituted, a fluorenyl group that may be substituted, a spirobifluorenyl group that may be substituted, a benzofluorenyl group that may be substituted, a phenanthyl group that may be substituted, a fluoranthenyl group that may be substituted, a triphenylenyl group that may be substituted, an anthryl group that may be substituted, a pyrenyl group that may be substituted, a carbazolyl group that may be substituted, a dibenzofuranyl group that may be substituted, and a dibenzothienyl group that may be substituted.

[0099]

[24] R a31to R a38 This hydrogen atom is a condensed ring compound described in any of

[20] to

[23] . Effects of the invention

[0100] According to one aspect of the present invention, a material for a photoelectric conversion device that contributes to the fabrication of a photoelectric conversion device having low dark current, high external quantum efficiency, and excellent responsiveness, and furthermore, a compound that contributes to the fabrication of a photoelectric conversion device having low dark current, high external quantum efficiency, and excellent responsiveness can be provided. Brief explanation of the drawing

[0101] FIG. 1 is a schematic cross-sectional view showing an example of a stacked configuration of a photoelectric conversion device for an imaging device including a material for a photoelectric conversion device for an imaging device according to one aspect of the present invention. Specific details for implementing the invention

[0102] Hereinafter, a material for a photoelectric conversion device according to one aspect of the present disclosure will be described in detail.

[0103] ≪ Materials for Photovoltaic Devices ≫

[0104] A condensed ring compound represented by the following formula (1) is suitably used as a material for a photoelectric conversion device. That is, a material for a photoelectric conversion device according to one aspect of the present disclosure includes a condensed ring compound represented by the following formula (1).

[0105]

[0106] Among the formula (1),

[0107] Ring A represents a structure indicated by the following formula (2);

[0108] R 1 to R 8Each independently comprises a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR 21 R 22 or -OR 23 Representing;

[0109] R 21 to R 23 Each represents an alkyl group having 1 to 18 carbon atoms that may be independently substituted, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, or a heteroaromatic group having 3 to 30 carbon atoms that may be substituted;

[0110] R 1 to R 8 They may combine with each other to form rings;

[0111] However, R 1 to R 4 At least one of the following is an alkyl group having 1 to 18 carbon atoms that may be substituted, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR 21 R 22 It is a group having a donor substituent selected from;

[0112]

[0113] Among the (2) formulas,

[0114] X 1 To X 4 Of these, the two adjacent atoms represent carbon atoms shared with ring B, and the rest are CR 15 Representing;

[0115] R 11to R 15 Each independently comprises a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR 24 R 25 or -OR 26 Representing;

[0116] R 24 to R 26 Each represents an alkyl group having 1 to 18 carbon atoms that may be independently substituted, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, or a heteroaromatic group having 3 to 30 carbon atoms that may be substituted;

[0117] R A represents an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, or a heteroaromatic group having 3 to 30 carbon atoms that may be substituted;

[0118] L represents an alkylene group having 1 to 18 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a divalent heteroaromatic group having 3 to 30 carbon atoms that may be substituted, or a single bond.

[0119] In the above formula (1), by having a group having the donor substituent as ring A and having the structure represented by the above formula (2), a material for a photoelectric conversion device comprising the compound represented by the above formula (1) can provide a photoelectric conversion device with low dark current, high external quantum efficiency, and excellent responsiveness. For this reason, the compound represented by the above formula (1) is suitablely used as a material for a photoelectric conversion device.

[0120] Specific examples and preferred aspects of the definitions in the above formulas (1) and (2) are as follows.

[0121] <R 1 to R 8 >

[0122] R 1 to R 8 Examples of alkyl groups having 1 to 18 carbon atoms that may be substituted as such include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isovaleryl group, n-hexyl group, i-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, cyclohexyl group, octyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-octadecyl group, n-tridecyl group, n-tetradecyl group, 2-ethylhexyl group, 3-ethylheptyl group, 3-ethyldecyl, 2-hexyldecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.

[0123] R 1 to R 8 Examples of alkeneyl groups having 1 to 18 carbon atoms include, for instance, an etheneyl group, a propeneyl group, a buteneyl group, a 2-methylpropeneyl group, an n-penteneyl group, a 2-methylbuteneyl group, an n-hexeneyl group, a 2-methylpenteneyl group, an n-hepteneyl group, an n-octenyl group, a 2-ethylhexeneyl group, an n-nonel group, a 2-ethylhepteneyl group, an n-deceneyl group, an n-dodeceneyl group, a cyclopenteneyl-1- group, a cyclohexeneyl-1- group, a cyclohepteneyl-1- group, and the like.

[0124] R 1 to R 8Examples of cycloalkyl groups having 1 to 18 carbon atoms include cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, cyclooctyl groups, cyclononyl groups, cyclodecyl groups, cyclolondecyl groups, cyclododecyl groups, etc. The cycloalkyl groups may be substituted with alkyl groups having 1 to 4 carbon atoms. Examples of alkyl groups having 1 to 4 carbon atoms include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, cyclopropylmethyl groups, 2-methylpropyl groups, 2,2-dimethylpropyl groups, cyclopropyl groups, tert-butyl groups, cyclobutyl groups, etc.

[0125] R 1 to R 8 Examples of bicycloalkyl groups having 1 to 18 carbon atoms include novonyl groups, 3-finanyl groups, bicyclo[3.1.0]hexyl groups, bicyclo[2.2.1]heptyl groups, bicyclo[2.2.2]octo-2-yl groups.

[0126] R 1 to R 8 Examples of tricycloalkyl groups having 1 to 20 carbon atoms include adamantyl groups, noradamantyl groups, diamantyl groups, etc.

[0127] R 1 to R 8As an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted as, for example, a phenyl group that may be substituted, a biphenylyl group that may be substituted, a terphenylyl group that may be substituted, a naphthyl group that may be substituted, an anthryl group that may be substituted, a phenanthryl group that may be substituted, a pyrenyl group that may be substituted, a crisenyl group that may be substituted, a benzocrysenyl group that may be substituted, a dibenzocrysenyl group that may be substituted, a fluorenyl group that may be substituted, a benzofluorenyl group that may be substituted, a fluoranthenyl group that may be substituted, a triphenylenyl group that may be substituted, a spirobifluorenyl group that may be substituted, a naphthylphenyl group that may be substituted, a phenylnaphthyl group that may be substituted, a naphthylnaphthyl group that may be substituted, a phenanthrylphenyl group that may be substituted, a diphenylfluorenyl group that may be substituted, and a group that may be substituted Examples include dibenzo[g, p]crisenyl groups.

[0128] R 1 to R 8As a heteroaromatic group having 3 to 30 carbon atoms that may be substituted as, for example, a dibenzofuranyl group that may be substituted, a dibenzothionyl group that may be substituted, a carbazolyl group that may be substituted, a dibenzofuranylphenyl group that may be substituted, a dibenzothionylphenyl group that may be substituted, a carbazolylphenyl group that may be substituted, a pyrrolyl group that may be substituted, a thienyl group that may be substituted, a furyl group that may be substituted, an imidazolyl group that may be substituted, a pyrazolyl group that may be substituted, a thiazolyl group that may be substituted, an isothiazolyl group that may be substituted, an oxazolyl group that may be substituted, an isoxazolyl group that may be substituted, a pyridyl group that may be substituted, a phenylpyridyl group that may be substituted, a pyridylphenyl group that may be substituted, a pyrimidyl group that may be substituted, a pyrazyl group that may be substituted 1,3,5-triazyl group, optionally substituted 1,3,5-triazylphenyl group, optionally substituted 1,3,5-triazylbiphenyl group, optionally substituted 4,6-diphenyl-1,3,5-triazyl group, optionally substituted indolyl group, optionally substituted benzo Chienil (Tienil?) group, substituted benzofuranyl group, substituted benzimidazolyl group, substituted indazolyl group, substituted benzothiazolyl group, substituted benzisothiazolyl group, substituted 2,1,3-benzothiadiazolyl group, substituted benzoxazolyl group, substituted benzisooxazolyl group, substituted 2,1,3-benzoxadiazolyl group, substituted quinolyl group, substituted isoquinolyl group, substituted quinoxalyl group, substituted quinazolyl group, substituted carbazolyl group, substituted 9-phenylcarbazolyl group, substituted 9-(4-biphenylyl)carbazolyl group, substituted dibenzo Chienil (Tienil?) Examples include a dibenzofuranyl group that may be substituted, a phenoxysaline group that may be substituted, a phenothiazine group that may be substituted, a phenazine group that may be substituted, a thiantrenyl group that may be substituted, etc.

[0129] R 21 to R 23 As an alkyl group having 1 to 18 carbon atoms that may be substituted as, the aforementioned R 1 to R 8 Examples include alkyl groups having 1 to 18 carbon atoms that may be substituted as such.

[0130] R 21 to R 23 As an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted as, the aforementioned R 1 to R 8 Examples include aromatic hydrocarbon groups having 6 to 30 carbon atoms that may be substituted as such.

[0131] R 21 to R 23 As a heteroaromatic group having 3 to 30 carbon atoms that may be substituted as, the aforementioned R 1 to R 8 Examples include heteroaromatic groups having 3 to 30 carbon atoms that may be substituted as such.

[0132] <R 11 to R 15 >

[0133] R 11 to R 15 As an alkyl group having 1 to 18 carbon atoms that may be substituted as, the aforementioned R 1 to R 8 Examples include alkyl groups having 1 to 18 carbon atoms that may be substituted as such.

[0134] R 11 to R 15As an alkeneyl group having 1 to 18 carbon atoms, the aforementioned R 1 to R 8 Examples include alkenyl groups having 1 to 18 carbon atoms.

[0135] R 11 to R 15 As a cycloalkyl group having 1 to 18 carbon atoms, the aforementioned R 1 to R 8 Examples include cycloalkyl groups having 1 to 18 carbon atoms.

[0136] R 11 to R 15 As a bicycloalkyl group having 1 to 18 carbon atoms, the aforementioned R 1 to R 8 Examples include bicycloalkyl groups having 1 to 18 carbon atoms.

[0137] R 11 to R 15 As a tricycloalkyl group having 1 to 20 carbon atoms, the aforementioned R 1 to R 8 Examples include tricycloalkyl groups having 1 to 20 carbon atoms as such.

[0138] R 11 to R 15 As an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted as, the aforementioned R 1 to R 8 Examples include aromatic hydrocarbon groups having 6 to 30 carbon atoms that may be substituted as such.

[0139] R 11 to R 15 As a heteroaromatic group having 3 to 30 carbon atoms that may be substituted as, the aforementioned R 1 to R 8Examples include heteroaromatic groups having 3 to 30 carbon atoms that may be substituted as such.

[0140] R 24 to R 26 As an alkyl group having 1 to 18 carbon atoms that may be substituted as, the aforementioned R 1 to R 8 Examples include alkyl groups having 1 to 18 carbon atoms that may be substituted as such.

[0141] R 24 to R 26 As an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted as, the aforementioned R 1 to R 8 Examples include aromatic hydrocarbon groups having 6 to 30 carbon atoms that may be substituted as such.

[0142] R 24 to R 26 As a heteroaromatic group having 3 to 30 carbon atoms that may be substituted as, the aforementioned R 1 to R 8 Examples include heteroaromatic groups having 3 to 30 carbon atoms that may be substituted as such.

[0143] <R A >

[0144] R A As an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted as, the aforementioned R 1 to R 8 Examples include aromatic hydrocarbon groups having 6 to 30 carbon atoms that may be substituted as such.

[0145] R A As a heteroaromatic group having 3 to 30 carbon atoms that may be substituted as, the aforementioned R 1 to R 8Examples include heteroaromatic groups having 3 to 30 carbon atoms that may be substituted as such.

[0146] <l>

[0147] Examples of alkylene groups having 1 to 18 carbon atoms as L include methylene groups, ethane-1,2-diyl groups, propane-1,3-diyl groups, butane-1,4-diyl groups, pentane-1,5-diyl groups, hexane-1,6-diyl groups, heptane-1,7-diyl groups, octane-1,8-diyl groups, nonane-1,9-diyl groups, and decane-1,10-diyl groups.

[0148] Examples of divalent aromatic hydrocarbon groups having 6 to 30 carbon atoms that may be substituted as L include, for instance, phenylene group, biphenylene group, terphenylene group, naphthylene group, phenylnaphthalene-diyl group, binaphthalene group, fluorene-diyl group, benzofluorene-diyl group, dibenzofluorene-diyl group, phenanthrene-diyl group, fluoranthene-diyl group, anthracene-diyl group, chrysene-diyl group, pyrene-diyl group, triphenylene-diyl group, or perylene-diyl group.

[0149] As a divalent heteroaromatic group having 3 to 30 carbon atoms that may be substituted as L, for example, pyrrole-diyl group, thiophene-diyl group, furan-diyl group, imidazole-diyl group, thiazole-diyl group, isothiazol-diyl group, oxazole-diyl group, isoxazole-diyl group, pyridine-diyl group, pyrimidine-diyl group, pyrazine-diyl group, triazine-diyl group, indole-diyl group, benzothiophene-diyl group, benzofuran-diyl group, benzimidazole-diyl group, benzothiazol-diyl group, benzisothiazole-diyl group, 2,1,3-benzothiadiazole-diyl group, benzoxazole-diyl group, Benzoisooxazole-diyl group, 2,1,3-benzoxadiazole-diyl group, thienothiophene-diyl group, dithienothiophene-diyl group, benzodithiophene-diyl group, quinoline-diyl group, isoquinoline-diyl group, quinoxaline-diyl group, phenanthroline-diyl group, dibenzothiophene-diyl group, benzothienobenzothiophene-diyl group, dibenzofuran-diyl group, carbazole-diyl group, phenoxazine-diyl group, phenothiazine-diyl group, thianthrene-diyl group, phenylthiophene-diyl group, diphenylthiophene-diyl group, phenylfuran-diyl group, diphenylfuran-diyl group, thiophene-diyl group, Examples include terthiophene-diyl groups, phenylpyridine-diyl groups, or bipyridine-diyl groups.

[0150] In the above equation (1), R 1 to R 8 It is preferable that any two adjacent ones combine with each other to form a ring represented by the following formula (3):

[0151]

[0152] Among the (3) formulas,

[0153] R 31 to R 34 Each independently comprises a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR 21 R 22 or -OR 23 Representing;

[0154] Adjacent R 31 to R 34 They may combine with each other to form a ring;

[0155] The carbon atom of * is R 1 to R 8 It represents a carbon atom in the six-membered aromatic ring of the above formula (1), in which two adjacent atoms of either one are bonded.

[0156] The preferred aspect of the definition in the above equation (3) is as follows.

[0157] <R 31 to R 34 >

[0158] R 31 to R 34 As an alkyl group having 1 to 18 carbon atoms that may be substituted as, the aforementioned R 1 to R 8 Examples include alkyl groups having 1 to 18 carbon atoms that may be substituted as such.

[0159] R 31 to R 34 As an alkeneyl group having 1 to 18 carbon atoms, the aforementioned R 1 to R 8 Examples include alkenyl groups having 1 to 18 carbon atoms.

[0160] R 31 to R 34 As a cycloalkyl group having 1 to 18 carbon atoms, the aforementioned R 1 to R 8 Examples include cycloalkyl groups having 1 to 18 carbon atoms.

[0161] R 31 to R 34 As a bicycloalkyl group having 1 to 18 carbon atoms, the aforementioned R 1 to R 8 Examples include bicycloalkyl groups having 1 to 18 carbon atoms.

[0162] R 31 to R 34 As a tricycloalkyl group having 1 to 20 carbon atoms, the aforementioned R 1 to R 8 Examples include tricycloalkyl groups having 1 to 20 carbon atoms as such.

[0163] R 31 to R 34 As an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted as, the aforementioned R 1 to R 8 Examples include aromatic hydrocarbon groups having 6 to 30 carbon atoms that may be substituted as such.

[0164] R 31 to R 34 As a heteroaromatic group having 3 to 30 carbon atoms that may be substituted as, the aforementioned R 1 to R 8 Examples include heteroaromatic groups having 3 to 30 carbon atoms that can be substituted as such.

[0165] It is preferable that the condensed ring compound represented by the above formula (1) is a condensed ring compound represented by the following formula (1A) or (1B):

[0166]

[0167] Among formulas (1A) and (1B), ring A, R 1 to R 8 and R 31 to R 34 is the ring A, R of the above equations (1) and (3). 1 to R 8 and R 31 to R 34 It represents the same energy as.

[0168] It is preferable that the condensed ring compound represented by the above formula (1) is a condensed ring compound represented by any one of the following formulas (1C) to (1E):

[0169]

[0170] Among formulas (1C) to (1E), R 1 to R 8 , R 11 to R 15 , R A and L is R of the above equations (1) and (2). 1 to R 8 , R 11 to R 15 , R A and represents groups such as L;

[0171] However, an alkyl group having 1 to 18 carbon atoms that may be substituted, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR 21 R 22 A group having a donor substituent selected from is R 1 to R 4 It may be at least one of them, and R 5 to R 8 At least one of them may be used.

[0172] In the condensation ring compounds represented by the above formulas (1C) to (1E), R 1 and R 2 , R 3 and R 4 , R 5 and R 6 or R 7 and R 8 It is preferable that one of them combines with each other to form a ring represented by the above formula (3).

[0173] In the condensed ring compounds represented by the above formulas (1), (1A) and (1B), it is preferable that ring A has a structure represented by the following formula (2A) or (2B):

[0174]

[0175] Among equations (2A) and (2B),

[0176] X 1 To X 3 represents a carbon atom shared with ring B, and

[0177] R 11 to R 15 , R A and L is R of the above equation (2). 11 to R 15 , R A It represents the same group as and L.

[0178] It is preferable that the condensed ring compound represented by the above formula (1) is a condensed ring compound represented by the following formula (1F):

[0179]

[0180] Among the formula (1F),

[0181] R 35 to R 38 Each independently comprises a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR 21 R 22 or -OR 23 Representing;

[0182] Adjacent R 35 to R 38 They may combine with each other to form rings;

[0183] R 1 to R 4 , R 11 to R 15 , R 31 to R 34 , R A and L is R of the above equations (1) and (3). 1 to R 4 , R 11 to R 15 , R 31 to R 34 , R A It represents the same group as and L.

[0184] In the condensation ring compound represented by the above formula (1F), the adjacent R 1 to R 4 and R 31 to R 38 It is desirable that the rings do not combine with each other to form a ring.

[0185] In the condensed ring compound represented by the above formula (1F), it is preferable that L be a phenylene group that may be substituted, a biphenylene group that may be substituted, a terphenylene group that may be substituted, a naphthylene group that may be substituted, or a single bond.

[0186] In the condensation ring compound represented by the above formula (1F), R 1 to R 4 , R 11 to R 15 , R 31 to R 38 and R A Each independently hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, n-hexyl group, cyclohexyl group, octyl group, decyl group, dodecyl group, octadecyl group, adamantyl group, diamantyl group, substituted phenyl group, substituted biphenylyl group, substituted terphenylyl group, substituted naphthyl group, substituted fluorenyl group, substituted spirobifluorenyl group, substituted benzoflurenyl group, substituted phenanthyl group, substituted fluoranthenyl group, substituted triphenylenyl group, substituted anthryl group, substituted pyrenyl group, substituted carbazolyl group, substituted dibenzofuranyl group, substituted Divenzotien Diary, -NR 21 R 22 and -OR 23 It is a group selected from the group consisting of;

[0187] R 21 to R 23 It is preferable that each of these is independently selected from the group consisting of a hydrogen atom, an adamantyl group, adiamantyl group, a substituted phenyl group, a substituted biphenylyl group, a substituted terphenylyl group, a substituted naphthyl group, a substituted fluorenyl group, a substituted spirobifluorenyl group, a substituted benzofluorenyl group, a substituted phenanthyl group, a substituted fluoranthenyl group, a substituted triphenylenyl group, a substituted anthryl group, a substituted pyrenyl group, a substituted carbazolyl group, a substituted dibenzofuranyl group, and a substituted dibenzothienyl group.

[0188] In the condensation ring compound represented by the above formula (1F), R 31 to R 38 It is desirable that this be a hydrogen atom.

[0189] Physical properties of condensation ring compounds

[0190] Below, the desirable properties of the condensed ring compound represented by formula (1) are described.

[0191] (HOMO value)

[0192] The HOMO value of the condensed ring compound represented by Equation (1) is not particularly limited, but is preferably 5.0 to 6.5 eV from the perspective of suitability for photoelectric conversion devices. Also, this HOMO value is a value obtained from the measurement of the number of photoelectrons in the atmosphere using an atmospheric photoelectron spectrometer for the deposited film.

[0193] (Band gap)

[0194] The band gap of the condensed ring compound represented by Equation (1) is not particularly limited, but is preferably 2.5 to 4.0 eV from the perspective of suitability for photoelectric conversion devices. Also, this band gap is a value obtained from the wavelength range of the absorption spectrum of the deposited film.

[0195] (LUMO value)

[0196] The LUMO value of the condensed ring compound represented by Equation (1) is not particularly limited, but is preferably 2.0 to 3.5 eV from the perspective of suitability for photoelectric conversion devices. Also, this LUMO value is a value obtained from the above HOMO value and band gap.

[0197] (Glass transition temperature)

[0198] The glass transition temperature of the condensed ring compound represented by Equation (1) is not particularly limited, but it is preferably 130°C or higher from the perspective of suitability for photoelectric conversion devices. Also, this glass transition temperature is a value obtained from differential scanning calorimetry.

[0199] (Molecular weight)

[0200] The molecular weight of the condensed ring compound represented by formula (1) is not particularly limited, but is preferably 600 or more and less than 1000 from the perspective of heat stability during sublimation.

[0201] <Specific examples of condensed ring compounds>

[0202] Below, preferred compounds are exemplified for the condensed ring compound represented by Formula (1), but the condensed ring compound is not limited to these compounds.

[0203] <Preferred Specific Example of a Condensed Ring Compound>

[0204] Below, preferred compounds are exemplified for the condensed ring compound represented by Formula (1), but the condensed ring compound is not limited to these compounds.

[0205] Among the backbones of (Aa) to (Ej) shown in Tables 1 to 3, a compound in which substituent R is one group n selected from the groups shown in Tables 4 to 6 is defined as (Lm-n).

[0206] Here, Lm represents any symbol from Aa to Ej, and n represents any integer from 1 to 115. For example, in the case of a compound called (Ab-2), it has the backbone of (Ab) and indicates that the substituent R of the backbone is a methyl group.

[0207]

[0208]

[0209]

[0210]

[0211]

[0212]

[0213] Applications of materials for photoelectric conversion devices

[0214] The aforementioned material for a photoelectric conversion device is suitably used, for example, as a material for a photoelectric conversion device for an imaging device. As a material for a photoelectric conversion device for an imaging device, for example, a charge transport material for a photoelectric conversion device for an imaging device or a charge blocking material for a photoelectric conversion device for an imaging device is preferred. As a charge transport material for a photoelectric conversion device for an imaging device, for example, a hole transport material for a photoelectric conversion device for an imaging device is preferred. As a charge blocking material for a photoelectric conversion device for an imaging device, for example, an electron blocking material for a photoelectric conversion device for an imaging device is preferred.

[0215] The aforementioned materials for photoelectric conversion devices are also suitably used as materials for organic electronic devices. Examples of organic electronic devices include organic electroluminescence devices and organic photoelectric conversion devices. Examples of materials for organic electronic devices include materials for organic electroluminescence devices and materials for organic photoelectric conversion devices. It is preferable to use the aforementioned materials for organic electronic devices as organic thin films.

[0216] Preferred aspects of a material for a photoelectric conversion device comprising the aforementioned condensed ring compound include an organic thin film comprising the material for the photoelectric conversion device, a photoelectric conversion device comprising the material for the photoelectric conversion device, a photoelectric conversion device comprising the material for the photoelectric conversion device in a photoelectric conversion layer, and a photoelectric conversion device comprising the material for the photoelectric conversion device in a hole transport layer or an electron blocking layer.

[0217] Hereinafter, as an example, a photoelectric conversion element for an imaging element according to the present embodiment will be described.

[0218] Photoelectric conversion device for imaging sensors

[0219] The photoelectric conversion element for an imaging element of this embodiment includes the aforementioned charge transport material for a photoelectric conversion element for an imaging element.

[0220] The configuration of the photoelectric conversion element for the imaging element is not particularly limited, but for example, the configurations (i) to (v) shown below may be cited.

[0221] (i) Lower electrode / photoelectric conversion layer / upper electrode

[0222] (ii) Bottom electrode / Electron transport layer (hole blocking layer) / Photoelectric conversion layer / Top electrode

[0223] (iii) Bottom electrode / Photoelectric conversion layer / Hole transport layer (Electron blocking layer) / Top electrode

[0224] (iv) Bottom electrode / Electron transport layer (hole blocking layer) / Photoconversion layer / Hole transport layer (Electron blocking layer) / Top electrode

[0225] (v) Bottom electrode / Electron transport layer (hole blocking layer) / Photoelectric conversion layer / Hole transport layer (Electron blocking layer) / Buffer layer / Top electrode

[0226] In addition, the buffer layer may be replaced with a layer having a different name or function as needed. Examples of layers having a different name or function include a hole injection layer, a work function adjustment layer, etc.

[0227] A preferred layer configuration of a photoelectric conversion element for an imaging device may 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. Another preferred layer configuration of a photoelectric conversion element for an imaging device may 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.

[0228] It is preferable that the photoelectric conversion device for an imaging device comprises the aforementioned photoelectric conversion device 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, it is preferable that the photoelectric conversion device for an imaging device comprises the aforementioned photoelectric conversion device material in the photoelectric conversion layer and / or the hole transport layer (electron blocking layer), and it is more preferable that the hole transport layer (electron blocking layer) comprises the aforementioned photoelectric conversion device material. Additionally, the photoelectric conversion device material may be included in a plurality of layers provided by the photoelectric conversion device for an imaging device.

[0229] Hereinafter, a photoelectric conversion element for an imaging element according to the present embodiment will be described in more detail with reference to FIG. 1, using the configuration of (v) as an example. FIG. 1 is a schematic cross-sectional view showing an example of a stacked configuration of a photoelectric conversion element for an imaging element including a hole transport material for a photoelectric conversion element for an imaging element or an electron blocking material for a photoelectric conversion element for an imaging element according to the present embodiment.

[0230] The photoelectric conversion element (100) for an imaging element of FIG. 1 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) in this order. In addition, in the photoelectric conversion element for an imaging element of the present embodiment, some of these layers may be omitted, or other layers may be added.

[0231] In the photoelectric conversion element (100) for an imaging element, light is incident from below the transparent lower electrode (2). Additionally, the photoelectric conversion element (100) for an imaging element applies a voltage such that among the charges (holes and electrons) generated in the photoelectric conversion layer (4), electrons move to the lower electrode (2) and holes move to the upper electrode (7). That is, the photoelectric conversion element (100) for an imaging element has the lower electrode (2) as an electron collecting electrode and the upper electrode (7) as a hole collecting electrode.

[0232] [Layer containing charge transport material for photoelectric conversion devices for imaging devices]

[0233] The photoelectric conversion device (100) for an imaging device comprises a photoelectric conversion device material for an imaging device in at least one layer selected from the group consisting of an electron transport layer (hole blocking layer) (3), a photoelectric conversion layer (4), a hole transport layer (electron blocking layer) (5), and a buffer layer (6). It is preferable that the photoelectric conversion device (100) for an imaging device comprises a charge transport material for an imaging device or a charge blocking material for an imaging device in the photoelectric conversion layer (4) and / or the hole transport layer (electron blocking layer) (5), and it is more preferable that the hole transport layer (electron blocking layer) comprises a charge transport material for an imaging device or a charge blocking material for an imaging device. Additionally, the charge transport material for the photoelectric conversion element for the imaging element or the charge blocking material for the photoelectric conversion element for the imaging element may be included in a plurality of layers provided by the photoelectric conversion element (100) for the imaging element.

[0234] Hereinafter, a photoelectric conversion device (100) for an imaging device is described, wherein the hole transport layer (electron blocking layer) (5) comprises a hole transport material for an imaging device or an electron blocking material for an imaging device.

[0235] [Board (1)]

[0236] There are no particular limitations on the substrate, and examples include glass plates, quartz plates, plastic plates, etc. In the case of a configuration in which light is incident from the side of the substrate (1), it is desirable for the substrate (1) to have high transmittance with respect to the wavelength of light (for example, transmittance of 80% or more, preferably transmittance of 90% or more).

[0237] [Lower electrode (2)]

[0238] A lower electrode (2) is installed on the substrate (1).

[0239] In the case of a photoelectric conversion element for an imaging device configured such that light passes through the lower electrode (2) and is incident on the photoelectric conversion layer, it is desirable that the lower electrode (2) has high transmittance with respect to the wavelength of the incident light (e.g., transmittance of 80% or more, preferably transmittance of 90% or more).

[0240] The transparent material used for the lower electrode (2) is not particularly limited. From the perspective of excellent light transmittance, the material constituting the lower electrode (2) may be, for example, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide, aluminum-doped tin oxide, magnesium indium oxide, nickel tungsten oxide, other metal oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, metal sulfides such as zinc sulfide.

[0241] Also, in the case of a photoelectric conversion element for an imaging device configured such that light is incident on the photoelectric conversion layer only from the upper electrode (7), the transmission characteristics of the lower electrode (2) are not important. Therefore, as an example of a material used for the lower electrode (2) in this case, it may be gold, iridium, molybdenum, palladium, platinum, etc.

[0242] [Electron transport layer (hole blocking layer) (3)]

[0243] Between the lower electrode (2) and the photoelectric conversion layer (4), an electron transport layer (hole blocking layer) (3) is installed.

[0244] The electron transport layer (hole blocking layer) (3) has the role of transporting electrons generated in the photoelectric conversion layer (4) to the lower electrode (2) and blocking holes generated in the photoelectric conversion layer (4) from moving to the lower electrode (2).

[0245] The electron transport layer (hole blocking layer) (3) may be a single-layer structure made of one or more types of materials, or a stacked structure made of multiple layers of the same composition or different compositions. The electron transport layer (hole blocking layer) (3) may be a two-layer structure including, for example, a layer adjacent to a photoelectric conversion layer (4) made of a material specialized for hole blocking properties, and a layer adjacent to a lower electrode (2) made of a material specialized for electron transport properties.

[0246] The electron transport layer (hole blocking layer) (3) may be a layer containing a conventionally known electron transport material. Examples of conventionally known electron transport materials include bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, BCP(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen(4,7-diphenyl-1,10-phenanthroline), BAlq(bis(2-methyl-8-quinolinoleate)-4-(phenylphenolate)aluminum), 4,6-bis(3,5-di(pyridine-4-yl)phenyl)-2-methylpyrimidine, N,N'-diphenyl-1,4,5,8-naphthalene carboxylic acid diimide, and Examples include N,N'-di(4-pyridyl)-1,4,5,8-naphthalene carboxylic acid diimide.

[0247] [Photoelectric conversion layer (4)]

[0248] A photoelectric conversion layer (4) is installed 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) includes a material having a photoelectric conversion function.

[0249] The photoelectric conversion layer (4) may be an organic material or an inorganic material, and it is sufficient if it can generate a signal charge according to the amount of light received. When the photoelectric conversion layer (4) is composed of an organic material, it may be a single-layer structure made of one or more types of materials, or a stacked structure made of multiple layers of the same composition or different compositions. Materials used for the photoelectric conversion layer (4) include n-type semiconductors and p-type semiconductors. The n-type semiconductor is an acceptor-type organic semiconductor, and a compound that is easy to accept electrons and has high electron transport is used. The p-type semiconductor is a donor-type organic semiconductor, and a compound that is easy to donate electrons and has high hole transport is used. When multiple materials are used for the photoelectric conversion layer (4), combinations thereof may include, for example, an n-type semiconductor and a p-type semiconductor, an n-type semiconductor and a compound with lower acceptor properties than the n-type semiconductor, a p-type semiconductor and a compound with lower donor properties than the p-type semiconductor, etc. Each ingredient may be of one type, or two or more types of ingredients may be used.

[0250] The photoelectric conversion layer (4) may include a pigment compound with excellent absorption of a specific light. The pigment compound may be a compound with lower acceptor properties than the n-type semiconductor, or a compound with lower donor properties than the p-type semiconductor. In terms of improving photoelectric conversion efficiency, it is preferable that the photoelectric conversion layer (4) further include a pigment compound in addition to the n-type semiconductor and the p-type semiconductor. 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, naphthalene tetracarboxylic acid diimide, hole transport materials, etc.

[0251] The photoelectric conversion layer (4) made of these materials may be formed, for example, by deposition using a mixed powder in which the powders of each material are mixed, or by co-depositing each material in any ratio.

[0252] Specific examples of coumarin derivatives include coumarin 6, coumarin 30, etc. Specific examples of quinacridone derivatives include N,N-dimethylquinacridone, etc. Specific examples of phthalocyanine derivatives include boron subphthalocyanine chloride, boron subnaphthalocyanine chloride (SubNC), F6-SubPC-OC6F5, Cl6-SubPC-OC6, etc.

[0253] Specific examples of fullerenes and their derivatives include

[60] fullerene,

[70] fullerene, [6,6]-phenyl-C61-butyric acid methyl (

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

[0254] Specific examples of hole transport materials include 9,9'-(9,9'-spirobi[9H-fluorene]-2,7'-diyl)bis[9H-carbazole], 2,7-diphenyl[1]benzothieno[3,2-b][1]benzothiophene (DiPh-BTBT), benzo[1,2-b:3,4-b':5,6-b'']trifuran compound, benzo[1,2-b:3,4-b':5,6-b''trithiophene compound, naphtho[1,2-b:5,6-b']dithiophene, naphtho[2,3-b]naphtho[2',3':4,5]thieno[2,3-d]thiophene, and benzo[1,2-b:4,5-b']difuran. Examples include benzo[1,2-b:4,5-b']dithiophene, benzo[1,2-b:4,5-b']bis[1]benzothiophene, naphtho[1,2-b:5,6-b']bis[1]benzothiophene, chryseno[1,2-b:8,7-b']dithiophene, [1]benzothieno[3,2-b][1]benzothiophene, compounds represented by the following formula (ic-1), compounds represented by the following formula (ic-2), etc.

[0255]

[0256] Additionally, the material having the aforementioned 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, layers adjacent to the photoelectric conversion layer (4) (electron transport layer (hole blocking layer) (3), hole transport layer (electron blocking layer) (5)) may contain the material having the photoelectric conversion function.

[0257] [Hole transport layer (electron blocking layer) (5)]

[0258] A hole transport layer (electron blocking layer) (5) is installed between the photoelectric conversion layer (4) and the buffer layer (6) described later.

[0259] The hole transport layer (electron blocking layer) (5) has the role of transporting holes generated in the photoelectric conversion layer (4) to the upper electrode (7) side and blocking electrons generated in the photoelectric conversion layer (4) from moving to the upper electrode (7) side. The hole transport layer (electron blocking layer) (5) preferably includes the aforementioned charge transport material for the photoelectric conversion element for the imaging element or the charge blocking material for the photoelectric conversion element for the imaging element.

[0260] The hole transport layer (electron blocking layer) (5) may be a single-layer structure made of one or more types of materials, or a stacked structure made of multiple layers of the same composition or different compositions. The hole transport layer (electron blocking layer) (5) may be a two-layer structure, for example, including a layer adjacent to a photoelectric conversion layer (4) made of a material specialized for electron blocking properties, and a layer adjacent to a buffer layer (6) made of a material specialized for hole transport properties.

[0261] The hole transport layer (electron blocking layer) (5) may include, in addition to the aforementioned photoelectric conversion element material for the imaging element, a conventionally known hole transport material. Preferred compounds and specific examples of the conventionally known hole transport material include the same as the hole transport material described in the item of the photoelectric conversion layer (4).

[0262] A buffer layer (6) is installed between the hole transport layer (electron blocking layer) (5) and the upper electrode (7) described later. When the upper electrode (7) is formed by a sputtering method, the buffer layer (6) serves to reduce damage to the organic layer (e.g., the hole transport layer (electron blocking layer) (5)) during sputtering. Additionally, by adjusting the work function of the buffer layer (6), it also serves to efficiently receive holes from the hole transport layer (electron blocking layer) (5), and is therefore also called a hole injection layer or a work function adjustment layer.

[0263] The material constituting the buffer layer (6) may be a known material, for example, naphthalene-1,4,5,8-tetracarboxylic acid dianhydride (NTCDA), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN), etc.

[0264] [Upper electrode (7)]

[0265] An upper electrode (7) is installed on the buffer layer (6). The material of the upper electrode (7) is not particularly limited and may be, for example, sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, silver, magnesium / silver mixture, aluminum, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al2O3) mixture, indium, lithium / aluminum mixture, rare earth metal, etc.

[0266] [Method of forming each layer]

[0267] Each layer other than the lower electrode (2) and the upper electrode (7) can be formed by thinning the material of each layer (further materials such as binding resin, solvent, etc., as needed) by known methods such as vacuum deposition, spin coating, casting, or the LB (Langmuir-Blodgett method). The thickness of each layer other than the lower electrode (2) and the upper electrode (7) is not particularly limited and can be appropriately selected depending on the situation. The thickness of each layer other than the lower electrode (2) and the upper electrode (7) is usually in the range of 5 nm or more and 5 μm or less.

[0268] The lower electrode (2) and the upper electrode (7) can be formed by thinning the electrode material by methods such as deposition or sputtering.

[0269] If the lower electrode (2) and the upper electrode (7) have a pattern, for example, the pattern can be formed by interposing a mask of the desired shape. Alternatively, after forming a thin film by deposition, sputtering, etc., the pattern of the desired shape may be formed by photolithography.

[0270] The film thickness of the lower electrode (2) and the upper electrode (7) may be 1 μm or less, and preferably 10 nm or more and 200 nm or less.

[0271] The lower electrode (2) and the upper electrode (7) can have their respective constituent materials replaced as needed (also called an inverted structure). In this structure, light passes through the upper electrode (7) and is incident on the photoelectric conversion layer (4), forming a photoelectric conversion element for an imaging device.

[0272] An imaging element equipped with a photoelectric conversion element according to the present embodiment can be applied, for example, to an imaging element such as a digital camera, a digital video camera, and an imaging element embedded in a mobile phone.

[0273] Although preferred embodiments of the present invention have been described above, the present invention is not limited to the above embodiments.

[0274] Hereinafter, a condensed ring compound according to one aspect of the present disclosure will be described in detail.

[0275] ≪ Condensed Ring Compounds ≫

[0276] A condensation ring compound according to one aspect of the present disclosure is represented by the following formula (4):

[0277]

[0278] Among the formulas (4),

[0279] Ring A represents a structure indicated by the following formula (5);

[0280] R a1 to R a8 Each independently comprises a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR a21 R a22 or -OR a23 Representing;

[0281] R a21 to R a23 Each represents an alkyl group having 1 to 18 carbon atoms that may be independently substituted, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, or a heteroaromatic group having 3 to 30 carbon atoms that may be substituted;

[0282] R a1 to R a8 They may combine with each other to form rings;

[0283] However, R a1 to R a4 At least one of the following is an alkyl group having 1 to 18 carbon atoms that may be substituted, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR a21 R a22 A group having a donor substituent selected from;

[0284] R a1 to R a8 Any two adjacent ones combine with each other, and a ring is formed as shown in the following equation (6):

[0285]

[0286] Among the (5) formulas,

[0287] X a1 To X a4 Of these, the two adjacent atoms represent carbon atoms shared with ring B, and the rest are CR a15 Representing;

[0288] R a11 to R a15 Each independently comprises a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR a24 R a25 or -OR a26 Representing;

[0289] R a24 to R a26 Each represents an alkyl group having 1 to 18 carbon atoms that may be independently substituted, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, or a heteroaromatic group having 3 to 30 carbon atoms that may be substituted;

[0290] R aA ...represents an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, or a heteroaromatic group having 3 to 30 carbon atoms that may be substituted;

[0291] L a It represents an alkylene group having 1 to 18 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a divalent heteroaromatic group having 3 to 30 carbon atoms that may be substituted, or a single bond.

[0292]

[0293] Among the formulas (6),

[0294] R a31 to R a34 Each independently comprises a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR a21 R a22 or -OR a23 Representing;

[0295] Adjacent R a31 to R a34 They may combine with each other to form a ring;

[0296] The carbon atom of * is R a1 to R a8 It represents a carbon atom in the six-membered aromatic ring of the above formula (4), in which two adjacent atoms of either one are bonded.

[0297] In the above formula (4), the compound represented by the above formula (4) is desirable for fabricating photoelectric conversion devices that have low dark current, high external quantum efficiency, and excellent responsiveness, by having a group having the above donor substituent as ring A and having the structure represented by the above formula (5). For this reason, the compound represented by the above formula (4) is suitablely used as a material for photoelectric conversion devices.

[0298] Specific examples and preferred aspects of the definitions in the above formulas (4) to (6) are as follows.

[0299] <R a1 to R a8 >

[0300] R a1 to R a8 Examples of alkyl groups having 1 to 18 carbon atoms that may be substituted as such include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isovaleryl group, n-hexyl group, i-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, cyclohexyl group, octyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-octadecyl group, n-tridecyl group, n-tetradecyl group, 2-ethylhexyl group, 3-ethylheptyl group, 3-ethyldecyl, 2-hexyldecyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, etc.

[0301] R a1 to R a8 Examples of alkeneyl groups having 1 to 18 carbon atoms include, for instance, an etheneyl group, a propeneyl group, a buteneyl group, a 2-methylpropeneyl group, an n-penteneyl group, a 2-methylbuteneyl group, an n-hexeneyl group, a 2-methylpenteneyl group, an n-hepteneyl group, an n-octenyl group, a 2-ethylhexeneyl group, an n-nonel group, a 2-ethylhepteneyl group, an n-deceneyl group, an n-dodeceneyl group, a cyclopenteneyl-1- group, a cyclohexeneyl-1- group, a cyclohepteneyl-1- group, and the like.

[0302] R a1 to R a8 Examples of cycloalkyl groups having 1 to 18 carbon atoms include cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, cyclooctyl groups, cyclononyl groups, cyclodecyl groups, cyclolondecyl groups, cyclododecyl groups, etc. The cycloalkyl groups may be substituted with alkyl groups having 1 to 4 carbon atoms. Examples of alkyl groups having 1 to 4 carbon atoms include methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, cyclopropylmethyl groups, 2-methylpropyl groups, 2,2-dimethylpropyl groups, cyclopropyl groups, tert-butyl groups, cyclobutyl groups, etc.

[0303] R a1 to R a8 Examples of bicycloalkyl groups having 1 to 18 carbon atoms include novonyl groups, 3-finanyl groups, bicyclo[3.1.0]hexyl groups, bicyclo[2.2.1]heptyl groups, bicyclo[2.2.2]octo-2-yl groups.

[0304] R 1 to R 8 Examples of tricycloalkyl groups having 1 to 20 carbon atoms include adamantyl groups, noradamantyl groups, diamantyl groups, etc.

[0305] R a1 to R a8 As an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted as, for example, a phenyl group that may be substituted, a biphenylyl group that may be substituted, a terphenylyl group that may be substituted, a naphthyl group that may be substituted, an anthryl group that may be substituted, a phenanthryl group that may be substituted, a pyrenyl group that may be substituted, a crisenyl group that may be substituted, a benzocrysenyl group that may be substituted, a dibenzocrysenyl group that may be substituted, a fluorenyl group that may be substituted, a benzofluorenyl group that may be substituted, a fluoranthenyl group that may be substituted, a triphenylenyl group that may be substituted, a spirobifluorenyl group that may be substituted, a naphthylphenyl group that may be substituted, a phenylnaphthyl group that may be substituted, a naphthylnaphthyl group that may be substituted, a phenanthrylphenyl group that may be substituted, a diphenylfluorenyl group that may be substituted, and a group that may be substituted Examples include dibenzo[g, p]crisenyl groups.

[0306] R a1 to R a8 As a heteroaromatic group having 3 to 30 carbon atoms that may be substituted as, for example, a dibenzofuranyl group that may be substituted, a dibenzothionyl group that may be substituted, a carbazolyl group that may be substituted, a dibenzofuranylphenyl group that may be substituted, a dibenzothionylphenyl group that may be substituted, a carbazolylphenyl group that may be substituted, a pyrrolyl group that may be substituted, a thienyl group that may be substituted, a furyl group that may be substituted, an imidazolyl group that may be substituted, a pyrazolyl group that may be substituted, a thiazolyl group that may be substituted, an isothiazolyl group that may be substituted, an oxazolyl group that may be substituted, an isoxazolyl group that may be substituted, a pyridyl group that may be substituted, a phenylpyridyl group that may be substituted, a pyridylphenyl group that may be substituted, a pyrimidyl group that may be substituted, a pyrazyl group that may be substituted 1,3,5-triazyl group, optionally substituted 1,3,5-triazylphenyl group, optionally substituted 1,3,5-triazylbiphenylyl group, optionally substituted 4,6-diphenyl-1,3,5-triazyl group, optionally substituted indolyl group, optionally substituted benzothienyl group, optionally substituted benzofuranyl group, optionally substituted benzimidazolyl group, optionally substituted indazolyl group, optionally substituted benzothiazolyl group, optionally substituted benzisothiazolyl group, optionally substituted 2,1,3-benzothiadiazolyl group, optionally substituted benzoxazolyl group, optionally substituted benzisooxazolyl group, optionally substituted 2,1,3-benzoxadiazolyl group, optionally substituted quinolyl group, optionally substituted isoquinolyl group, optionally substituted Optional quinoxalyl group, optional substituted quinazolyl group, optional substituted carbazolyl group, optional substituted 9-phenylcarbazolyl group, optional substituted 9-(4-biphenylyl)carbazolyl group, optional substituted dibenzothienyl group,Examples include a dibenzofuranyl group that may be substituted, a phenoxysaline group that may be substituted, a phenothiazine group that may be substituted, a phenazine group that may be substituted, a thiantrenyl group that may be substituted, etc.

[0307] R a21 to R a23 As an alkyl group having 1 to 18 carbon atoms that may be substituted as, the aforementioned R a1 to R a8 Examples include alkyl groups having 1 to 18 carbon atoms that may be substituted as such.

[0308] R a21 to R a23 As an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted as, the aforementioned R a1 to R a8 Examples include aromatic hydrocarbon groups having 6 to 30 carbon atoms that may be substituted as such.

[0309] R a21 to R a23 As a heteroaromatic group having 3 to 30 carbon atoms that may be substituted as, the aforementioned R a1 to R a8 Examples include heteroaromatic groups having 3 to 30 carbon atoms that can be substituted as such.

[0310] <R a11 to R a15 >

[0311] R a11 to R a15 As an alkyl group having 1 to 18 carbon atoms that may be substituted as, the aforementioned R a1 to R a8 Examples include alkyl groups having 1 to 18 carbon atoms that may be substituted as such.

[0312] R a11 to R a15 As an alkeneyl group having 1 to 18 carbon atoms, the aforementioned R a1 to R a8 Examples include alkenyl groups having 1 to 18 carbon atoms.

[0313] R a11 to R a15 As a cycloalkyl group having 1 to 18 carbon atoms, the aforementioned R a1 to R a8 Examples include cycloalkyl groups having 1 to 18 carbon atoms.

[0314] R a11 to R a15 As a bicycloalkyl group having 1 to 18 carbon atoms, the aforementioned R a1 to R a8 Examples include bicycloalkyl groups having 1 to 18 carbon atoms.

[0315] R a11 to R a15 As a tricycloalkyl group having 1 to 20 carbon atoms, the aforementioned R a1 to R a8 Examples include tricycloalkyl groups having 1 to 20 carbon atoms as such.

[0316] R a11 to R a15 As an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted as, the aforementioned R a1 to R a8 Examples include aromatic hydrocarbon groups having 6 to 30 carbon atoms that may be substituted as such.

[0317] R a11 to R a15 As a heteroaromatic group having 3 to 30 carbon atoms that may be substituted as, the aforementioned R a1 to R a8 Examples include heteroaromatic groups having 3 to 30 carbon atoms that can be substituted as such.

[0318] R a24 to R a26 As an alkyl group having 1 to 18 carbon atoms that may be substituted as, the aforementioned R a1 to R a8 Examples include alkyl groups having 1 to 18 carbon atoms that may be substituted as such.

[0319] R a24 to R a26 As an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted as, the aforementioned R a1 to R a8 Examples include aromatic hydrocarbon groups having 6 to 30 carbon atoms that may be substituted as such.

[0320] R a24 to R a26 As a heteroaromatic group having 3 to 30 carbon atoms that may be substituted as, the aforementioned R a1 to R a8 Examples include heteroaromatic groups having 3 to 30 carbon atoms that can be substituted as such.

[0321] <R A >

[0322] R aA As an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted as, the aforementioned R a1 to R a8 Examples include aromatic hydrocarbon groups having 6 to 30 carbon atoms that may be substituted as such.

[0323] R aA As a heteroaromatic group having 3 to 30 carbon atoms that may be substituted as, the aforementioned R a1 to R a8 Examples include heteroaromatic groups having 3 to 30 carbon atoms that can be substituted as such.

[0324] <L a >

[0325] Examples of alkylene groups having 1 to 18 carbon atoms as La include methylene groups, ethane-1,2-diyl groups, propane-1,3-diyl groups, butane-1,4-diyl groups, pentane-1,5-diyl groups, hexane-1,6-diyl groups, heptane-1,7-diyl groups, octane-1,8-diyl groups, nonane-1,9-diyl groups, and decane-1,10-diyl groups.

[0326] L a Examples of divalent aromatic hydrocarbon groups having 6 to 30 carbon atoms that may be substituted include, for instance, phenylene groups, biphenylene groups, terphenylene groups, naphthylene groups, phenylnaphthalene-diyl groups, binaphthalene groups, fluorene-diyl groups, benzofluorene-diyl groups, dibenzofluorene-diyl groups, phenanthrene-diyl groups, fluoranthene-diyl groups, anthracene-diyl groups, chrysene-diyl groups, pyrene-diyl groups, triphenylene-diyl groups, or perylene-diyl groups.

[0327] L a As a divalent heteroaromatic group having 3 to 30 carbon atoms that may be substituted as, for example, a pyrrole-diyl group, a thiophene-diyl group, a furan-diyl group, an imidazole-diyl group, a thiazole-diyl group, an isothiazol-diyl group, an oxazole-diyl group, an isoxazole-diyl group, a pyridine-diyl group, a pyrimidine-diyl group, a pyrazine-diyl group, a triazine-diyl group, an indole-diyl group, a benzothiaphen-diyl group, a benzofuran-diyl group, a benzimidazole-diyl group, a benzothiazol-diyl group, a benzisothiazole-diyl group, a 2,1,3-benzothiadiazole-diyl group, a benzoxazole-diyl group, Benzoisooxazole-diyl group, 2,1,3-benzoxadiazole-diyl group, thienothiophene-diyl group, dithienothiophene-diyl group, benzodithiophene-diyl group, quinoline-diyl group, isoquinoline-diyl group, quinoxaline-diyl group, phenanthroline-diyl group, dibenzothiophene-diyl group, benzothienobenzothiophene-diyl group, dibenzofuran-diyl group, carbazole-diyl group, phenoxazine-diyl group, phenothiazine-diyl group, thianthrene-diyl group, phenylthiophene-diyl group, diphenylthiophene-diyl group, phenylfuran-diyl group, diphenylfuran-diyl group, thiophene-diyl group, Examples include terthiophene-diyl groups, phenylpyridine-diyl groups, or bipyridine-diyl groups.

[0328] <R a31 to R a34 >

[0329] R a31 to R a34 As an alkyl group having 1 to 18 carbon atoms that may be substituted as, the aforementioned R a1 to R a8 Examples include alkyl groups having 1 to 18 carbon atoms that may be substituted as such.

[0330] R a31 to R a34 As an alkeneyl group having 1 to 18 carbon atoms, the aforementioned R a1 to R a8 Examples include alkenyl groups having 1 to 18 carbon atoms.

[0331] R a31 to R a34 As a cycloalkyl group having 1 to 18 carbon atoms, the aforementioned R a1 to R a8 Examples include cycloalkyl groups having 1 to 18 carbon atoms.

[0332] R a31 to R a34 As a bicycloalkyl group having 1 to 18 carbon atoms, the aforementioned R a1 to R a8 Examples include bicycloalkyl groups having 1 to 18 carbon atoms.

[0333] R a31 to R a34 As a tricycloalkyl group having 1 to 20 carbon atoms, the aforementioned R a1 to R a8 Examples include tricycloalkyl groups having 1 to 20 carbon atoms as such.

[0334] R a31 to R a34 As an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted as, the aforementioned R a1 to R a8 Examples include aromatic hydrocarbon groups having 6 to 30 carbon atoms that may be substituted as such.

[0335] R a31 to R a34 As a heteroaromatic group having 3 to 30 carbon atoms that may be substituted as, the aforementioned R a1 to R a8 Examples include heteroaromatic groups having 3 to 30 carbon atoms that can be substituted as such.

[0336] It is preferable that the condensed ring compound represented by the above formula (4) is a condensed ring compound represented by the following formula (4A) or (4B):

[0337]

[0338] Among formulas (4A) and (4B), ring A, R a1 to R a8 and R a31 to R a34 is the ring A, R of the above equations (4) and (6). a1 to R a8 and R a31 to R a34 It represents the same energy as.

[0339] In the condensed ring compounds represented by the above formulas (4), (4A) and (4B), R a1 and R a2 , R a3 and R a4 , R a5 and R a6 or R a7 and R a8 It is preferable that one of them combines with each other to form a ring represented by the above formula (6).

[0340] In the condensed ring compounds represented by the above formulas (4A) and (4B), it is preferable that ring A has a structure represented by the following formula (5A) or (5B):

[0341]

[0342] Among equations (5A) and (5B),

[0343] X a1 To X a3 represents a carbon atom shared with ring B, and

[0344] R a11 to R a15 , R aA and L a is R of the above equation (5). a11 to R a15 , R aA and L a It represents the same energy as.

[0345] It is preferable that the condensed ring compound represented by the above formula (4A) or (4B) is a condensed ring compound represented by the following formula (4C):

[0346]

[0347] Among the formula (4C),

[0348] R a35 to R a38 Each independently comprises a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR a21 R a22 or -OR a23 Representing;

[0349] Adjacent R a35 to R a38 They may combine with each other to form rings;

[0350] R a1 to R a4 , R a11 to R a15 , R a31 to R a34 , R aA and L a is R of the above equations (4) and (6). a1 to R a4 , R a11 to R a15 , R a31 to R a34 , R aA and L a It represents the same energy as.

[0351] In the condensation ring compound represented by the above formula (4C), the adjacent R a1 to R a4 and R a31 to R a38 It is desirable that the rings do not combine with each other to form a ring.

[0352] In the condensation ring compound represented by the above formula (4C), L a It is preferable that the group be a phenylene group that may be substituted, a biphenylene group that may be substituted, a terphenylene group that may be substituted, a naphthylene group that may be substituted, or a single bond.

[0353] In the condensation ring compound represented by the above formula (4C), R a1 to R a4 , R a11 to R a15 , R a31 to R a38 and R aA Each independently hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, n-hexyl group, cyclohexyl group, octyl group, decyl group, dodecyl group, octadecyl group, adamantyl group, diamantyl group, substituted phenyl group, substituted biphenylyl group, substituted terphenylyl group, substituted naphthyl group, substituted fluorenyl group, substituted spirobifluorenyl group, substituted benzoflurenyl group, substituted phenanthyl group, substituted fluoranthenyl group, substituted triphenylenyl group, substituted anthryl group, substituted pyrenyl group, substituted carbazolyl group, substituted dibenzofuranyl group, substituted Divenzotien Diary, -NR a21 R a22 and -OR a23 It is a group selected from the group consisting of;

[0354] R a21 to R a23 It is preferable that each of these independently be a group selected from the group consisting of a hydrogen atom, an adamantyl group, adiamantyl group, a substituted phenyl group, a substituted biphenylyl group, a substituted terphenylyl group, a substituted naphthyl group, a substituted fluorenyl group, a substituted spirobifluorenyl group, a substituted benzofluorenyl group, a substituted phenanthyl group, a substituted fluoranthenyl group, a substituted triphenylenyl group, a substituted anthryl group, a substituted pyrenyl group, a substituted carbazolyl group, a substituted dibenzofuranyl group, and a substituted dibenzothienyl group.

[0355] In the condensation ring compound represented by the above formula (4C), R a31 to R a38 It is desirable that this be a hydrogen atom.

[0356] Physical properties of condensation ring compounds

[0357] The preferred HOMO value, band gap, LUMO value, glass transition temperature, and molecular weight of the condensed ring compound represented by Equation (4) are the same as the preferred HOMO value, band gap, LUMO value, glass transition temperature, and molecular weight of the condensed ring compound represented by Equation (1) in the aforementioned ≪material for photoelectric conversion device≫.

[0358] <Preferred Specific Example of a Condensed Ring Compound>

[0359] A preferred embodiment of the condensed ring compound represented by formula (4) is the same as a preferred embodiment of the condensed ring compound represented by formula (1) in the aforementioned "material for photoelectric conversion device".

[0360] Uses of Condensed Ring Compounds

[0361] The use of the condensed ring compound represented by formula (4) is the same as the use described in <Uses of materials for photoelectric conversion devices> in the aforementioned ≪Materials for photoelectric conversion devices≫.

[0362] [Example]

[0363] The present invention will be described in more detail below based on embodiments, but the present invention is not to be interpreted as being limited in any way by these embodiments.

[0364] [Synthesization Example 1: Synthesis of Compound (Bn-77)]

[0365]

[0366] (Synthesis of Compound (P-1))

[0367] Compound (P-1) was synthesized by the method described in Patent No. 7127418.

[0368] (Synthesis of Compound (P-2))

[0369] Under a nitrogen atmosphere, 1.8 g (5.0 mmol) of compound (P-1), 1.3 g (6.0 mmol) of dibenzothiophen-2-boronic acid, 22 mg (0.1 mmol) of palladium acetate, 111 mg (0.2 mmol) of 1,1'-bis(diphenylphosphino)ferrocene, 50 mL of tetrahydrofuran, and 5 mL of an aqueous potassium carbonate solution with a concentration of 2 M were added to a 200 mL glass container and stirred at 75°C for 12 hours. After cooling to room temperature, 50 mL of pure water was added and stirred, and the precipitated solid was recovered by filtration and washed with pure water and methanol, thereby isolating 2.0 g of colorless powder of compound (P-2) (yield 85%).

[0370] (Synthesis of Compound (P-3))

[0371] Under a nitrogen atmosphere, 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, 5.2 g (32 mmol) of ferric chloride (FeCl3) was added, and the mixture was stirred for 20 minutes at 0°C. Then, 100 mL of methanol was added to the reaction solution and stirred. The precipitated solid was recovered by filtration, and 1.6 g of pale yellow powder of compound (P-3) was isolated by washing with pure water and methanol (yield 81%).

[0372] (Synthesis of Compound (P-4))

[0373] 1.6 g (3.4 mmol) of compound (P-3), 1.2 g (6.8 mmol) of metachloroperbenzoic acid, and 68 mL of dichloromethane were added to a 200 mL glass container under a nitrogen stream and stirred at room temperature for 12 hours. Then, 50 mL of a saturated aqueous sodium thiosulfate solution was added to the reaction solution to separate the liquids. The organic layer obtained from the separation was concentrated, and the precipitated solid was washed with methanol, thereby isolating 1.5 g of a pale yellow powder of compound (P-4) (yield 88%).

[0374] (Synthesis of Compound (P-5))

[0375] Under a nitrogen atmosphere, 1.5 g (3.0 mmol) of compound (P-4), 0.88 g (3.6 mmol) of N-phenyl-4-biphenylamine, 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 orthoxylene were added to a 100 mL glass container and stirred at 140 °C for 24 hours. Then, 40 mL of methanol was added to the reaction solution and stirred. The precipitated solid was recovered by filtration, and 1.6 g of pale yellow powder of compound (P-5) was isolated by washing with pure water and methanol (yield 75%).

[0376] (Synthesis of Compound (Bn-77))

[0377] Under a nitrogen atmosphere, 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 potassium bis(trimethylsilyl)amide toluene solution, and 25 mL of dioxane were added to a 200 mL glass container, and the mixture was stirred at 120 °C for 12 hours. Subsequently, 50 mL of pure water was added to the reaction solution and stirred. The precipitated solid was recovered by filtration, and 0.88 g of a pale yellow powder of compound (Bn-77) was isolated by recrystallization with toluene (yield 52%). The identification of the obtained compound (Bn-77) is 1 It was performed by H-NMR.

[0378] 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)

[0379] [Synthesization Example 2: Synthesis of Compound (Cg-79)]

[0380]

[0381] (Synthesis of Compound (Q-1))

[0382] Under a nitrogen atmosphere, 7.6 g (32 mmol) of compound 1-bromo-2-methoxynaphthalene, 10 g (35 mmol) of 9-phenylcarbazole-2-boronic acid, 144 mg (0.64 mmol) of palladium acetate, 610 mg (1.3 mmol) of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (Xphos), 160 mL of 1,4-dioxane, and 24 mL of a 2 M aqueous potassium phosphate solution were added to a 500 mL glass container, and the mixture was stirred at 100°C for 18 hours. After cooling to room temperature, the organic layer obtained by separating with toluene was concentrated. After dissolving the precipitated solid in acetone, methanol was added and stirred, the precipitated solid was recovered by filtration, and 12.2 g of compound (Q-1) was isolated (yield 95%) by washing with methanol.

[0383] (Synthesis of Compound (Q-2))

[0384] Under a nitrogen atmosphere, 39 mL of a 1 M dichloromethane solution of boron tribromide was added to 12 g (30 mmol) of compound (Q-1) and 30 mL of chloroform in a 100 mL glass container, and the mixture was stirred at room temperature for 16 hours. After adding pure water, the reaction solution was separated with toluene to concentrate the resulting organic layer. The precipitated solid was dissolved in acetone, methanol was added and stirred, the precipitated solid was recovered by filtration, and 7.7 g of compound (Q-2) was isolated (yield 67%) by washing with methanol.

[0385] (Synthesis of Compound (Q-3))

[0386] Under a nitrogen atmosphere, 5.6 mL of triethylamine was added dropwise to 7.7 g (20 mmol) of compound (Q-2) and 100 mL of chloroform in a 300 mL glass container at 0 °C and stirred for 1 hour at 0 °C. Then, 4.9 mL of trifluoromethanesulfonic acid anhydride was added dropwise to this solution at 0 °C and stirred at room temperature for 24 hours. After adding an aqueous sodium bicarbonate solution, the reaction solution was separated with toluene to concentrate the resulting organic layer. The precipitated solid was dissolved in toluene, methanol was added and stirred, the precipitated solid was recovered by filtration, and 8.6 g of compound (Q-3) was isolated by washing with methanol (yield 82%).

[0387] (Synthesis of Compound (Q-4))

[0388] Under a nitrogen atmosphere, 6.2 g (12 mmol) of compound (Q-3), 3.7 g (14 mmol) of 4-chloro-[2-(pyrrolidin-1-yldiazenyl)phenyl]boronic acid, 0.20 g (0.24 mmol) of dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium·dichloromethane (PdCl2(dppf)·CH2Cl2), 4.5 mL of 4 M aqueous sodium hydroxide solution, and 60 mL of 1,4-dioxane were added to a 200 mL glass container and stirred at 100 °C for 12 hours. After cooling to room temperature, the organic layer obtained by separating with toluene was concentrated. After dissolving the precipitated solid in acetone, methanol was added and stirred, the precipitated solid was recovered by filtration, and by washing with methanol, 2.9 g of compound (Q-4) was isolated (yield 46%).

[0389] (Synthesis of Compound (Q-5))

[0390] Under a nitrogen atmosphere, 2.9 g (5.0 mmol) of compound (Q-3) and 50 mL of chlorobenzene were added to a 200 mL glass container, and the solution was cooled to 0°C while stirring. Then, 1.9 g (6.5 mmol) of ferric tribromide 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 and separated. The solution was then separated with chloroform, and the resulting organic layer was concentrated. The resulting solid was dissolved in toluene and passed through alumina. By concentrating the resulting organic solvent, 1.3 g of compound (Q-5) was isolated (yield 54%).

[0391] (Synthesis of Compound (Cg-79))

[0392] Under a nitrogen atmosphere, 1.3 g (2.8 mmol) of compound (Q-5), 1.2 g (3.6 mmol) of N,N-bisbiphenylamine, 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 orthoxylene were added to a 100 mL glass container, and 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. The obtained solid was washed with a 1:1 mixed solution of ethyl acetate and hexane, and by filtering the solid, 1.3 g of yellow powder of compound (Cg-79) was isolated (yield 60%). The identification of the obtained compound (Cg-79) is 1 It was performed by H-NMR.

[0393] 1 H-NMR(CDCl3) δ(ppm): 9.03(d, J=8.4Hz, 1H), 8.81(d, J=8.0Hz, 1H), 8.56(d, J=8.8, 1H), 8.43(d, J=7.6Hz, 1H), 8.36(d, =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)

[0394] (Comparative Example 1)

[0395] As Comparative Example 1, a compound (X1) represented by the following formula was used. In addition, compound (X1) was synthesized according to the method disclosed in Japanese Patent Publication No. 2019-034939.

[0396]

[0397] (Comparative Example 2)

[0398] As Comparative Example 2, a compound (Y1) represented by the following formula was used.

[0399]

[0400] [Synthesization Example 3: Synthesis of Comparative Compound (Y1)]

[0401]

[0402] (Synthesis of compound (y-1))

[0403] Compound (y-1) was synthesized according to the method described in Japanese Patent Publication No. 2016-147846.

[0404] (Synthesis of compound (y-2))

[0405] Under a nitrogen atmosphere, 1.4 g (2.9 mmol) of compound (y-1) and 90 mL of chloroform were added to a 200 mL glass container, and the solution was cooled to 0°C while stirring. Then, 4.7 g (29 mmol) of iron trichloride and 20 mL of nitromethane were added, and the mixture was stirred for 90 minutes. After adding pure water to the reaction solution, the reaction solution was separated with chloroform to concentrate the resulting organic layer. The resulting crude product was purified by silica gel column chromatography (eluent: ethyl acetate:hexane = 1:9) to obtain 0.87 g of compound (y-2) (yield 63%).

[0406] (Synthesis of Compound (Y1))

[0407] Under a nitrogen atmosphere, 0.87 g (1.8 mmol) of compound (y-2), 0.38 g (2.2 mmol) of diphenylylamine, 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 orthoxylene were added to a 100 mL glass container, and the mixture was stirred at 140 °C for 4 hours. After adding an aqueous ammonium chloride solution to the reaction solution, the reaction solution was separated with toluene to concentrate the resulting organic layer. The resulting crude product was purified by silica gel column chromatography (eluent: ethyl acetate:hexane = 1:9), thereby isolating 0.79 g of the yellow powder of compound (Y1) (yield 76%). The identification of the obtained compound (Y1) is 1 It was performed by H-NMR.

[0408] 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)

[0409] (Glass transition temperature)

[0410] Measurements were taken using the DSC7020, a product of Hitachi High-Tech Corporation. The results are shown in Table 7.

[0411] (HOMO value)

[0412] As the HOMO value of the compound obtained in the synthesis example, the HOMO value of the deposited film of the compound (100 nm film deposited on a quartz substrate at a rate of 0.10 nm / sec) was measured using an atmospheric photoelectron spectrometer (AC-3) manufactured by RIKEN KEIKI Co., Ltd. The results are shown in Table 7.

[0413]

[0414] <Device Example 1 (See FIG. 1)>

[0415] As shown in FIG. 1, an imaging element (100) was fabricated as a photoelectric conversion element having a stacked configuration 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), and the dark current, external quantum efficiency, and responsiveness of the imaging element were evaluated.

[0416] (Preparation of substrate (1) and first electrode (2))

[0417] As a substrate having a first electrode on its surface, an ITO transparent electrode attached glass substrate was prepared in which an indium tin oxide (ITO) film (film thickness 110 nm) with a width of 2 mm was patterned in a stripe shape. Then, the substrate was cleaned with isopropyl alcohol, and then surface treatment was performed by ozone ultraviolet cleaning.

[0418] (Preparation for vacuum deposition)

[0419] On a substrate that had undergone surface treatment after cleaning, vacuum deposition of each layer was performed using the vacuum deposition method, and each layer was formed in a stacked manner. First, the glass substrate was introduced into the vacuum deposition bath, and 7.0×10 -5 The pressure was reduced to Pa. Then, in the following order, each layer was constructed according to the tabernacle conditions.

[0420] (Fabrication of the hole blocking layer (3))

[0421] A hole blocking layer (3) was fabricated by sublimating purified 4,6-bis(3,5-di(pyridine-4-yl)phenyl)-2-methylpyrimidine and depositing a 10 nm film at a rate of 0.03 nm / sec.

[0422] (Fabrication of the photoelectric conversion layer (light receiving layer) (4))

[0423] A photoelectric conversion layer (4) was fabricated by depositing N,N-dimethylquinacridone and C60 in a ratio of 4:1 (mass ratio) to a thickness of 120 nm. The deposition rate was 0.15 nm / sec.

[0424] (Fabrication of the electron blocking layer (5))

[0425] The compound (Bn-77) was deposited at a rate of 0.10 nm / second to form a 10 nm film, thereby producing an electron blocking layer (5).

[0426] (Production of the radial transport layer (6))

[0427] A 10 nm film of compound 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN) was deposited at a rate of 0.10 nm / sec to produce a hole transport layer (6).

[0428] (Fabrication of the second electrode (7))

[0429] Finally, a metal mask was placed so as to go directly to the ITO stripe on the substrate, and the second electrode (7), which is the upper electrode, was formed. Specifically, the second electrode (7) was fabricated by forming a silver film of 80 nm at a speed of 0.1 nm / second.

[0430] Based on the above, an imaging photoelectric conversion element (100) with an area of ​​4 mm² as shown in FIG. 1 was fabricated. In addition, each film thickness was measured using a stylus-type film thickness measuring instrument (DEKTAK, Bruker product).

[0431] In addition, this device was sealed in a glove box with a nitrogen atmosphere and oxygen and moisture concentration of 1 ppm or less. Sealing was performed using a glass sealing cap and a film-forming substrate (device) with bisphenol F type epoxy resin (product of Nagase ChemteX Corporation).

[0432] When a voltage of 2.6 V was applied to the imaging element fabricated as described above, the current in the dark (dark current), external quantum efficiency, and response time (responsiveness) were evaluated. The dark current was evaluated using the Source Measure Unit 2636B from Keithley Instruments, Inc. For the measurement of external quantum efficiency, a solar cell spectral sensitivity measuring device (SOMA OPT LTD. product) was used. The wavelength of the irradiation light was 560 nm, and measurements were performed at an intensity of 50 μW / cm². The response time was measured by irradiating the light pulse and the time from irradiation until the current value returned to the level before irradiation.

[0433] In addition, the dark current, external quantum efficiency, and response time are relative values ​​based on the results in Device Comparison Example 1 as the reference value (1.00). A lower value for dark current indicates superior performance, a higher value for external quantum efficiency indicates superior performance, and a lower value for response time indicates superior performance. The obtained measurement results are shown in Table 2.

[0434] <Device Example 2, Device Comparative Examples 1 to 2>

[0435] In fabricating the electron blocking layer (5) of Device Example 1, the imaging photoelectric conversion devices of Device Example 2, Device Comparative Example 1, and Device Comparative Example 2 were fabricated and evaluated in the same manner as Device Example 1, except that the compound (Cg-79), comparative compound (X1), and comparative compound (Y1) were used in order, respectively, instead of the compound (Bn-77). The obtained measurement results are shown in Table 8.

[0436]

[0437] As shown in Table 8, the device of the example using a specific photoelectric conversion device material for an imaging device had a suppressed dark current compared to the device of the comparative example, a high external quantum efficiency was obtained, and the responsiveness was also excellent. Explanation of the symbols

[0438] 1: Substrate 2: First electrode 3: Hole blocking layer 4: Photoelectric conversion layer (photoreceiving layer) 5: Electron blocking layer 6: Precision Transport Layer 7: Second electrode 100: Imaging element (photovoltaic converter)< / l>

Claims

Claim 1 A material for a photoelectric conversion device containing a condensed ring compound represented by the following formula (1): In formula (1), ring A represents a structure expressed by the following formula (2); R 1 to R 8 Each independently comprises a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR 21 R 22 or -OR 23 Represents;R 21 to R 23 Each represents an alkyl group having 1 to 18 carbon atoms that may be independently substituted, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, or a heteroaromatic group having 3 to 30 carbon atoms that may be substituted; R 1 to R 8 They may combine with each other to form a ring; provided, R 1 to R 4 At least one of the following is an alkyl group having 1 to 18 carbon atoms that may be substituted, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR 21 R 22 It is a group having a donor substituent selected from; In formula (2), X 1 To X 4 Of these, the two adjacent atoms represent carbon atoms shared with ring B, and the rest are CR 15 Represents;R 11 to R 15 Each independently comprises a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR 24 R 25 or -OR 26 Represents;R 24 to R 26 Each represents an alkyl group having 1 to 18 carbon atoms that may be independently substituted, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, or a heteroaromatic group having 3 to 30 carbon atoms that may be substituted; R A represents an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted or a heteroaromatic group having 3 to 30 carbon atoms that may be substituted; L represents an alkylene group having 1 to 18 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a divalent heteroaromatic group having 3 to 30 carbon atoms that may be substituted, or a single bond. Claim 2 In paragraph 1, R 1 to R 8 A material for a photoelectric conversion device in which any two adjacent ones are combined with each other to form a ring represented by the following formula (3): In Equation (3), R 31 to R 34 Each independently comprises a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR 21 R 22 or -OR 23 Representing; adjacent R 31 to R 34 They may bond with each other to form a ring; and the carbon atom of * is R 1 to R 8 It represents a carbon atom in the six-membered aromatic ring of the above formula (1), in which two adjacent atoms of either one are bonded. Claim 3 A material for a photoelectric conversion device according to claim 1 or 2, wherein the condensed ring compound represented by formula (1) is a condensed ring compound represented by the following formula (1A) or (1B): [In formulas (1A) and (1B), ring A, R 1 to R 8 and R 31 to R 34 is the ring A, R of the above equations (1) and (3). 1 to R 8 and R 31 to R 34 [Represents a similar energy]. Claim 4 A material for a photoelectric conversion device according to claim 1, wherein the condensed ring compound represented by the above formula (1) is a condensed ring compound represented by any one of the following formulas (1C) to (1E): [In formulas (1C) to (1E), R 1 to R 8 , R 11 to R 15 , R A and L is R of the above equations (1) and (2). 1 to R 8 , R 11 to R 15 , R A and representing a group such as L; provided that an alkyl group having 1 to 18 carbon atoms that may be substituted, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR 21 R 22 A group having a donor substituent selected from is R 1 to R 4 It may be at least one of them, and R 5 to R 8 [At least one of them may be used]. Claim 5 In paragraph 2 or 4, R 1 and R 2 , R 3 and R 4 , R 5 and R 6 or R 7 and R 8 A material for a photoelectric conversion device in which one of the above is combined to form a ring represented by the above formula (3). Claim 6 In paragraph 3, a material for a photoelectric conversion device wherein ring A of the condensed ring compound represented by the above formula (1) exhibits a structure represented by the following formula (2A) or (2B): [Of equations (2A) and (2B), X 1 To X 3 represents a carbon atom shared with ring B, and R 11 to R 15 , R A and L is R of the above equation (2). 11 to R 15 , R A [and represents groups such as L]. Claim 7 A material for a photoelectric conversion device according to claim 2 or 6, wherein the condensed ring compound represented by the above formula (1) is a condensed ring compound represented by the following formula (1F): [Equation (1F) in, R 35 to R 38 Each independently comprises a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR 21 R 22 or -OR 23 Representing; adjacent R 35 to R 38 They may combine with each other to form rings;R 1 to R 4 , R 11 to R 15 , R 31 to R 34 , R A and L is R of the above equations (1) and (3). 1 to R 4 , R 11 to R 15 , R 31 to R 34 , R A [and represents groups such as L]. Claim 8 In Paragraph 7, adjacent R 1 to R 4 and R 31 to R 38 A material for photoelectric conversion devices that does not form rings by bonding to each other. Claim 9 A material for a photoelectric conversion device according to claim 8, wherein L may be substituted with a phenylene group, may be substituted with a biphenylene group, may be substituted with a terphenylene group, may be substituted with a naphthylene group, or a single bond. Claim 10 In Paragraph 9, R 1 to R 4 , R 11 to R 15 , R 31 to R 38 and R A Each independently a hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-octadecyl group, adamantyl group, diamantyl group, a substituted phenyl group, a substituted biphenylyl group, a substituted terphenylyl group, a substituted naphthyl group, a substituted fluorenyl group, a substituted spirobifluorenyl group, a substituted benzoflurenyl group, a substituted phenanthyl group, a substituted fluoranthenyl group, a substituted triphenylenyl group, a substituted anthryl group, a substituted pyrenyl group, a substituted carbazolyl group, a substituted dibenzofuranyl group, Dibenzotien diary that may be substituted, -NR 21 R 22 and -OR 23 It is a group selected from the group consisting of;R 21 to R 23 A material for a photoelectric conversion device, each independently selected from the group consisting of a hydrogen atom, an adamantyl group, adiamantyl group, a substituted phenyl group, a substituted biphenylyl group, a substituted terphenylyl group, a substituted naphthyl group, a substituted fluorenyl group, a substituted spirobifluorenyl group, a substituted benzofluorenyl group, a substituted phenanthyl group, a substituted fluoranthenyl group, a substituted triphenylenyl group, a substituted anthryl group, a substituted pyrenyl group, a substituted carbazolyl group, a substituted dibenzofuranyl group, and a substituted dibenzothienyl group. Claim 11 In Paragraph 10, R 31 to R 38 This hydrogen atom is a material for photoelectric conversion devices. Claim 12 An organic thin film comprising a material for a photoelectric conversion device as described in any one of claims 1 to 11. Claim 13 A photoelectric conversion device comprising a material for a photoelectric conversion device described in any one of claims 1 to 11. Claim 14 A photoelectric conversion device comprising a material for a photoelectric conversion device described in any one of claims 1 to 11 in a photoelectric conversion layer. Claim 15 A photoelectric conversion device comprising a material for a photoelectric conversion device described in any one of claims 1 to 11 in a hole transport layer or an electron blocking layer. Claim 16 A material for a photoelectric conversion element described in any one of claims 1 to 11, used in a photoelectric conversion element for an imaging element. Claim 17 Condensed ring compound represented by the following formula (4): In equation (4), ring A represents the structure indicated by the following equation (5); R a1 to R a8 Each independently comprises a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR a21 R a22 or -OR a23 Represents;R a21 to R a23 Each represents an alkyl group having 1 to 18 carbon atoms that may be independently substituted, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, or a heteroaromatic group having 3 to 30 carbon atoms that may be substituted; R a1 to R a8 They may combine with each other to form a ring; provided, R a1 to R a4 At least one of the following is an alkyl group having 1 to 18 carbon atoms that may be substituted, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR a21 R a22 A group having a donor substituent selected from;R a1 to R a8 Any two adjacent ones combine with each other, and a ring is formed as shown in the following formula (6); Among equation (5), X a1 To X a4 Of these, the two adjacent atoms represent carbon atoms shared with ring B, and the rest are CR a15 Represents;R a11 to R a15 Each independently comprises a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR a24 R a25 or -OR a26 Represents;R a24 to R a26 Each represents an alkyl group having 1 to 18 carbon atoms that may be independently substituted, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, or a heteroaromatic group having 3 to 30 carbon atoms that may be substituted; R aA ...represents an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, or a heteroaromatic group having 3 to 30 carbon atoms that may be substituted; L a ...represents an alkylene group having 1 to 18 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a divalent heteroaromatic group having 3 to 30 carbon atoms that may be substituted, or a single bond; In formula (6), R a31 to R a34 Each independently comprises a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR a21 R a22 or -OR a23 Representing; adjacent R a31 to R a34 They may bond with each other to form a ring; and the carbon atom of * is R a1 to R a8 It represents a carbon atom in the six-membered aromatic ring of the above formula (4), in which two adjacent atoms of either one are bonded. Claim 18 In claim 17, the condensed ring compound represented by the above formula (4) is a condensed ring compound represented by the following formula (4A) or (4B): [Among formulas (4A) and (4B), ring A, R a1 to R a8 and R a31 to R a34 is the ring A, R of the above equations (4) and (6). a1 to R a8 and R a31 to R a34 [Represents a similar energy]. Claim 19 In paragraph 18, a condensed ring compound in which ring A represents a structure represented by the following formula (5A) or (5B): [Of equations (5A) and (5B), X a1 To X a3 represents a carbon atom shared with ring B, and R a11 to R a15 , R aA and L a is R of the above equation (5). a11 to R a15 , R aA and L a [Represents a similar energy]. Claim 20 In claim 19, the condensed ring compound represented by the above formula (4A) or (4B) is a condensed ring compound represented by the following formula (4C): [Equation (4C), R a35 to R a38 Each independently comprises a hydrogen atom, an alkyl group having 1 to 18 carbon atoms that may be substituted, an alkenyl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, a bicycloalkyl group having 1 to 18 carbon atoms, a tricycloalkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms that may be substituted, a heteroaromatic group having 3 to 30 carbon atoms that may be substituted, and -NR a21 R a22 or -OR a23 Representing; adjacent R a35 to R a38 They may combine with each other to form rings;R a1 to R a4 , R a11 to R a15 , R a31 to R a34 , R aA and L a is R of the above equations (4) and (6). a1 to R a4 , R a11 to R a15 , R a31 to R a34 , R aA and L a [Represents a similar energy]. Claim 21 In paragraph 20, the condensation ring compound represented by the above formula (4C) is adjacent to R a1 to R a4 and R a31 to R a38 Condensed ring compounds that do not combine to form a ring. Claim 22 In Paragraph 21, L a A condensed ring compound in which a phenylene group that may be substituted, a biphenylene group that may be substituted, a terphenylene group that may be substituted, a naphthylene group that may be substituted, or a single bond. Claim 23 In Paragraph 22, R a1 to R a4 , R a11 to R a15 , R a31 to R a38 and R aA Each independently a hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-octadecyl group, adamantyl group, diamantyl group, a substituted phenyl group, a substituted biphenylyl group, a substituted terphenylyl group, a substituted naphthyl group, a substituted fluorenyl group, a substituted spirobifluorenyl group, a substituted benzoflurenyl group, a substituted phenanthyl group, a substituted fluoranthenyl group, a substituted triphenylenyl group, a substituted anthryl group, a substituted pyrenyl group, a substituted carbazolyl group, a substituted dibenzofuranyl group, Dibenzotien diary that may be substituted, -NR a21 R a22 and -OR a23 It is a group selected from the group consisting of;R a21 to R a23 A condensed ring compound, each independently selected from the group consisting of a hydrogen atom, an adamantyl group, adiamantyl group, a substituted phenyl group, a substituted biphenylyl group, a substituted terphenylyl group, a substituted naphthyl group, a substituted fluorenyl group, a substituted spirobifluorenyl group, a substituted benzofluorenyl group, a substituted phenanthyl group, a substituted fluoranthenyl group, a substituted triphenylenyl group, a substituted anthryl group, a substituted pyrenyl group, a substituted carbazolyl group, a substituted dibenzofuranyl group, and a substituted dibenzothienyl group. Claim 24 In Paragraph 23, R a31 to R a38 This hydrogen atom, a condensed ring compound.

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